Environment-friendly ethylene oxide, propylene oxide and downstream products

Abstract

The present invention relates to a process for the preparation of ethylene oxide or propylene oxide comprising (b) reacting hydrogen with a carbon oxide to form methanol, (c) converting methanol from step (b) to ethylene and / or propylene, (d) reacting ethylene and / or propylene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gas or from air or from seawater or other natural water or obtained from a biological process, for example obtained from a fermentation process from waste or biomass, and / or wherein the hydrogen in step (b) is at least partially obtained by water decomposition, the water decomposition preferably uses energy generated at least in part from non-fossil resources; the present invention relates to a process for the preparation of ethanolamine, a process for the preparation of alkoxylated compounds, a process for the preparation of alkoxylated diamines, oligoamines and polyamines, or alkoxylated polyethyleneimine, a process for the preparation of alkoxylated polyethyleneimine, a process for the preparation of surfactants, and a process for the preparation of alkoxylated polyethyleneimine, a process for the preparation of alkoxylated polyethyleneimine, a process for the preparation of alkoxylated polyethyleneimine, a process for the preparation of alkoxylated polyethyleneimine, a process for the preparation of alkoxylated compounds, and a process for the preparation of alkoxylated compounds. Each process is based on said process for the preparation of ethylene oxide or propylene oxide; the polyethyleneimine, the ethanolamine, the alkoxylated compound, the surfactant, the alkoxylated diamine, the oligomeric amine, the polyamine and the alkoxylated polyethyleneimine can be obtained through the method; the present invention relates to alkoxylated polyethyleneimine, ethanolamine, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and uses of alkoxylated polyethyleneimine, ethanolamine, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines; a composition, which is a laundry detergent, a cleaning composition or a fabric and home care product, containing at least an alkoxylated diamine, an oligoamine and a polyamine or an alkoxylated polyethyleneimine, or a surfactant; polyethyleneimine, ethanolamine, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimine having a reduced amount of fossil-based hydrogen content, thus having an overall reduced cradle-to-gate product carbon footprint.

Description

[0001] The present invention relates to a process for the production of ethylene oxide or propylene oxide comprising the steps of:

[0002] (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol,

[0003] (c) converting the methanol from step (b) to ethylene and / or propylene,

[0004] (d) reacting the ethylene and / or propylene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide,

[0005] wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gas or from air or from seawater or other natural water or obtained from a biological process, for example from a fermentation process from waste or biomass,

[0006] and / or

[0007] wherein the hydrogen in step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least partially from non-fossil resources;

[0008] A process for the production of ethanolamine, wherein the process comprises steps (b), (c) and (d) of the process for the production of ethylene oxide or propylene oxide, with the following steps:

[0009] (a) reacting hydrogen with nitrogen to form ammonia, reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol, and

[0010] (e) converting the ammonia from step (a) to ethanolamine in one or more steps with the ethylene oxide from step (d),

[0011] wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least partially from non-fossil resources;

[0012] A process for the production of polyethyleneimine, wherein the process comprises steps (a), (b), (c), (d) and (e) of the process for the production of ethanolamine and additionally the following steps:

[0013] (f) separating monoethanolamine from the ethanolamine obtained in step (e);

[0014] (g) converting the monoethanolamine from step (f) to ethyleneimine, preferably by catalytic gas phase synthesis,​

[0015] and

[0016] (h) polymerizing the ethyleneimine obtained in step (g) to polyethyleneimine,

[0017] wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water splitting, preferably by electrolysis, using energy generated at least partially from non-fossil resources;

[0018] A process for the preparation of an alkoxylated compound comprising

[0019] i) 20 wt-% to < 100 wt-% of ethylene oxide units and / or propylene oxide units,

[0020] ii) 0 wt-% to 30 wt-% of at least one alkylene oxide unit different from ethylene oxide units and propylene oxide units,

[0021] iii) > 0 wt-% to 80 wt-% of at least one starter unit having a Zerevitinoff-active hydrogen atom,

[0022] wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%,

[0023] the process comprising steps (b), (c) and (d) of the process for the preparation of ethylene oxide or propylene oxide, in addition to the following steps:

[0024] (e0) in one or more steps, reacting the ethylene oxide and / or propylene oxide obtained in step (d) and, optionally, the at least one alkylene oxide different from ethylene oxide and propylene oxide, with the at least one starter unit having a Zerevitinoff-active hydrogen atom to form an alkoxylated compound,

[0025] wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gas or from air or from seawater or other natural water, or obtained from a biological process, for example from a fermentation process from waste or biomass;

[0026] A process for the preparation of an alkoxylated diamine, oligoamine and polyamine or alkoxylated polyethyleneimine, any of which individually or together “the compound”, wherein the process comprises steps (a), (b), (c) and (d) of the process according to the process for the preparation of ethanolamine and additionally the following steps:

[0027] e1 ) in one or more steps, using known methods, converting the ethylene oxide and / or propylene oxide from step (d) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide, respectively, to an alkoxylated diamine, an oligoamine and a polyamine or an alkoxylated polyethylenimine,

[0028] wherein the hydrogen in steps (a) and (b) is obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium based on the total hydrogen content of ≤ 100 ppm, preferably in the range of from 10 to ≤ 95 ppm, more preferably in the range of from 10 to ≤ 90 ppm, most preferably in the range of from 10 to ≤ 80 ppm;

[0029] A process for the preparation of an alkoxylated polyethylenimine (“compound”), wherein the process comprises steps (a), (b), (c), (d), (e), (f), (g) and (h) of the process for the preparation of a polyethylenimine and additionally the following steps:

[0030] (i) alkoxylating the polyethylenimine from step (g) with ethylene oxide and / or propylene oxide and optionally further ingredients such as other alkylene oxides and / or lactones to obtain an alkoxylated polyethylenimine,

[0031] wherein the hydrogen in steps (a) and (b) is obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium based on the total hydrogen content of ≤ 100 ppm, preferably in the range of from 10 to ≤ 95 ppm, more preferably in the range of from 10 to ≤ 90 ppm, most preferably in the range of from 10 to ≤ 80 ppm,

[0032] wherein preferably step (g) is carried out in gas phase or in liquid phase;

[0033] A process for the manufacture of a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or is produced with hydrogen, wherein the process comprises the following steps:

[0034] (a) reacting hydrogen with nitrogen to form ammonia,

[0035] (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol,

[0036] (c) and (d) converting the methanol from step (b) to ethylene and further to ethylene oxide with oxygen,

[0037] (e) converting the ammonia from step (a) into ethanolamine in one or more steps with ethylene oxide from step (d), and

[0038] (f) separating monoethanolamine, diethanolamine and triethanolamine from the ethanolamines obtained in step (e),

[0039] (g0) converting any products from steps a), b), c), d) and e) into a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen in at least one known process step,

[0040] to obtain a surfactant comprising less deuterium based on the total hydrogen content compared to the same surfactant obtained only from chemicals based on fossil sources,

[0041] wherein the hydrogen in steps (a) and (b) obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm, based on the total hydrogen content;

[0042] Polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines obtainable by the above described process, the use of polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines;

[0043] A composition which is a laundry detergent, cleaning composition or fabric and home care product, containing at least alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines (any of which alone or together "compounds"), or surfactants, in a concentration of the at least one compound of preferably from about 0.1 % to about 20 % by weight relative to the total weight of such composition or product, or, and in case the composition comprises surfactants, in a concentration of the at least one compound of from about 0.1 % to about 50 % by weight relative to the total weight of such composition or product;

[0044] compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines having a reduced amount of fossil-based hydrogen content and thus an overall reduced cradle to gate product carbon footprint; and

[0045] compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines which are thus obtained with an overall reduced cradle to gate product carbon footprint (compared to polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines which are not obtained with at least partially carbon dioxide captured or obtained from industrial flue gases or from air or from seawater or other natural water from a biological process).

[0046] Furthermore, the present invention relates to a process for preparing polyethyleneimines with a low product carbon footprint (PCF) in good yield based at least partially on energy generated from non-fossil resources, a process for preparing ethanolamines with a low product carbon footprint (PCF) in good yield based at least partially on energy generated from non-fossil resources, polyethyleneimines and ethanolamines preferably having a low product carbon footprint (PCT) obtained by the process of the present invention, polyethyleneimines are particularly stable when used for carbon capture, and the use of the polyethyleneimines of the present invention and the ethanolamines of the present invention as CO2 absorbents in a CO2 capture process.

[0047] Human carbon dioxide emissions and other greenhouse gases are warming the Earth’s atmosphere, leading to climate change. Global warming has various negative effects, such as rising sea levels, increased risk of floods, droughts, and other extreme weather events.

[0048] Therefore, at the 2015 Paris Climate Summit, the international community agreed to limit the rise in temperature to “well below” 2°C, with efforts to limit it to 1.5°C above pre-industrial levels. The 1.5°C target was reaffirmed at the COP27 United Nations Climate Change Conference in November 2022. This can only be achieved with a rapid reduction in global greenhouse gas emissions.

[0049] In addition to the most important anthropogenic greenhouse gas (GHG), carbon dioxide (CO2), there are other gases defined as greenhouse gases by the Intergovernmental Panel on Climate Change (IPCC) such as CH4, SF6, N2O, hydrofluorocarbons (HFC), perfluorocarbons (PFC). The various gases contribute to the greenhouse effect to different extents and remain in the atmosphere for different periods of time. In order to make the effects of the different greenhouse gases comparable, the IPCC has defined the so-called "global warming potential". This index indicates the warming effect of a certain amount of greenhouse gas compared to CO2 over a defined period of time (usually 100 years). For example, methane has 28 times the climate effect of CO2, but it does not remain in the atmosphere for long. The environmental effect of nitrous oxide also exceeds that of CO2 almost 300 times. In this way, the most relevant greenhouse gases can be combined and calculated as CO2 equivalents. CO2 equivalents are abbreviated as "CO2e".

[0050] According to the Greenhouse Gas Protocol (WBCSD, WRI, 2011), greenhouse gas emissions are classified into so-called scopes 1, 2 and 3 parts.

[0051] Scope 1 is the direct CO2e emissions generated in the production processes in the factories owned or controlled by the reporting company. They are generated, for example, by

[0052] emissions from chemical reactions,

[0053] emissions originating from waste disposal without energy use (e.g. flares),

[0054] emissions from fuel and residue incineration in the processing plants owned by the company.

[0055] Scope 2 is the indirect CO2e emissions generated by purchased energy (such as electricity, steam, heat and cooling) available via, for example, a grid connection and used by the utilities of the factory of the company.

[0056] Scope 3 upstream CO2e emissions are the sum of all indirect emissions, for example generated from the use of raw materials purchased from other suppliers, including indirect emissions from transport up to the cradle of generation and fuel extraction consumed by all product processing plants in the complete value chain. It is important to note that this can include emissions from more than one company, as the total emissions from, for example, purchased raw materials up to the cradle must be included. This sum of indirect emissions is also referred to as backpack emissions.

[0057] Scope 3 downstream CO2e emissions include indirect greenhouse gas emissions associated with the company's value chain related to goods and services sold and indirect greenhouse gas emissions emitted after they leave the company's ownership or control. This includes, for example, emissions associated with additional transportation and transformation, up to the end of the end product life cycle, and emissions associated with final disposal of waste.

[0058] However, in the case of alkoxylated compounds and processes for their preparation, in the present application, the "material carbon" in the polymer product is considered to be the only additional CO2 emissions of Scope 3 downstream (end of life cycle "graveyard") emissions; all other emissions in the product customer and consumer use phase (e.g. emissions associated with transportation and use) are outside the scope.

[0059] The product carbon footprint (PCF) sums up the total greenhouse gas (GHG) emissions generated by a product through the different stages of its life cycle. For example, the cradle-to-gate (partial) PCF considers all processes from the extraction of resources to the manufacture of the precursors and the manufacture of the end product itself up to the point where it leaves the company's gate (all product-related direct GHG emissions, including removals from Scope 1, 2 and 3 upstream). The cradle-to-grave PCF encompasses the complete life cycle of a product, including emissions from the use phase of the product and at the end of life (all product-related direct GHG emissions, including removals from Scope 1, 2 and 3 upstream and downstream).

[0060] The system boundary definitions according to the GHG Protocol are shown in Figure 1

[0061] Unless otherwise stated, the PCF in the present application refers to the cradle-to-gate PCF. In the case of alkoxylated compounds and processes for their preparation, the "total cradle-to-gate PCF" means the total PCF of the respective alkoxylated compound from cradle to gate. Likewise for other compounds of the present application, the "total cradle-to-gate PCF" means the total PCF of the respective compound from cradle to gate.

[0062] However, in the case of alkoxylated compounds and processes for their preparation, in the present application, the "material carbon" in the polymer product is considered to be the only additional CO2 emissions of Scope 3 downstream (end of life cycle "graveyard") emissions; all other emissions in the product customer and consumer use phase (e.g. emissions associated with transportation and use) are outside the scope.

[0063] One important factor for reducing global greenhouse gas emissions, in particular CO2 emissions, is quantitative knowledge about how much greenhouse gas emissions are associated with a product along the production value chain and along its life cycle. The product carbon footprint (PCF) can help to find the answer. ​

[0064] Product carbon footprint (PCF) is the most well-established method for determining the climate impact of a product, and many methods for calculating PCF are known in the field.

[0065] US 2022 / 0107618 A1, US 2022 / 0108327 A1 and US 2022 / 0108326 A1, for example, relate to computer-implemented methods for determining the carbon footprint of products in manufacturing processes at a production plant, particularly products in interconnected manufacturing processes.

[0066] Product carbon footprint helps identify, analyze, and, with appropriate measures, reduce or (ideally) completely avoid climate-related impacts in the form of greenhouse gas emissions.

[0067] Consumers' growing interest in "green products" has led many companies to manufacture and sell products with environmental attributes. Major retailers have begun encouraging their suppliers to clearly label the carbon footprint of their products.

[0068] The biodegradability of the alkoxylated compounds according to the present invention is determined based on currently effective OECD guidelines.

[0069] The OECD distinguishes six biodegradation forms in its guidelines, as follows (OECD, 1981b, 1991, 1992a, 1992b, 2001, 2002, 2004a, 2008) (see https: / / www.ecetoc.org / technical-report-123 / measured-partitioning-property-data / biodegradation / definitions-according-to-oecd / ).

[0070] (i) Final biodegradation (mineralization): The level of degradation achieved when the test compound is fully utilized by microorganisms, resulting in the production of carbon dioxide, water, mineral salts and new microbial cell components (biomass).

[0071] (ii) Primary biodegradation (biotransformation): Changes in the chemical structure of a substance caused by biological processes, resulting in the loss of the substance's specific properties.

[0072] (iii) Easily biodegradable: Any classification of chemicals that have passed certain specific screening tests for ultimate biodegradability; these tests are so rigorous that it is assumed that such compounds will be rapidly and completely biodegraded in aquatic environments under aerobic conditions.

[0073] (iv) Inherently Biodegradable: Classification of a chemical that has clear evidence of biodegradation (primary or ultimate) in any test of biodegradability.

[0074] (v) Half-life (t0.5): The time taken for 50% conversion of the test substance when conversion can be described by first order kinetics; it is independent of initial concentration.

[0075] (vi) Disappearance time 50 (DT50): The time for the initial concentration of the test substance to decrease by 50 percent.

[0076] The alkoxylated compounds according to the present application are generally tested according to OECD 301 B for their readiness to biodegrade.

[0077] Test No. 301 : Ready Biodegradability (https: / / www.oecd-ilibrary.org / environment / test-no-301-ready-biodegradability_9789264070349-en)

[0078] This test guideline describes six methods that allow the screening of chemicals for ready biodegradability in aerobic aqueous media. These methods are: DOC reduction (301 A), CO2 evolution (modified Sturm test) (301 B), MITI (I) (Ministry of International Trade and Industry, Japan) (301 C), closed bottle (301 D), modified OECD screening (301 E) and pressure build-up respirometry (301 F).

[0079] A solution or suspension of the test substance to be unequivocally identified / described is inoculated into mineral medium and incubated under aerobic conditions in the dark or in diffuse light. A run blank with inoculum but without test substance allows the determination of the endogenous activity of the inoculum. A reference compound (aniline, sodium acetate or sodium benzoate) is run in parallel to check the functioning of the procedure. Typically, the test lasts for 28 days. At least two flasks or vessels containing test substance plus inoculum, and at least two flasks or vessels containing only inoculum should be used; a single vessel is sufficient for the reference compound. Typically, after degradation, parameters such as DOC, CO2 production and oxygen uptake are determined. For the respirometric method, the pass level for ready biodegradability is 70% removal of DOC and 60% ThOD or ThCO2 production. These pass values must be achieved in a 10-day window within the 28-day period of the test.

[0080] The ethylene glycol and propylene glycol moieties (i.e. alkylene oxide units) in alkoxylated compounds have a significant impact on the product carbon footprint of alkoxylated compounds. Therefore, it is an object to achieve compounds based on ethylene glycol and / or propylene glycol (in the present invention referred to as alkoxylated compounds, since besides ethylene glycol and propylene glycol one or more additional alkylene glycols can be present) wherein the ethylene oxide and / or propylene oxide employed in the synthesis of the alkoxylated compounds is prepared by the specific process of the present invention.

[0081] Furthermore, ethylene oxide and propylene oxide are universal starting materials for many downstream products such as polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligo- and polyamines, and alkoxylated polyethyleneimines.

[0082] Polyethyleneimines (PEI) are versatile polymers which can be used for various purposes such as, but not limited to, detergents, adhesives, water treatment agents and cosmetics. Furthermore, PEI is used in paper manufacturing as well as in flocculation processes or as raw material in the field of biotechnology.

[0083] Ethanolamines are flammable, corrosive, colorless, viscous liquids produced by the reaction between ammonia and ethylene oxide (EO). Discovered many years ago, ethanolamines are key ingredients in many important product formulations such as cosmetics and personal hygiene products, agricultural products, wood preservative chemicals, soaps and detergents, gas treatment agents. They can also be used in the production of non-ionic detergents, emulsifiers and soaps, and in emulsified paints, polishes and cleaning agents. There are three main commercial types of ethanolamines: monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA). The formation of MEA, DEA, or TEA depends on whether one, two, or three ethylene oxide molecules react with an ammonia molecule, and the product ratio can be adjusted by raw material feed composition and processing conditions. MEA, DEA and TEA can be separated after synthesis, for example by distillation, in order to manufacture high purity chemical materials with orders of magnitude 99% purity according to the needs of the application use.

[0084] Further, PEI as well as MEA, DEA and / or TEA can be used as a carbon dioxide (CO2) capture agent. The amino groups in PEI react with CO2, thereby binding it and removing it from the relevant emission gas source or even ambient air. The bound CO2 can be desorbed in order to concentrate the carbon dioxide, allowing for certain reuse of PEI, MEA, DEA and / or TEA. Generally, over time, the inherent capture efficiency loss can be compensated with fresh material and optimizing the overall CO2 capture performance through product and process innovation is an ongoing work. Due to the fact that according to scientists, billions of tons of CO2 have to be removed from the atmosphere every year in order to achieve climate goals, there is a high demand for these sorbent materials.

[0085] However, the preparation steps of ethanolamines and especially ethyleneimine (EI) as a precursor of polyethyleneimine (PEI) and the required raw materials are highly energy demanding.

[0086] Ammonia is a key precursor in the production of MEA, which in turn is a key precursor in the production of EI and PEI. Due to the development of the Haber-Bosch process for the production of ammonia, the vast majority of ammonia is manufactured by direct synthesis from hydrogen and nitrogen in the presence of a catalyst, especially an iron-containing catalyst. In modern processes, a large amount of hydrogen is thus provided from natural gas by steam reforming.

[0087] Thus, the production process of ethanolamines and polyethyleneimine has its negative impact on its carbon footprint, including a large consumption of fossil-based natural resources and energy from cradle to grave.

[0088] Vargese Anish Mathai et al., International Journal of Greenhouse Gas Control, Volume 96, 3 March 2020 is a review on CO2 capture sorbents functionalized by polymers with amines.

[0089] Weissermel Klaus et al., Industrial Organic Chemistry, 27 May 2003, pages 145-192, deals with the oxidation products of ethylene. Among others, ethanolamines are disclosed in chapter 7.2.3 (page 159). It is mentioned that ethylene oxide reacts with ammonia to form a mixture of the three theoretically possible ethanolamines with high selectivity (see also table 7-5 on page 159).

[0090] US 6,495,609 B1 relates to carbon dioxide recovery in ethylene to ethylene oxide production processes. According to US 6,495,609 B1 a process for recovering carbon dioxide from an ethylene oxide production process is disclosed, wherein the recovered carbon dioxide is used as a carbon source from ethanol synthesis. Carbon dioxide is used to produce a synthesis gas stream, and then the synthesis gas stream is used to produce methanol.

[0091] GB 2,464,691 A relates to the manufacture of methanol from agricultural cellulose / lignin materials. It is disclosed that cellulose / lignin by-products remaining after the cultivation of agricultural products are converted by thermal oxidation into carbon dioxide, and in another section of the synthesis plant, hydrogen is produced by electrolysis. The hydrogen is then reacted with the carbon dioxide to produce methanol.

[0092] It is therefore an object of the present invention to provide environmentally friendly polyethyleneimines and ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), and an environmentally friendly process for their manufacture in good yield, while the process should use as little fossil-based energy as possible. The ethanolamines and polyethyleneimines should be especially useful for carbon capture.

[0093] The polyethyleneimines and ethanolamines should not be based on a starting material based on a biomass feedstock or a biomass balanced feedstock. In the meaning of the present invention, carbon oxides like CO and CO2 are not considered to be a biomass feedstock. Biomass balancing and biomass balanced feedstocks are for example described in https: / / www.basf.com / global / documents / en / sustainability / we-produce-safely-and-efficiently / resources-and-ecosystems / BASFs_biomass-balance-approach.pdf

[0094] It is an object to solve by a process for preparing a polyethyleneimine, wherein the process comprises the following steps:

[0095] (a) reacting hydrogen with nitrogen to form ammonia,

[0096] (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol,

[0097] (c) converting the methanol from step (b) to ethylene,

[0098] (d) reacting the ethylene from step (c) with oxygen to form ethylene oxide,

[0099] (e) converting the ammonia from step (a) into ethanolamine in one or more steps with ethylene oxide from step (d),

[0100] (f) separating monoethanolamine from the ethanolamine obtained in step (e);

[0101] (g) converting the monoethanolamine from step (f) into ethylene imine, preferably by catalytic gas phase synthesis,

[0102] and

[0103] (h) polymerizing the ethylene imine obtained in step (g) to polyethylene imine,

[0104] wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water splitting, preferably by electrolysis, which water splitting, preferably electrolysis, uses energy generated at least partially from non-fossil resources.

[0105] The process of the present application is not based on starting materials based on biomass feedstock or biomass balanced feedstock.

[0106] Surprisingly, it has been found that the overall product yield of polyethylene imine as well as also ethanolamine (mentioned below) prepared according to the process of the present application is higher than in processes starting only with conventional fossil-based hydrogen and carbon from e.g. fossil-based synthesis gas and / or hydrocarbon cracker sources.

[0107] To solve this purpose, the relevant PCF of polyethylene imine and ethanolamine as well as the upstream compounds in the preparation of both is calculated based on the following guideline: “The Product Carbon Footprint Guideline for the Chemical Industry”, published by TfS (Together for Sustainability), Version 2.0, November 2022 (https: / / www.tfs-initiative.com) (in the following: “TfS guideline”). The guideline is “auditable”, compliant with ISO, and accepted by the GHG Protocol and further “open source”, available to the global industry using chemical materials.

[0108] The Applicant’s unique Verbund system creates an efficient value chain stretching from basic chemicals all the way to consumer products. This makes it possible to collect reliable data on greenhouse gas (GHG) emissions generated (especially by polyethylenimine and ethanolamine and upstream compounds in the process of their preparation) in different stages of the life cycle of products within and outside the Verbund owned by the company, especially from cradle to gate (upstream on scopes 1, 2 and 3).

[0109] As mentioned above, the processes for the preparation of polyethylenimine, especially the precursor ethylenimine and ethanolamine, and ammonia and ethylene oxide are energy demanding, and many of the steps (a) to (h) of the process for the preparation of polyethylenimine can be carried out by alternative processes. The inventors have found a process for the preparation of polyethylenimine, wherein each step is optimized or at least prepared for obtaining a polyethylenimine with a low carbon footprint.

[0110] Ethylenimine (aziridine) is industrially produced from monoethanolamine, for example via two commercial routes. The catalytic gas phase dehydration process requires an oxide catalyst and very high temperatures (350°C - 450°C) to achieve dehydration and 3-ring closure. In another aspect, in the liquid phase process, monoethanolamine is converted to its sulfate ester, which undergoes base-induced sulfate elimination under relatively mild conditions. The older process requires amination of 1,2-dichloroethane and cyclization of 2-chloroethylamine.

[0111] According to the textbook Ullmann’s Encyclopedia of Industrial Chemistry, “Aziridines”, 2012 Wiley-VCH Verlag GmbH & Co. KGaA Weinheim; DOI: 10.1002 / 14376007.a03 239.pub2, Chapter 4.4., the high energy demand is considered a drawback of the catalytic gas phase synthesis, which makes this process unattractive for the preparation of polyethylenimine with a low carbon footprint. In addition, the relatively low selectivity of “up to 90%” and monoethanolamine conversion of only “40% to 80%” require recirculation of large amounts of unconverted monoethanolamine and additionally removal of e.g. high-boiling amine side components as waste material with high energy demand (heating / cooling / heating). The carbon content of the waste material generated from the relatively low overall yield adds significant CO2e emissions to the PCF.

[0112] The commercial liquid phase process as described in chapter 4.3 of the above mentioned Ullmann’s Encyclopedia of Industrial Chemistry “Aziridines” achieves yields of 85% to 90% and thus a significantly lower waste output compared to other processes. The mentioned relative higher raw material costs of the liquid phase process are not the focus of the present invention.

[0113] However, a precise analysis of the different process steps for obtaining polyethyleneimine and a comparison with alternative processes surprisingly revealed that the greenhouse gas (GHG) emissions generated by converting monoethanolamine to ethyleneimine by catalytic gas phase synthesis (step g)) are significantly lower than the GHG emissions generated by converting monoethanolamine to ethyleneimine by other processes. Thus, the PCF of ethyleneimine and thus of polyethyleneimine obtained by catalytic gas phase synthesis is significantly lower than the PCF of ethyleneimine and polyethyleneimine obtained by other processes (only step g) is different in the processes for preparing ethyleneimine and polyethyleneimine).

[0114] The inventors further found that polyethyleneimine having an especially low PCF is obtained based on ethyleneimine prepared by catalytic gas phase synthesis, wherein the hydrogen used for preparing ammonia and methanol, i.e. the starting material for preparing ammonia and ethylene oxide, is at least partially obtained by water splitting, preferably electrolysis, based on electrical power generated at least partially from non-fossil resources.

[0115] In the meaning of the present invention, the product carbon footprint (PCF) sums up the total greenhouse gas (GHG) emissions generated by a product over the different stages of its life cycle. The cradle to gate product carbon footprint (PCT) sums up the total greenhouse gas (GHG) emissions generated by a product within scope 1, 2 and scope 3 upstream, as specified in the above mentioned “TfS Guidelines” and as shown in the relevant boundary conditions in Figure 1 .

[0116] Unless otherwise specified, PCF in the present application refers to cradle to gate PCF. “Total cradle to gate PCF” means the total PCF of the respective compound from cradle to gate.

[0117] A highly relevant factor for determining the PCF is in addition to the input ratio and the implicit emissions of the starting materials used and the input ratio and implicit emissions of the energy required in each production step of the specific product. In the process of the present application for the preparation of ethanolamine and in the process for the preparation of polyethyleneimine, in all steps (a) to (h) and the step of generating hydrogen, energy in the form of heating energy (e.g. steam) and / or electric power is used as contributor in the PCF.

[0118] In all steps (a) to (h) of the process of the present application and the step of generating hydrogen, energy in the form of heating energy (e.g. steam) and / or electric power is used. According to the process of the present application, the energy (electric power) used for generating hydrogen in step (a) and / or (b), preferably the energy used for generating hydrogen in step (a) and / or (b) and the energy used in one or more of steps (a) to (h) is at least partially generated from non-fossil resources.

[0119] By precise analysis of the different process steps for obtaining polyethyleneimine according to the present application it has been found that the most relevant energy demand steps in the order of their energy demand in relation to the product obtained in said steps are step (g), the step of generating hydrogen, and steps (a), (b), (c) and (f). Therefore, preferably, the energy used in the step of generating hydrogen and in step (g), more preferably the energy used in the step of generating hydrogen, step (g) and step (c), most preferably the energy used in the step of generating hydrogen and in steps (g), (c) and (b), further most preferably the energy used in the step of generating hydrogen and steps (a), (b), (c), (f) and (g), even further most preferably the energy used in the step of generating hydrogen and in steps (a) to (h) of the process of the present application is at least partially generated from non-fossil resources.

[0120] It has been surprisingly found that not only the step of generating hydrogen and step (g) are highly energy demanding steps in a process for the preparation of polyethyleneimine, but also steps (c) and (b) and steps (a) and (f). Therefore, only if the energy used at least in step (c) and preferably at least in steps (c) and (b), more preferably at least in steps (c), (b), (a) and (f) (in addition to the step of generating hydrogen and step (g)) is at least partially generated from non-fossil resources, polyethyleneimine and ethanolamine with a particularly low total cradle-to-gate product carbon footprint is achieved.

[0121] According to the TfS requirements, all process steps until the production of the final product have to be considered in the PCF of the final product - thus a product such as ethanolamine and polyethyleneimine with an extremely high processing as mentioned below with a low total cradle-to-gate product carbon footprint would not be expected by the skilled person to be achievable. Obviously, these products require energy-intensive starting materials and many subsequent energy-intensive process steps.

[0122] However, it should be considered that measures to use at least partially energy generated from non-fossil resources are not sufficient to obtain a particularly low cradle-to-gate PCF for polyethyleneimine. In addition, the yield of each process step and thus the minimum waste generation is a strong lever. One further important factor is the conversion of monoethanolamine to ethyleneimine by catalytic gas phase synthesis as claimed in step (g) of the process of the present invention.

[0123] The term "at least partially from non-fossil resources" means that in further embodiments of the present invention, part of the energy can still be produced from fossil fuels, preferably natural gas, especially for the process for preparing polyethyleneimine and for the process for preparing ethanolamine, and for all processes of the present invention, since the combustion of natural gas leads to much lower carbon dioxide emissions per megajoule of energy produced compared to the combustion of coal. However, the part of the energy produced from fossil fuels in the processes of the present invention should be as low as possible, preferably < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10%. In one embodiment, the energy is generated from non-fossil resources only.

[0124] Further preferably, at least a part of the energy used in the processes of the present invention is utilized from excess energy generated in other exothermic chemical processes (typical examples: acrylic acid, formaldehyde or ethylene oxide production) other than the process steps of the present invention, for example in a chemical "Verbund" production plant which distributes excess energy (for example as steam) to the consumers of endothermic processes. The excess steam can replace steam generated from fossil fuels and be allocated as CO2e credit to the source of the exothermic process, thus balancing the CO2-balance as described in the "TfS PCF Guidelines". Such a Verbund plant is preferably supplied with additional energy generated from non-fossil resources.

[0125] According to local legislation, various methods for certifying and tracking "energy portfolios" have been established. Certificates such as "non-fossil certificate contracts" are a common practice to track the rate of non-fossil energy used in industrial processes and related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / ).

[0126] Further preferably, especially for the process for preparing polyethyleneimine and for the process for preparing ethanolamine and for all processes of the present application in a further embodiment of the present application, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in the process of the present application is generated from non-fossil resources.

[0127] Preferably, the energy is at least partially generated from non-fossil resources selected from the group consisting of solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydro power (tidal power, wave power, hydroelectric dams, riverine hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), renewable fraction of waste energy, nuclear energy and mixtures thereof.

[0128] In a further embodiment, the energy is at least partially generated from non-fossil resources selected from renewable resources, preferably selected from the group consisting of solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydro power (tidal power, wave power, hydroelectric dams, riverine hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), renewable fraction of waste and mixtures thereof.

[0129] The types of energy resources mentioned above are generally known to the person skilled in the art. Preferred energy resources are mentioned below.

[0130] By the process of the present application for preparing polyethyleneimine, the greenhouse gas (GHG) emissions upstream on scopes 1, 2 and scope 3 (cradle to gate) generated from polyethyleneimine, i.e. the total cradle to gate product carbon footprint (PCF) of polyethyleneimine, compared to the product carbon footprint of polyethyleneimine typically prepared, is preferably reduced by > 50%.

[0131] In the meaning of the present application, polyethyleneimine typically or conventionally prepared preferably has the meaning that hydrogen and synthesis gas are provided by steam reforming of natural gas and the conversion of monoethanolamine to ethyleneimine in step (g) of the present application is carried out by a liquid phase process, wherein in said conventional process mainly no non-fossil energy is used.

[0132] In a preferred process of the present application for preparing polyethyleneimine, the polyethyleneimine obtained in step (h) has a total cradle-to-gate product carbon footprint of < 8.0 kg CO2e / kg polyethyleneimine, preferably < 7.0 kg CO2e / kg polyethyleneimine, more preferably < 6 kg CO2e / kg polyethyleneimine, further more preferably < 5 kg CO2e / kg polyethyleneimine, most preferably < 4.0 kg CO2e / kg polyethyleneimine, further most preferably < 3.0 kg CO2e / kg polyethyleneimine, even further most preferably < 2.0 kg CO2e / kg polyethyleneimine, very most preferably < 1.5 kg CO2e / kg polyethyleneimine. This means that the greenhouse gas (GHG) emissions upstream of ranges 1, 2 and range 3 (cradle-to-gate) by the polyethyleneimine of the process according to the present application are typically < 8.0 kg CO2e / kg polyethyleneimine, preferably < 7.0 kg CO2e / kg polyethyleneimine, more preferably < 6 kg CO2e / kg polyethyleneimine, further more preferably < 5 kg CO2e / kg polyethyleneimine, most preferably < 4.0 kg CO2e / kg polyethyleneimine, further most preferably < 3.0 kg CO2e / kg polyethyleneimine, even further most preferably < 2.0 kg CO2e / kg polyethyleneimine, very most preferably < 1.5 kg CO2e / kg polyethyleneimine.

[0133] In the present application, the product carbon footprint given in kg CO2e / kg product relates to the active product (100% product). For example, in case of preparing a 50 wt.% aqueous PEI, only the active product without water and other impurities is accounted for the total cradle-to-gate product carbon footprint.

[0134] The present application further relates to a polyethyleneimine obtainable by the process for preparing a polyethyleneimine according to the present application.

[0135] (i) at least partially by water decomposition, preferably electrolysis and (ii) hydrogen obtained based on energy generated at least partially from non-fossil resources, preferably twice, into the value chain process according to the application for the production of ethanolamines and polyethyleneimines, i.e. in step (a) (production of ammonia) and step (b) (production of methanol as source for the manufacture of ethylene). Furthermore, the carbon source for the production of ethanolamines and polyethyleneimines, i.e. in step (b) (production of methanol), is also carbon oxides, preferably carbon dioxide. Thus, the by-product spectrum of ammonia and methanol employed in the process according to the application for the preparation of ethanolamines and polyethyleneimines is different from the by-product spectrum of ammonia and methanol obtained by conventional processes, i.e. using synthesis gas "syngas", which is a combination of different amounts of H2, CO and CO2, often derived from gasifying coal or natural gas. Methanol obtained conventionally, for example, usually contains more methyl formate, acetone and higher alcohols (> C3), and ammonia obtained conventionally usually contains more sulfur compounds and unsaturated hydrocarbon impurities than methanol and ammonia obtained by the process according to the application. Thus, the by-product spectrum of ethylene manufactured by cracking fossil-based hydrocarbon raw materials such as naphtha or natural gas, which is used in conventionally obtained ethylene oxide, is even more different from ethylene oxide according to the application.

[0136] The different product spectrum of ethylene, respectively ammonia and methanol, is also reflected in the downstream products, i.e. in the ethanolamines and polyethyleneimines obtained according to the application.

[0137] It has surprisingly been found that the polyethyleneimines obtained by the process of the application are further characterized by a different ratio of primary, secondary and tertiary amino groups compared to polyethyleneimines obtained by conventional processes. The share of secondary amino groups increases at the expense of the share of primary amino groups in the polyethyleneimines prepared according to the application. Said ratio of primary, secondary and tertiary amino groups in the polyethyleneimines of the application is beneficial for the stability of the polyethyleneimines during carbon capture (primary amino groups generally decompose faster than secondary amino groups under conditions occurring during cyclic exposure at, for example, up to 110 °C during the CO2 desorption phase).

[0138] The present invention further relates to polyethyleneimines having a total cradle-to- gate product carbon footprint of < 8.0 kg CO2e / kg polyethyleneimine, preferably < 7.0 kg CO2e / kg polyethyleneimine, more preferably < 6 kg CO2e / kg polyethyleneimine, further more preferably < 5 kg CO2e / kg polyethyleneimine, most preferably < 4.0 kg CO2e / kg polyethyleneimine, further most preferably < 3.0 kg CO2e / kg polyethyleneimine, even further most preferably < 2.0 kg CO2e / kg polyethyleneimine, very most preferably < 1.5 kg CO2e / kg polyethyleneimine. The present application teaches all necessary steps for obtaining polyethyleneimines having the mentioned specific total cradle-to-gate product carbon footprint.

[0139] Many carbon labels, which indicate the PCF of a given product, are known. The world’s first carbon label, the Carbon Reduction Label, shows the embodied carbon footprint in a product and was first introduced in the UK in 2006 by Carbon Trust. The Guideline “The Product Carbon Footprint Guideline for the Chemical Industry”, published by TfS (Together for Sustainability), Version 2.0, November 2022 (TfS Guideline), which is used in the present application as a basis for the calculation of the total cradle-to-gate PCF, is “open source”, i.e. available to everyone. Thus, a person skilled in the art can calculate the specific product carbon footprint of a polyethyleneimine prepared by different methods and using raw materials and energy available at a specific location, and polyethyleneimines prepared by different methods with distinguishable material and energy inputs can be clearly distinguished by different cradle-to-gate product carbon footprints.

[0140] Preferably, in the process of the present invention for preparing polyethyleneimines, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of typically < 0.6 kg CO2e / kg ammonia, preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia. This means that the greenhouse gas (GHG) emissions upstream of ranges 1, 2 and range 3 (cradle-to-gate) generated from ammonia according to the process of the present invention are typically < 0.6 kg CO2e / kg ammonia, preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia.

[0141] The present application further relates to ammonia having a total cradle-to- gate product carbon footprint of < 0.6 kg CO2e / kg ammonia, preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia. The present application teaches all necessary steps for obtaining ammonia having the mentioned specific total cradle-to-gate product carbon footprint.

[0142] More preferably, in the process of the present application for the preparation of polyethyleneimine, the ethylene oxide obtained in step (d) has a total cradle-to-gate product carbon footprint of generally < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide. This means that the greenhouse gas (GHG) emissions upstream of ranges 1, 2 and range 3 (cradle-to-gate) generated from ethylene oxide according to the process of the present application are generally < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide.

[0143] The present application further relates to ethylene oxide having a total cradle-to- gate product carbon footprint of < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide. The present application teaches all necessary steps for obtaining ethylene oxide having the mentioned specific total cradle-to-gate product carbon footprint.

[0144] Furthermore, more preferably, in the process of the present application for the preparation of polyethyleneimine, the ethanolamine obtained in step (e) has a total cradle-to-gate product carbon footprint of generally < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine. This means that the greenhouse gas (GHG) emissions upstream of ranges 1, 2 and range 3 (cradle-to-gate) generated from ethanolamine according to the process of the present application are generally < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine.

[0145] The present invention further relates to ethanolamine having a total cradle-to- gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine. The present application teaches all necessary steps for obtaining ethanolamine having the mentioned specific total cradle-to-gate product carbon footprint.

[0146] Most preferably, in the process of the present invention for the preparation of polyethyleneimine, the ethyleneimine obtained in step (g) has a total cradle-to-gate product carbon footprint of typically < 7.5 kg CO2e / kg ethyleneimine, more preferably < 6.5 kg CO2e / kg ethyleneimine, most preferably 4.5 kg CO2e / kg ethyleneimine. This means that the greenhouse gas (GHG) emissions upstream of ranges 1, 2 and range 3 (cradle-to-gate) from ethyleneimine generated according to the process of the present invention are preferably < 7.5 kg CO2e / kg ethyleneimine, more preferably < 6.5 kg CO2e / kg ethyleneimine, most preferably 4.5 kg CO2e / kg ethyleneimine.

[0147] The present invention further relates to ethyleneimine having a total cradle-to- gate product carbon footprint of < 7.5 kg CO2e / kg ethyleneimine, more preferably < 6.5 kg CO2e / kg ethyleneimine, most preferably 4.5 kg CO2e / kg ethyleneimine. The present application teaches all necessary steps for obtaining ethyleneimine having the mentioned specific total cradle-to-gate product carbon footprint.

[0148] It is known to the skilled person that the products of the “ammonia value chain” (such as ethanolamine, ethyleneimine and polyethyleneimine) are typically already highly emission-relevant at the beginning of this important value chain. Therefore, the addition of the emissions in the various energy-intensive process steps required for the downstream end products reflected in the PCF of ethanolamine, ethyleneimine and polyethyleneimine should lead to very high final PCF numbers for these highly processed products of the ammonia value chain. It is therefore completely unexpected that it is possible to provide ethanolamine, ethyleneimine and polyethyleneimine as far downstream products of the “ammonia value chain” having such low total cradle-to-gate product carbon footprints as mentioned above.

[0149] The present invention preferably relates to a process for the preparation of polyethyleneimine, wherein the process comprises the following steps:

[0150] (a) reacting hydrogen gas with nitrogen gas to form ammonia, wherein the ammonia obtained in step (a) preferably has a total cradle-to-gate product carbon footprint of < 0.6 kg CO2e / kg ammonia, preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia,

[0151] (b) reacting hydrogen gas with a carbon oxide, preferably carbon dioxide, to form methanol,

[0152] (c) converting the methanol from step (b) to ethylene,

[0153] (d) reacting the ethylene from step (c) with oxygen to form ethylene oxide, wherein the ethylene oxide obtained in step (e) has a total cradle-to-gate product carbon footprint of < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide,

[0154] (e) converting the ammonia from step (a) to ethanolamine with the ethylene oxide from step (d) in one or more steps, wherein the ethanolamine obtained in step (e) preferably has a total cradle-to-gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine,

[0155] (f) separating monoethanolamine from the ethanolamine obtained in step (e);

[0156] (g) converting the monoethanolamine from step (f) to ethylene imine by catalytic gas phase synthesis, wherein the ethylene imine obtained in step (g) preferably has a total cradle-to-gate product carbon footprint of < 7.5 kg CO2e / kg ethylene imine, more preferably < 6.5 kg CO2e / kg ethylene imine, most preferably 4.5 kg CO2e / kg ethylene imine,

[0157] and

[0158] (h) polymerizing the ethyleneimine obtained in step (g) to polyethyleneimine, wherein the polyethyleneimine obtained in step (i) has a total cradle-to-gate product carbon footprint of < 8.0 kg CO2e / kg polyethyleneimine, preferably < 7.0 kg CO2e / kg polyethyleneimine, more preferably < 6 kg CO2e / kg polyethyleneimine, further more preferably < 5 kg CO2e / kg polyethyleneimine, most preferably < 4.0 kg CO2e / kg polyethyleneimine, further most preferably < 3.0 kg CO2e / kg polyethyleneimine, even further most preferably < 2.0 kg CO2e / kg polyethyleneimine, very most preferably < 1.5 kg CO2e / kg polyethyleneimine,

[0159] wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water decomposition, preferably by electrolysis, using energy generated at least partially from non-fossil resources, the hydrogen in step (a) and / or step (b) preferably having a total cradle-to-gate product carbon footprint of < 5 kg CO2e / kg hydrogen, preferably < 4.6 kg CO2e / kg hydrogen, more preferably < 3.5 kg CO2e / kg hydrogen, most preferably < 2.5 kg CO2e / kg hydrogen, further most preferably < 2 kg CO2e / kg hydrogen, more preferably, the hydrogen in step (a) and step (b) has a total cradle-to-gate product carbon footprint of < 5 kg CO2e / kg hydrogen, preferably < 4.6 kg CO2e / kg hydrogen, more preferably < 3.5 kg CO2e / kg hydrogen, most preferably < 2.5 kg CO2e / kg hydrogen, further most preferably < 2 kg CO2e / kg hydrogen.

[0160] In a preferred process for preparing polyethyleneimine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.6 kg CO2e / kg ammonia, preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia.

[0161] In a more preferred process for preparing polyethyleneimine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.6 kg CO2e / kg ammonia, preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia, and the ethanolamine obtained in step (e) has a total cradle-to-gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine.

[0162] In a most preferred process for preparing polyethyleneimine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia, the ethanolamine obtained in step (e) has a total cradle-to-gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine, and the ethyleneimine obtained in step (g) has a total cradle-to-gate product carbon footprint of < 7.5 kg CO2e / kg ethyleneimine, more preferably < 6.5 kg CO2e / kg ethyleneimine, most preferably 4.5 kg CO2e / kg ethyleneimine.

[0163] In a further most preferred process for preparing polyethyleneimine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia, the ethanolamine obtained in step (e) has a total cradle-to-gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine, the ethyleneimine obtained in step (g) has a total cradle-to-gate product carbon footprint of < 7.5 kg CO2e / kg ethyleneimine, more preferably < 6.5 kg CO2e / kg ethyleneimine, most preferably 4.5 kg CO2e / kg ethyleneimine, and the polyethyleneimine obtained in step (h) has a total cradle-to-gate product carbon footprint of preferably < 7.0 kg CO2e / kg polyethyleneimine, more preferably < 6 kg CO2e / kg polyethyleneimine, further more preferably < 5 kg CO2e / kg polyethyleneimine, most preferably < 4.0 kg CO2e / kg polyethyleneimine, further most preferably < 3.0 kg CO2e / kg polyethyleneimine, even further most preferably < 2.0 kg CO2e / kg polyethyleneimine, very most preferably < 1.5 kg CO2e / kg polyethyleneimine.

[0164] The present application further relates to a process for preparing polyethyleneimine, wherein the process comprises the following steps:

[0165] (a) reacting hydrogen with nitrogen to form ammonia, wherein the ammonia obtained in step (b) has a total cradle-to-gate product carbon footprint of preferably < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia,

[0166] (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol,

[0167] (c) converting the methanol from step (b) to ethylene,

[0168] (d) reacting the ethylene from step (c) with oxygen to form ethylene oxide, wherein the ethylene oxide obtained in step (d) has a total cradle-to-gate product carbon footprint of preferably < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide,

[0169] (e) converting the ammonia from step (a) to ethanolamine in one or more steps with ethylene oxide from step (d), wherein the ethanolamine obtained in step (f) has a total cradle-to- gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine,

[0170] wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water splitting, preferably by electrolysis, using energy generated at least partially from non-fossil resources, the hydrogen in step (a) and / or step (b) has a total cradle-to-gate product carbon footprint of < 5 kg CO2e / kg hydrogen, preferably < 4.6 kg CO2e / kg hydrogen, more preferably < 3.5 kg CO2e / kg hydrogen, most preferably < 2.5 kg CO2e / kg hydrogen, further most preferably < 2 kg CO2e / kg hydrogen, more preferably the hydrogen in step (a) and step (b) has a total cradle-to-gate product carbon footprint of < 5 kg CO2e / kg hydrogen, preferably < 4.6 kg CO2e / kg hydrogen, more preferably < 3.5 kg CO2e / kg hydrogen, most preferably < 2.5 kg CO2e / kg hydrogen, further most preferably < 2 kg CO2e / kg hydrogen.

[0171] In a preferred process for preparing ethanolamine, the ethylene oxide obtained in step (d) has a total cradle-to-gate product carbon footprint of < 1.2 kg CO2e / kg ethylene oxide, more preferably < 0.8 kg CO2e / kg ethylene oxide, most preferably < 0.8 kg CO2e / kg ethylene oxide.

[0172] In a preferred process for preparing ethanolamine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia.

[0173] In a preferred process for preparing ethanolamine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia, and the ethylene oxide obtained in step (d) has a total cradle-to-gate product carbon footprint of < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide.

[0174] In the most preferred process for preparing ethanolamine, the ammonia obtained in step (a) has a total cradle-to-gate product carbon footprint of < 0.4 kg CO2e / kg ammonia, more preferably < 0.15 kg CO2e / kg ammonia, the ethylene oxide obtained in step (d) has a total cradle-to-gate product carbon footprint of < 1.2 kg CO2e / kg ethylene oxide, preferably < 0.8 kg CO2e / kg ethylene oxide, more preferably < 0.6 kg CO2e / kg ethylene oxide, and the ethanolamine obtained in step (e) has a total cradle-to-gate product carbon footprint of < 1.6 kg CO2e / kg ethanolamine, preferably < 1.2 kg CO2e / kg ethanolamine, more preferably < 0.9 kg CO2e / kg ethanolamine.

[0175] By the process for preparing ethanolamine according to the present application, the greenhouse gas (GHG) emissions upstream of ranges 1, 2 and range 3 (cradle-to-gate) from ethanolamine generation, i.e. the total cradle-to-gate product carbon footprint (PCF) of ethanolamine, are preferably reduced by > 50% compared to the product carbon footprint of ethanolamine typically prepared.

[0176] In the meaning of the present application, ethanolamine typically or conventionally prepared preferably has the meaning that hydrogen and synthesis gas are provided by steam reforming of natural gas.

[0177] The present application further relates to ethanolamine obtainable by the process for preparing ethanolamine according to the present application. The total cradle-to-gate product carbon footprint of ethanolamine obtainable by the process according to the present application is mentioned above.

[0178] As mentioned above, the different by-product spectrum of ammonia and methanol obtained by the process of the present application compared to the by-product spectrum of fossil-based ammonia and fossil-based synthesis gas and / or hydrocracker source in conventional processes is also reflected in the ethanolamine (downstream product) according to the present application.

[0179] The process for preparing polyethyleneimine comprises steps (a) to (h) as mentioned above and the generation of hydrogen:

[0180] The preparation (generation) of hydrogen in step (a) and / or step (b), preferably in steps (a) and (b), is obtained at least partially by water splitting, preferably by electrolysis, using energy generated at least partially from non-fossil resources:

[0181] This step involves providing hydrogen obtained at least partially by water decomposition, preferably by electrolysis, using energy generated at least partially from non-fossil resources.

[0182] The term "at least partially by water decomposition" means that a portion of the hydrogen can still be produced by other methods, typically by steam reforming of natural gas and / or other light hydrocarbons, partial oxidation of heavier hydrocarbons and coal gasification, preferably by steam reforming of natural gas and / or other light hydrocarbons. However, the portion of hydrogen produced in step (a) and / or (b) by other methods than by water decomposition should be as low as possible.

[0183] Preferably, in step (a) of the process of the present application, < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10% of the hydrogen is produced by other methods than by water decomposition. In one embodiment, the hydrogen in step (a) is produced exclusively by water decomposition, preferably by electrolysis.

[0184] Preferably, in step (b) of the process of the present application, < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10% of the hydrogen is produced by other methods than by water decomposition. In one embodiment, the hydrogen in step (b) is produced exclusively by water decomposition, preferably by electrolysis.

[0185] More preferably, in steps (a) and (b) of the process of the present application, < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10% of the hydrogen is produced by other methods than by water decomposition. In one embodiment, the hydrogen in step (a) is produced exclusively by water decomposition, preferably by electrolysis.

[0186] Preferably, the hydrogen in step (a) and / or step (b) has a total cradle-to- gate product carbon footprint of < 5 kg CO2e / kg hydrogen, preferably < 4.6 kg CO2e / kg hydrogen, more preferably < 3.5 kg CO2e / kg hydrogen, most preferably < 2.5 kg CO2e / kg hydrogen, further most preferably < 2 kg CO2e / kg hydrogen, more preferably, the hydrogen in step (a) and step (b) has a total cradle-to-gate product carbon footprint of < 5 kg CO2e / kg hydrogen, preferably < 4.6 kg CO2e / kg hydrogen, more preferably < 3.5 kg CO2e / kg hydrogen, most preferably < 2.5 kg CO2e / kg hydrogen, further most preferably < 2 kg CO2e / kg hydrogen.

[0187] The term "at least partially derived from non-fossil resources" is described above.

[0188] Alkoxylated compounds such as polyalkylene glycols and compounds comprising an alkylene glycol group are used in various industrial fields and have high performance when used in, for example, home care products, cosmetic products, pharmaceutical products, food industry, construction materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metal working fluids and transmission fluids, antifoams, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metal working fluids, agrochemicals such as pesticides, textile and leather auxiliaries, bio-processing, fuel performance packages and poly(urethane) applications.

[0189] A review on polyalkylene glycols is given in Chem. Rev. [Chemical Reviews] 2016, 116, 2170-2243. Therein it is described that polyalkylene glycols are aliphatic polyethers, which are generated by ring-opening polymerization (ROP) of epoxide monomers, especially ethylene oxide (EO), propylene oxide (PO) and to a smaller extent butylene oxide (BO). Characteristic properties of polyether-based materials are due to their unique backbone, especially their high flexibility leading to low glass transitions below -60 °C, and due to the C-O-C bond their hydrophilicity.

[0190] Poly(ethylene glycol) (or polyethylene glycol) is the gold standard biocompatible polymer for pharmaceutical, cosmetic and medical applications and is used in an extremely wide range of products ranging from skin care products to tablet formulations and food additives. Higher molecular weight polymers of EO are commonly referred to as poly(ethylene oxide) (PEO) or sometimes poly(oxyethylene) (POE), while polymers with a molecular weight below 30,000 g / mol are referred to as poly(ethylene glycol) (PEG). The abbreviation mPEG denotes a monomethyl ether-capped PEG with a single terminal hydroxyl group, which can be further functionalized for synthesis with PEG block copolymers or bioconjugation, often referred to as "PEGylation".

[0191] For lower molecular weight poly(propylene oxide) (PPO), commonly named poly(propylene glycol) (or polypropylene glycol) (PPG), is typically produced by ROP of PO. In contrast to PEG or PEO, PPO is not water soluble at room temperature. However, rather low molecular weight PPG is soluble in aqueous solutions at low temperatures. The base initiated polymerization of PO in industry mainly relies on potassium hydroxide and an alcohol as initiator. Since a major part of PO is used for the preparation of star polymers, so-called polyether-polyols, typically a multifunctional initiator is used, such as glycerol, pentaerythritol, or sorbitol. Star-shaped polyether polyols based on PPO play a key role in the synthesis of polyurethane soft foams due to their chain flexibility (i.e. low glass transition) and their amorphous nature. Typically, PPG is used in lubricants, antifoams, softeners, rheology modifiers, poly(urethane) applications, and non-ionic surfactants, often in combination with PEG (e.g. as block copolymers).

[0192] In contrast to EO and PO, 1,2-epoxybutane monomer (BO) has to be produced in a two-step industrial process and cannot be obtained by direct oxidation of the corresponding olefin. The synthesis relies on the oxidation of butadiene to vinyl oxirane and subsequent hydrogenation. The properties of poly(epoxybutane) (or polybutylene glycol) (PBO) are similar to PPO, however, as expected, it is more hydrophobic. The high hydrophobicity of PBO is advantageous for several applications, e.g. for polyurethanes which have to be stable against water or hot water vapor. Small amounts of PBO added to lubricants can be used to improve their properties. In several cases, BO is used as a comonomer to modify the properties of other polyethers, i.e. to increase their non-polar and amorphous structure. The increased hydrophobicity of PBO is an advantage for surfactants combining PEO and PBO blocks.

[0193] In the present application, the expressions “polyalkylene glycol”, “polyethylene glycol”, “polypropylene glycol”, “polybutylene glycol” are used for the respective polymer or polymer block of any molecular weight.

[0194] Customers and consumers of e.g. household care products, skin care products, tablet formulations, food additives urge producers to avoid putting non-degradable components into the cycle, which will inevitably accumulate in the environment. Most prominent are microplastics and water-soluble performance polymers. However, another goal is to improve the carbon footprint and greenhouse gas accounting of such products in general. The dilemma is that with any improvement in biodegradability, the industry converts the potential sink of carbon and CO2 into a specified release of CO2 into the atmosphere, as any substance claiming biodegradability will be broken down and at least 60% of the carbon content must be converted into CO2 after 28 days (OECD 301B). In this sense and time frame, producers are urged to worsen their overall product carbon footprint (PCF) as those scope 3 (downstream) emissions are also part of the equation. For some of these products, such as many surfactants, the use of bio-raw materials is considered an option. However, land use and water footprint are also heavy burdens on the environment and society, especially when talking about bulk products such as alkoxylates; not to mention that ca. 25% of global GHG are the result of agriculture and food production.

[0195] It is a further object of the present invention to provide a solution to said dilemma, i.e. to provide alkoxylates with a low cradle to grave (i.e. including scope 3 downstream ) product carbon footprint (PCF) and generally at the same time with good biodegradability.

[0196] In the present application, the "material carbon" in a polymeric product is considered the only additional CO2 emission of the end-of-life "grave" emissions; all other emissions in the use phase of the product by the customer and consumer (e.g. emissions related to transport and use) are out of scope.

[0197] It is an object to achieve a method for preparing an alkoxylate compound comprising

[0198] i) 20 wt-% to < 100 wt-%, preferably 30 wt-% to < 99.3 wt-% of ethylene oxide units and / or propylene oxide units,

[0199] ii) 0 wt-% to 30 wt-%, preferably 0.5 wt-% to 20 wt-% of at least one alkylene oxide unit different from ethylene oxide units and propylene oxide units,

[0200] iii) > 0 wt-% to 80 wt-%, preferably 0.2 wt-% to 70 wt-% of at least one starter unit having a Zel'evitnoff active hydrogen atom,

[0201] wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%,

[0202] The method comprises the following steps:

[0203] (b) reacting hydrogen with carbon dioxide to form methanol,

[0204] (c) converting the methanol from step (b) to ethylene and / or propylene,

[0205] (d) reacting the ethylene and / or propylene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and

[0206] (e0) in one or more steps, reacting the ethylene oxide and / or propylene oxide obtained in step (d) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide with the at least one starter unit having a Zelinskyjnov-active hydrogen atom to form an alkoxylated compound,

[0207] wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gas or from air or from seawater or other natural water or obtained from a biological process, such as a fermentation process from waste or biomass, preferably wherein the hydrogen in step (b) is at least partially obtained by water splitting, preferably by electrolysis, of this water splitting, preferably this electrolysis, preferably using energy generated at least partially from non-fossil resources.

[0208] This object is further achieved by an alkoxylated compound obtainable by the method according to the present application and by an alkoxylated compound having a total cradle-to-gate product carbon footprint of typically < 8.88 C - 0.253 E + 1.33 P -0.940, preferably < 8.38 C - 0.330 E + 1.12 P - 0.829, more preferably < 7.89 C - 0.406 E +0.898 P - 0.718, most preferably < 7.40 C - 0.483 E + 0.681 P - 0.606, further most preferably <6.90 C - 0.560 E + 0.464 P - 0.495, further most preferably < 6.48 C - 0.489 E + 0.239 P - 0.436, further most preferably < 6.06 C - 0.418 E - 0.014 P - 0.377, further most preferably <5.64 C - 0.347 E - 0.211 P - 0.318, even further most preferably < 5.21 C - 0.276 E -0.436 P - 0.259, wherein C is the mass ratio of the carbon content in the alkoxylated compound, E is the mass ratio of the EO-content in the alkoxylated compound, and P is the mass ratio of the “sum of PO and other alkoxides than PO and EO” content in the alkoxylated compound, wherein each mass ratio ranges from 0 to 1 and the sum of the mass ratios of C + E + P is 1.

[0209] The alkoxylated compound of the present application preferably meets the biodegradability requirements set out in OECD 301 B.

[0210] The object is further achieved by the use of the alkoxylated compound of the present application in household care products, cosmetic products, pharmaceutical products, the food industry, construction materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metal working fluids and transmission fluids, antifoams, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metal working fluids, agrochemicals such as pesticides, textile and leather auxiliaries, bio-processing, fuel performance packages and poly(urethane) applications.

[0211] The present application further relates to a process for preparing ethylene oxide or propylene oxide, comprising the steps of:

[0212] (b) reacting hydrogen with carbon dioxide to form methanol,

[0213] (c) converting the methanol from step (b) to ethylene and / or propylene,

[0214] (d) reacting the ethylene and / or propylene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide,

[0215] wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gases or from air or from seawater or other natural water, or obtained from a biological process, such as a fermentation process from waste or biomass,

[0216] and / or

[0217] wherein the hydrogen in step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy at least partially generated from non-fossil resources.

[0218] The present application further relates to the ethylene oxide obtained in step (d) having a total cradle-to-gate product carbon footprint of < 1.7 kg CO2e / kg ethylene oxide, preferably < 1.6 kg CO2e / kg ethylene oxide, more preferably < 1.5 kg CO2e / kg ethylene oxide, further more preferably < 1.4 kg CO2e / kg ethylene oxide, most preferably < 1.3 kg CO2e / kg ethylene oxide, further most preferably < 1.2 kg CO2e / kg ethylene oxide, further most preferably < 1.1 kg CO2e / kg ethylene oxide, even further most preferably < 1.0 kg CO2e / kg ethylene oxide, even further most preferably < 0.9 kg CO2e / kg ethylene oxide, even further most preferably < 0.8 kg CO2e / kg ethylene oxide, even further most preferably < 0.7 kg CO2e / kg ethylene oxide, even further most preferably < 0.6 kg CO2e / kg ethylene oxide, even further most preferably < 0.5 kg CO2e / kg ethylene oxide, even further most preferably < 0.4 kg CO2e / kg ethylene oxide, even further most preferably < 0.3 kg CO2e / kg ethylene oxide, and the propylene oxide obtained in step (c) having a total cradle-to-gate product carbon footprint of < 3.4 kg CO2e / kg propylene oxide, preferably < 3.3 kg CO2e / kg propylene oxide, more preferably < 3.2 kg CO2e / kg propylene oxide, further more preferably < 3.1 kg CO2e / kg propylene oxide, most preferably < 3.0 kg CO2e / kg propylene oxide, further most preferably < 2.9 kg CO2e / kg propylene oxide, even further most preferably < 2.8 kg CO2e / kg propylene oxide, even further most preferably < 2.7 kg CO2e / kg propylene oxide, even further most preferably < 2.6 kg CO2e / kg propylene oxide, even further most preferably < 2.5 kg CO2e / kg propylene oxide, even further most preferably < 2.4 kg CO2e / kg propylene oxide, even further most preferably < 2.3 kg CO2e / kg propylene oxide.

[0219] The products in the process and steps (b), (c) and (d) of the present application are not based on a starting material based on a biomass feedstock or a biomass balanced feedstock.

[0220] The terms ethene and propene are the IUPAC names of the compounds of the formula CH2=CH2 and CH3CH=CH2, which are also known as ethylene and propylene.

[0221] The IUPAC name of the term ethylene oxide as used in the present application is oxirane (C2H4O).

[0222] In the meaning of the present application, propylene oxide is 1,2-propylene oxide. The IUPAC name of the term propylene oxide as used in the present application is 2-methyloxirane (C3H6O). An alternative name is 1,2-propylene oxide.

[0223] An ethylene oxide unit is the reacted form of ethylene oxide in an alkoxylated compound, a propylene oxide unit is the reacted form of propylene oxide in an alkoxylated compound, and an alkylene oxide unit is the reacted form of an alkylene oxide in an alkoxylated compound.

[0224] The term "alkoxylated compound" as used in the present application encompasses alkoxylated compounds composed of at least one ethylene oxide unit and / or propylene oxide unit and at least one starter unit having a Zelinsky active hydrogen atom.

[0225] According to REACH (Article 3(5)) (Regulation (EC) No 1907 / 2006 of the European Parliament and of the Council of 18 December 2006 on REACH), a polymer is defined as a substance that meets the following criteria:

[0226] (a) more than 50 percent by weight of the substance consists of polymer molecules (see definition below); and,

[0227] (b) the amount of polymer molecules of the same molecular weight must be less than 50 percent by weight of the substance.

[0228] In the context of this definition:

[0229] A "polymer molecule" is a molecule containing a sequence of at least 3 monomeric units, which are covalently bound to at least one other monomeric unit or other reactant.

[0230] A "monomeric unit" means the reacted form of a monomeric substance in a polymer (to identify one or more monomeric units in the chemical structure of a polymer, the mechanism of polymer formation can be considered, for example).

[0231] A "sequence" is a contiguous string of monomeric units that are covalently bonded to one another and are uninterrupted by units other than monomeric units. The contiguous string of monomeric units can follow any network within a polymer structure.

[0232] "Other reactants" refer to molecules that can be connected to one or more sequences of monomeric units but cannot be considered monomers under the relevant reaction conditions used in the polymer formation process.

[0233] As used herein, the term "polymer" includes both homopolymers and copolymers. A "polymer" is linear or branched.

[0234] To address this objective, the relevant PCF of the alkoxylated compound and of the upstream compounds in its preparation is calculated based on the following guideline: "The Product Carbon Footprint Guideline for the Chemical Industry", published by TfS (Together for Sustainability), version 2.0, November 2022 (https: / / www.tfs-initiative.com) (in the following: "TfS guideline"). The guideline is "auditable", compliant with ISO, and accepted by the GHG Protocol and further "open source", available to the global industry using chemical materials.

[0235] The Applicant's unique Verbund system creates an efficient value chain that extends from the base chemicals all the way to the consumer products. This makes it possible to collect reliable data on the greenhouse gas (GHG) emissions generated (in particular by the alkoxylated compound and by the upstream compounds in the process of its preparation) at different stages of the life cycle of the products within and outside the Verbund owned by the company, from cradle to gate (upstream ranges 1, 2 and 3) and from cradle to grave (upstream and downstream ranges 1, 2 and 3).

[0236] In the present application, the "material carbon" in the polymer product is considered to be the only additional CO2 emissions at the end-of-life "grave" emissions; all other emissions in the product customer and consumer use phase (e.g. emissions related to transport and use) are outside the scope.

[0237] The process for the preparation of alkoxylated compounds, especially the precursor ethylene oxide and propylene oxide, is energy demanding and many of the steps (b) to (e0) of the process for the preparation of alkoxylated compounds can be performed by alternative methods. The inventors found a process for the preparation of alkoxylated compounds, wherein each step is optimized or at least prepared for obtaining alkoxylated compounds with a low carbon footprint.

[0238] For the solution of the dilemma of any improvement in biodegradability, one idea of the present invention is that the industry transforms the potential sink of carbon and CO2 into the certified release of CO2 into the atmosphere mentioned above in more detail is the reuse of the CO2 released into the atmosphere in the process for the preparation of alkoxylated compounds.

[0239] This goal is achieved in the process of the present invention by the selection of the reaction of hydrogen with carbon dioxide as methanol preparation step (b), wherein the carbon dioxide is at least partially, preferably completely captured from industrial flue gases or from air or from seawater or other natural water or obtained from fermentation processes from waste or biomass.

[0240] It is known to the person skilled in the art that alkoxylated compounds with a high propylene oxide and higher epoxide (i.e. epoxides different from ethylene oxide and propylene oxide) content always have a higher cradle-to-grave PCF compared to alkoxylated compounds with a high ethylene oxide content, because the implicit emissions of propylene oxide are much higher than the implicit emissions of ethylene oxide. However, it was surprisingly found that the trend is turned around by using the process of the present invention (CO2 capture, preferably electrolytic H2, preferably green energy in one or more of steps (b) to (e0)). After a precise analysis of the different method steps for obtaining the alkoxylated compounds according to the present invention, it turned out that products with an increased content of propylene oxide and higher epoxides have decreasing a cradle-to-grave PCF. This means that, when turning to low-emission raw materials and processes, the trend is turned around for products with a high propylene oxide and higher epoxide content (see Figure 8 ).

[0241] In a preferred embodiment of the present invention, the propylene oxide in step (d) is thus obtained by oxidation of propylene with hydrogen peroxide as oxidizing agent.

[0242] It is to be considered that different large scale processes for the production of propylene oxide are known in the art, namely the chlorohydrin process (CHPO; multi-step process which proceeds via the addition of hypochlorous acid to propylene to form a chlorohydrin intermediate which is subsequently dehydrochlorinated to the epoxide), oxidation of propylene with organic peroxides including tert-butyl hydroperoxide and ethylbenzene hydroperoxide (MTBE PO process: by-product includes tert-butyl alcohol (TBA) for the preparation of methyl tert-butyl ethyl (MTBE); SMPO process: by-product includes ethylbenzene for styrene production); cumene hydroperoxide process (CHP; use of cumene hydroperoxide (CHP) for the epoxidation of propylene; CHP is obtained by oxidation of cumene with air; upon release of oxygen to propylene, CHP is converted to cumyl alcohol which can be dehydrated to a-methylstyrene which in turn can be hydrogenated back to cumene); and the hydrogen peroxide process (HPPO; production of propylene oxide from propylene and hydrogen peroxide).

[0243] The inventors further found that when the hydrogen gas used in step (b) for the preparation of methanol is obtained at least partially by water splitting, preferably electrolysis, based on electrical power generated at least partially from non-fossil resources, an alkoxylated compound with an especially low PCF is obtained.

[0244] Since it was found by precise analysis of the different process steps for obtaining an alkoxylated compound, especially steps (b), (c) and (d), to be essential for obtaining an alkoxylated compound with a low cradle-to-grave product carbon footprint, the present invention further relates to a process for the preparation of ethylene oxide or propylene oxide as mentioned above.

[0245] Steps (b), (c) and (d) in the process of the present invention for the preparation of ethylene oxide or propylene oxide are identical to steps (b), (c) and (d) in the process of the present invention for the preparation of an alkoxylated compound, and the definitions of process steps (b), (c) and (d) above and below apply to both processes.

[0246] More preferably, in the process for the preparation of an alkoxylated compound, energy in the form of thermal energy and / or electrical power is used in step (b) and in one or two of the further steps (c), (d) and (e0), and the energy used is generated at least partially from non-fossil resources. Most preferably, energy in the form of thermal energy and / or electrical power is used in all steps (b) to (e0), and the energy used in steps (b) to (e0) is generated at least partially from non-fossil resources.

[0247] More preferably, in the process for preparing ethylene oxide or propylene oxide, in step (b) and in one or both of the further steps (c) and (d), energy in the form of thermal energy and / or electrical power is used and the energy used is at least partially generated from non-fossil resources. Most preferably, in all steps (b) to (d), energy in the form of thermal energy and / or electrical power is used and the energy used in steps (b) to (d) is at least partially generated from non-fossil resources.

[0248] According to the TfS requirements, all processing steps until the production of the final end product have to be considered in the PCF of the final product - thus a highly processed product such as an alkoxylated compound with a low overall cradle-to-grave product carbon footprint as mentioned below would not be expected by the skilled person to be achievable. It is obvious that these products require energy-intensive starting materials and many subsequent energy-intensive processing steps.

[0249] However, it should be considered that measures using carbon dioxide which is at least partially captured or obtained from industrial flue gases or from air or from seawater or other natural water or obtained from fermentation processes from waste or biomass are not sufficient to obtain a particularly low cradle-to-grave PCF of alkoxylated compounds. Furthermore, it has been found that the yield of each process step and thus the minimum waste generation is a strong lever. One further important factor is the selection of the specific process for preparing ethylene and propylene (steps (b) and (c)) and in preferred embodiments the selection of the specific process for obtaining propylene oxide (step (d)).

[0250] In the process for preparing ethylene oxide and propylene oxide and alkoxylated compounds, the term "at least partially from non-fossil resources" means that part of the energy can still be produced from fossil fuels, preferably natural gas, since the combustion of natural gas leads to much lower carbon dioxide emissions per megajoule of energy produced compared to the combustion of coal. However, the part of the energy produced from fossil fuels should be as low as possible, preferably ≤ 50%, more preferably ≤ 30%, most preferably ≤ 20%, further most preferably ≤ 10% of the energy in one or two of steps (b), preferably (b) and the further steps (c), (d) and (e0), more preferably all steps (b) to (e0) is generated from fossil resources.

[0251] Further preferably, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in step (b), preferably in one or both of step (b) and the further steps (c), (d) and (e0), more preferably in all steps (b) to (e0) is generated from non-fossil resources.

[0252] Most preferably, in the process for preparing an alkoxylated compound, the energy in step (b), preferably in one or both of step (b) and the further steps (c), (d) and (e0), more preferably in all steps (b) to (e0) is generated from non-fossil resources only.

[0253] Most preferably, in the process for preparing ethylene oxide or propylene oxide, the energy in step (b), preferably in one or both of step (b) and the further steps (c) and (d), more preferably in all steps (b) to (e0) is generated from non-fossil resources only.

[0254] In a further preferred embodiment, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in the process of the present application is generated from non-fossil resources.

[0255] Generally, the energy used in steps (b), (c), (d) and (e0) is used in the form of thermal energy and / or electrical power.

[0256] Further preferably, at least a part of the energy used in the process of the present application is utilized from excess energy generated in other exothermic chemical processes (typical examples: acrylic acid, formaldehyde or ethylene oxide production) than the process steps of the present application, e.g. in a chemical "Verbund" production plant which distributes the excess energy (e.g. as steam) to the heat-consuming process consumers. The excess steam can replace steam generated from fossil fuels and is allocated to the exothermic process sources as a CO2e credit, balancing the CO2-balance as described in the "TfS PCF Guidelines". Such a Verbund plant is preferably supplied with additional energy generated from non-fossil resources.

[0257] Depending on local legislation, various methods for certifying and tracking "energy portfolios" have been established. Certificates such as "non-fossil certificate contracts" are a common practice to track the ratio of non-fossil energy used in industrial processes and related (e.g. in the "TfS PCF Guidelines"). https: / / www.ekoenergy.org / ecolabel / criteria / tracking / .

[0258] Preferably, the energy is at least partially generated from non-fossil resources selected from the group consisting of solar energy (thermal, photovoltaic and concentrated solar power), wind, hydroelectric power (tidal power, wave power, hydroelectric dams, riverine hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), renewable fraction of waste energy, nuclear energy and mixtures thereof.

[0259] In further embodiments, the energy is at least partially generated from non-fossil resources selected from renewable resources, preferably selected from the group consisting of solar energy (thermal, photovoltaic and concentrated solar power), wind, hydroelectric power (tidal power, wave power, hydroelectric dams, riverine hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), renewable fraction of waste and mixtures thereof.

[0260] The types of energy resources mentioned above are generally known to the person skilled in the art. Preferred energy resources are mentioned below.

[0261] The alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines, alkoxylated polyethyleneimines and surfactants of the present invention are known as such and are widely used today or just recently disclosed as further detailed below and are thus known to the person skilled in the art.

[0262] Due to the development of the Haber-Bosch process for the production of ammonia, the vast majority of ammonia is manufactured by direct synthesis from hydrogen and nitrogen in the presence of a catalyst, in particular an iron-containing catalyst. Particular care is required to provide the starting materials hydrogen and nitrogen. They should exhibit a high purity and be essentially free of catalyst poisons such as carbon monoxide and sulfur compounds such as H2S and SO2. In modern processes, a large amount of hydrogen is provided from natural gas by steam reforming.

[0263] However, the petrochemical steam reforming process has its negative impact in terms of its carbon footprint, including the consumption of large amounts of fossil-based natural resources and energy.

[0264] Today, it is important that the origin of hydrogen and downstream compounds obtained by clean energy can be tracked in a reliable manner. This is particularly important to ensure that:

[0265] The production of hydrogen and downstream compounds complies with sustainability standards.

[0266] The renewable attribute is not double-counted.

[0267] Therefore, companies are increasingly focusing on the procurement of green energy. Therefore, a tracking system must be developed for the origin of the energy used in the production of hydrogen and downstream compounds.

[0268] US 2011 / 136097 relates to a method for determining the origin of a foodstuff, more specifically for determining the geographical and / or biological origin of a foodstuff containing an alcohol or a sugar by using specific isotope ratios of sugars, for example from different plants, which are influenced by climatic conditions and the region of origin as an isotopic "fingerprint" of specific plants.

[0269] However, the deuterium content utilized in the present invention is not a natural "fingerprint", but a finding that the deuterium content of hydrogen gas obtained by electrolysis of water is lower than the deuterium content naturally occurring in hydrogen gas. Further, the geographical region of origin is not determined, but the process of hydrogen gas production.

[0270] US 6,495,609 relates to a method for recovering carbon dioxide from an ethylene oxide production process and using the recovered carbon dioxide as a carbon source for methanol synthesis. However, the hydrogen gas used in the method of US 6,495,609 is present in a synthesis gas such as natural gas or a refinery tail gas.

[0271] GB 2 464 691 A relates to the manufacture of methanol from agricultural cellulose / lignin materials. In a first section of the synthesis plant, the cellulose / lignin by-products remaining after harvesting of the agricultural products are converted by thermal oxidation into carbon dioxide. In another section of the synthesis plant, hydrogen is produced by electrolysis and then reacted with the carbon dioxide to produce methanol.

[0272] WO 2016 / 149507 A1 relates to the oxidative coupling of methane for obtaining a large number of different products. For example, claim 217 discloses a method for producing oxalate compounds.

[0273] US 7,119,231 B2 relates to a method for preparing an alkanolamine by reacting ammonia with an alkylene oxide in the presence of a catalyst in a reaction space to give a mono-, di- or trialkanolamine or a mixture of two or three of these compounds. There is no hint on the deuterium content of the hydrogen containing compounds employed in US 7,119,231 B2 or on the use of non-fossil energy sources.

[0274] FR 2 851 564 A1 relates to a method for preparing ethylene oxide and ethanolamine. As in FR 2 851 564 A1, there is no hint on the presence of deuterium in the hydrogen containing compounds or on the use of non-fossil energy sources.

[0275] US 2008 / 0283411 A1 relates to a method for converting carbon and hydrogen sources into hydrocarbons. It is mentioned that the method and apparatus are useful for the production of fossil fuel replacement energy, storage of renewable energy, sequestration of carbon dioxide from the atmosphere, offsetting global warming, and storage of carbon dioxide in liquid fuels.

[0276] WO 2015 / 102985 A1 relates to a method for preparing ethanolamines, which method comprises reacting a water-ammonia solution with ethylene oxide. However, there is no hint in WO 2015 / 102985 A1 on the production of hydrogen by electrolysis, the use of renewable energy and the presence of deuterium in the hydrogen-containing compounds disclosed in WO 2015 / 102985 A1.

[0277] DE 195 34 493 A1 relates to a process for preparing aziridine in the presence of a fine-particle shell catalyst. The aziridine is prepared by dehydration of an alkanolamine in the presence of the catalyst. However, neither the electrolysis of water for the production of hydrogen nor the deuterium content of the hydrogen-containing compounds mentioned in DE 195 34 493 A1 nor the use of renewable energy is mentioned in DE 195 34 493 A1.

[0278] It is therefore a further object of the present application to provide environmentally friendly alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines ("compounds of the present application") and an environmentally friendly process for their manufacture, which process uses as little fossil-based energy as possible, ideally no fossil-based energy, and thus increases CO2 emissions only as little as possible, ideally not at all.

[0279] This object is also achieved by using the molar fraction of deuterium in the hydrogen bound in the compounds of the present application based on the hydrogen gas for tracing the origin, in particular the energy origin, of the hydrogen bound in those compounds of the present application based on hydrogen gas; a method for tracing the origin, in particular the energy origin, of the hydrogen bound in downstream compounds based on hydrogen gas by determining the molar fraction of deuterium in the hydrogen bound in said compounds of the present application is also part of the present application.

[0280] Methods for determining the molar fraction of deuterium in hydrogen gas and downstream compounds based on hydrogen gas are known to the person skilled in the art and include mass spectrometry and NMR techniques.

[0281] In particular, the object is achieved by a process for the production of alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines using ethylene oxide and / or propylene oxide, preferably ethylene oxide, based on non-fossil sources, which are then used in known manner for the production of the compounds of the present application, wherein the molar fraction of deuterium is lower than in a product made using ethylene oxide (EO) and / or propylene oxide (PO), preferably EO, from fossil-based sources only. The deuterium content in the product using EO and / or PO, preferably EO, based on non-fossil sources is preferably at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, such as more than 60, 70, 80 or even 90 percent lower compared to a product using EO and / or PO, preferably EO, based on fossil sources only, such percentage being based on the total hydrogen content of the units derived from EO and / or PO, preferably EO, having reacted with the compounds of the present application.

[0282] In a further embodiment of the present application, the object is achieved by a process for the production of alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines, wherein the process comprises the following steps:

[0283] (a0) providing hydrogen gas having a molar fraction of deuterium based on a total hydrogen content of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm, by electrolysis based on electrical power generated at least partially from non-fossil energy sources,

[0284] (a) reacting the hydrogen gas from step (a0) with nitrogen to form ammonia,

[0285] (b) reacting the hydrogen gas from step (a0) with a carbon oxide, preferably carbon dioxide, to form methanol,

[0286] (c) converting the methanol from step (c) to ethylene and / or propylene, preferably ethylene, and (d) further converting, preferably with oxygen or an oxidizing agent, to ethylene oxide and / or propylene oxide, preferably ethylene oxide,

[0287] (e1) converting the ethylene oxide and / or propylene oxide, preferably ethylene oxide, from step (d) to alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines in one or more steps using known methods.

[0288] In a further embodiment of the present application, the object is achieved by a process for the production of alkoxylated polyethyleneimines, wherein the process comprises the following steps:

[0289] (a0) providing hydrogen gas having a molar fraction of deuterium based on the total hydrogen content of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm, by electrolysis based on electrical power generated at least partially from non-fossil energy sources,

[0290] (a) reacting the hydrogen gas from step (a0) with nitrogen to form ammonia,

[0291] (b) reacting the hydrogen gas from step (a0) with a carbon oxide, preferably carbon dioxide, to form methanol,

[0292] (c) converting the methanol from step (c) to ethylene and / or propylene, preferably ethylene, and (d) further, preferably with oxygen, to ethylene oxide and / or propylene oxide, preferably ethylene oxide,

[0293] (e) converting the ammonia from step (b) to ethanolamine in one or more steps with the ethylene oxide from step (d), and

[0294] (f) separating the monoethanolamine from the ethanolamine obtained in step (e),

[0295] (g) converting the monoethanolamine to ethylene imine,

[0296] (h) polymerizing the ethylene imine from step (g) to polyethylene imine; and

[0297] (i) alkoxylating the polyethylene imine from step (g) with ethylene oxide and / or propylene oxide, preferably ethylene oxide, and optionally further ingredients such as other alkylene oxides and / or lactones, to obtain an alkoxylated polyethylene imine.

[0298] Further, it is important that the origin of the hydrogen gas and downstream compounds obtained by clean energy can be tracked in a reliable way.

[0299] This is especially to ensure that:

[0300] the production of hydrogen gas and downstream compounds complies with sustainability standards.

[0301] the renewable property is not double counted.

[0302] Companies increasingly value the procurement of green energy. Therefore, tracking systems have to be developed for the origin of the energy used in the preparation of hydrogen gas and downstream compounds.

[0303] This objective is also achieved by using the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds to trace the source, particularly the energy source, of the hydrogen and hydrogen-based downstream compounds, wherein these compounds are preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide; and a method for tracing the source, particularly the energy source, of hydrogen and said hydrogen-based downstream compounds by determining the molar fraction of deuterium in the hydrogen and hydrogen-based downstream compounds, wherein these compounds are preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide.

[0304] Methods for determining the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds are known to those skilled in the art. A suitable method is described in the examples of this application.

[0305] Due to further advances in science and technology, and consequently, the development of increasingly sophisticated measurement techniques, the resolution of measurement methods used to determine deuterium content relative to total hydrogen content is expected to become increasingly precise, making even more accurate determinations possible in the future, and thus enabling the differentiation between minute differences. However, the invention disclosed herein will not be altered by such scientific advancements, but merely the increased likelihood of detecting the invention.

[0306] Another environmental benefit of the environmentally friendly alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimides according to the invention is their use in carbon capture methods, because the alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimides according to the invention are produced using as little fossil-based energy as possible, ideally without using fossil-based energy, at least relative to the content derived from EO and / or PO, preferably EO, and indeed thus only increase, ideally without increasing, CO2 emissions by as little as possible.

[0307] Of course, if environmentally friendly methods are also employed for other components (such as amines), then the present invention will be even more environmentally friendly. Therefore, the present invention also covers such even more environmentally friendly products, wherein the amines used, as well as other optional components such as the previously mentioned other epoxides and lactones, are derived from or made from renewable or even better non-fossil sources. Such sources are known to date.

[0308] Therefore, another embodiment of the present invention is the use of alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide according to the present invention as liquid or solid CO2 absorbents in CO2 capture methods.

[0309] Methods for preparing alkoxylated diamines, oligoamines and polyamines, as well as alkoxylated polyethylimides, are described in detail, including the various method steps mentioned above.

[0310] It is a further object of the present application to provide environmentally friendly surfactants with a low molar fraction of deuterium, wherein these surfactants comprise at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen.

[0311] This object further encompasses an environmentally friendly process for their manufacture, which uses as little fossil-based energy as possible, ideally no fossil-based energy, so that such a process thus only increases CO2 emissions as little as possible, ideally not at all; a further object is the molar fraction of deuterium in hydrogen and thus in such surfactants based on hydrogen, which comprise at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen, for tracing the origin of the hydrogen, in particular the energy source, and thus the use of such surfactants based on hydrogen, which comprise at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen.

[0312] Methods for determining the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen are known to the person skilled in the art and include mass spectrometry and NMR techniques.

[0313] In particular, this object is achieved by the surfactants of the present application comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or produced with hydrogen when using a process comprising the following steps: producing hydrogen from a non-fossil-based source, optionally producing methanol, ammonia, ethanolamine or ethylene or ethylene oxide in a further step, then using it or a combination thereof using known means to produce the surfactants of the present application in various sequences, wherein the molar fraction of deuterium is lower than the molar fraction of deuterium in products made using only hydrogen, methanol, ammonia, ethanolamine or ethylene or ethylene oxide from fossil-based sources, each of them individually as "starting material" as well as at least two of them as "starting material". The deuterium content in products using non-fossil-based starting material(s) is preferably at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, such as more than 60, 70, 80 or even 90 percent lower compared to products using only fossil-based materials, such percentage being based on the total hydrogen content originating from the units of the starting material(s) that have reacted with the compounds of the present application.

[0314] In a further embodiment of the present application, this object is achieved by a process for the manufacture of surfactants, such surfactants comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or being produced with hydrogen, wherein the process comprises the following steps:

[0315] (a0) providing hydrogen gas having a molar fraction of deuterium based on the total hydrogen content of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm, by electrolysis based on electrical power generated at least partially from non-fossil energy sources,

[0316] (a) reacting the hydrogen gas from step (a0) with nitrogen to form ammonia,

[0317] (b) reacting the hydrogen gas from step (a0) with a carbon oxide, preferably carbon dioxide, to form methanol,

[0318] (c) converting the methanol from step (b) to ethylene and (d) further to ethylene oxide, preferably with oxygen,

[0319] (e) converting the ammonia from step (a) to ethanolamine in one or more steps with ethylene oxide from step (d), and

[0320] (f) separating mono-, di- and tri-ethanolamine from the ethanolamine obtained in step (e),

[0321] (g0) converting any product from steps a), b), c), d) and e) to a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or hydrogen, in at least one known process step,

[0322] to obtain a surfactant comprising less deuterium based on the total hydrogen content compared to the same surfactant obtained from chemicals based on fossil sources only.

[0323] The present invention further relates to a method for tracing surfactants back to their origin, especially to an energy source, by using the molar fraction of deuterium in the hydrogen gas and thus in the surfactants of the present invention based on such hydrogen gas, and based on non-fossil resources as well.

[0324] Methods for determining the molar fraction of deuterium in hydrogen gas and downstream compounds based on hydrogen gas are known to the person skilled in the art and are mentioned above and below. A suitable method is described in the example of the present application.

[0325] A further environmental benefit of the environmentally friendly surfactants according to the present application is their use in carbon capture processes, as the surfactants according to the present application are produced using as little fossil-based energy as possible, ideally no fossil-based energy, at least relative to production from hydrogen and carbon (via carbon dioxide or carbon monoxide from non-fossil-based sources) and - optionally - methanol, ammonia, ethanolamine or ethylene or oxirane production via the use of such hydrogen gas from non-fossil-based sources, and do indeed therefore only increase, ideally not increase, CO2 emissions as little as possible.

[0326] Of course, the present application would be even more environmentally friendly if also the other ingredients required for the production of the surfactants such as alcohols, fatty acids etc. would also be produced in an environmentally friendly manner and - more preferably - such ingredients would also be derived from non-fossil-based sources. The present application therefore also encompasses such even more environmentally friendly products, wherein the other ingredients employed for the production of the final surfactants are derived from or made from renewable or even better non-fossil-based sources. Such sources are already known to date for at least some of those other ingredients such as methanol and higher alcohols, fatty acids, fatty alcohols etc.

[0327] A further embodiment of the present application is the use of the surfactants according to the present application in CO2 capture processes as liquid or solid CO2 absorbents.

[0328] A further embodiment of the present application is the use of the surfactants according to the present application in compositions, products or formulations, wherein such compositions, products or formulations are those as currently known for conventionally produced surfactants used in such compositions, products or formulations - apart from the difference in deuterium content - chemically identical surfactants.

[0329] The process for the manufacture of the surfactants of the present application is detailed, which comprises various process steps as described above.

[0330] The molar fraction of deuterium in hydrogen gas and hydrogen gas-based downstream compounds is given in this application in ppm based on the total hydrogen content, which is the mol-ppm content of deuterium based on the total hydrogen content (in hydrogen gas or in the compound in question, respectively).

[0331] The deuterium content of hydrogen gas and hydrogen gas-based downstream compounds is given in this application in atom-ppm based on the total molar hydrogen content (total tritium 1 H and deuterium 2 H atoms. The terms "deuterium content" and "molar fraction of deuterium" are used synonymously throughout the application.

[0332] In physical organic chemistry, the kinetic isotope effect is the change in the rate of a chemical reaction when one of the atoms in a reactant is replaced by one of its isotopes. Formally, it involves the lightest (k) atoms... L ) and weight (k H The rate constant k of a reaction involving isotopic substitution reactants (isotopic configurations). L / k H The ratio of the two isotopes. This change in reaction rate is a quantum mechanical effect, primarily caused by the heavier isotope configuration having a lower vibrational frequency compared to its lighter counterpart. In most cases, this means that the heavier isotope requires a larger energy input to reach the transition state, and therefore has a slower reaction rate.

[0333] The isotopic rate change is most significant when the relative mass change is largest because the effect is related to the vibrational frequencies of the affected bonds. For example, replacing hydrogen atoms (H) with their isotope deuterium (D) represents a 100% increase in mass, while using... 13 C replaces 12 At C, the mass increases by only 8%. Reactions involving CH bonds typically occur 6-10 times faster than those involving corresponding CD bonds, while... 12 C reaction is only greater than the corresponding 13 C reacts 4% faster.

[0334] The first-order kinetic isotope effect can be observed when bonds with isotope atoms form or break. The second-order kinetic isotope effect is observed when bonds with isotope atoms in the reactants remain unbroken or unformed. The second-order kinetic isotope effect is often much smaller than the first-order kinetic isotope effect; however, the second-order deuterium isotope effect can be as large as 1.4 per deuterium atom.

[0335] Methods for manufacturing alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethylimide, alkoxylated polyethylimide and surfactants according to the present invention include providing hydrogen gas having a molar share of deuterium based on a total hydrogen content of less than 90 ppm by electrolysis of electricity generated at least partially from non-fossil energy sources (sometimes described in the specification of the invention as step (a0)).

[0336] Electricity is generated at least in part from non-fossil resources.

[0337] The term "at least partially" means that a portion of the electricity can still be generated from fossil fuels, preferably natural gas, because the combustion of natural gas results in much lower carbon dioxide emissions per megajoule of electricity compared to the combustion of coal. However, the portion of the electricity generated from fossil fuels should be as low as possible, preferably ≤ 50%, preferably ≤ 30%, most preferably ≤ 20%, and further most preferably ≤ 10%. In one embodiment, the electricity is generated solely from non-fossil resources.

[0338] According to local legislation, various methods for the certification and tracking of "energy portfolios" have been established. Certificates such as "non-fossil certificate contracts" are a common practice to track the rate of non-fossil energy used in industrial processes and related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / )

[0339] Preferably, the electricity is at least partially generated from wind, solar (thermal, photovoltaic and concentrated solar), hydroelectric (tidal energy, wave energy, hydroelectric dams, riverine hydrodynamics), geothermal energy, environmental or industrial heat captured by heat pumps, bioenergy (biofuels, biomass), renewable parts of waste energy or nuclear energy (fission).

[0340] In another embodiment, the electricity is at least partially generated from renewable resources, preferably wind, solar (thermal, photovoltaic and concentrated solar), hydroelectric (tidal energy, wave energy, hydroelectric dams, riverine hydrodynamics), geothermal energy, environmental heat captured by heat pumps, bioenergy (biofuels, biomass), or renewable parts of waste.

[0341] The types of electricity resources mentioned above are generally known to the person skilled in the art. Preferred energy resources are mentioned below.

[0342] In the description, with regard to the process for the preparation of alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants, step (a0) is mentioned:

[0343] (a0) providing hydrogen gas having a molar fraction of deuterium based on the total hydrogen content of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm, by electrolysis based on electricity generated at least partially from non-fossil energy.

[0344] At the end of the method claims 12 (process for the preparation of alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines), 13 (process for the preparation of alkoxylated polyethyleneimines) and 14 (process for the preparation of surfactants), the same features are disclosed:

[0345] "wherein the hydrogen in steps (a) and (b) is obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium based on the total hydrogen content of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm."

[0346] The definition regarding the molar share of deuterium generally applies to all embodiments of the process for preparing alkoxylated diamines, oligo- and polyamines or alkoxylated polyethylenimines, alkoxylated polyethylenimines and surfactants. Specific embodiments regarding particular processes are mentioned above and below.

[0347] The definition regarding electrolysis based on electrical power, in particular electrical power generated at least partially from non-fossil energy sources, also generally applies to all embodiments of the process for preparing alkoxylated diamines, oligo- and polyamines or alkoxylated polyethylenimines, alkoxylated polyethylenimines and surfactants. However, the definition also applies to other inventive processes for preparing ethylene or propylene oxides, ethanolamines, polyethylenimines and alkoxylated compounds. Specific embodiments regarding particular processes are mentioned above and below.

[0348] Steps (b), (c) and (d) in the inventive process for preparing ethylene or propylene oxides are generally identical to steps (b), (c) and (d) in the inventive processes for preparing ethanolamines, polyethylenimines, alkoxylated compounds, alkoxylated diamines, oligo- and polyamines, alkoxylated polyethylenimines and surfactants, and the definitions of the process steps (b), (c) and (d) above and below apply to all processes.

[0349] Specific embodiments of steps (b), (c) and (d) in the inventive processes for preparing ethylene or propylene oxides, ethanolamines, polyethylenimines, alkoxylated compounds, alkoxylated diamines, oligo- and polyamines, alkoxylated polyethylenimines and surfactants, as well as specific embodiments of additional steps for preparing ethanolamines, polyethylenimines, alkoxylated compounds, alkoxylated diamines, oligo- and polyamines, alkoxylated polyethylenimines and surfactants are mentioned below.

[0350] Steps (a), (b), (c), (d) and (e) in the process of the present invention for the preparation of ethanolamines are generally identical with steps (a), (b), (c), (d) and (e) in the processes of the present invention for the preparation of polyethyleneimines, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants, and the definitions of the process steps (a), (b), (c), (d) and (e) above and below apply to all processes mentioned in this paragraph.

[0351] The following refers to specific embodiments of steps (a), (b), (c), (d) and (e) in the processes of the present invention for the preparation of polyethyleneimines, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants, and to specific embodiments of additional steps for the preparation of polyethyleneimines, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants.

[0352] Steps (a), (b), (c), (d), (e), (f) and (g) in the processes of the present invention for the preparation of polyethyleneimines are generally identical with steps (a), (b), (c), (d), (e), (f) and (g) in the processes of the present invention for the preparation of alkoxylated polyethyleneimines and surfactants, and the definitions of the process steps (a), (b), (c), (d), (e), (f) and (g) above and below apply to all processes mentioned in this paragraph.

[0353] The following refers to specific embodiments of steps (a), (b), (c), (d), (e), (f) and (g) in the processes of the present invention for the preparation of polyethyleneimines, alkoxylated polyethyleneimines and surfactants, and to specific embodiments of additional steps for the preparation of polyethyleneimines, alkoxylated polyethyleneimines and surfactants.

[0354] Steps (a), (b), (c), (d), (e), (f), (g) and (h) in the processes of the present invention for the preparation of polyethyleneimines are generally identical with steps (a), (b), (c), (d), (e), (f), (g) and (h) in the processes of the present invention for the preparation of alkoxylated polyethyleneimines, and the definitions of the process steps (a), (b), (c), (d), (e), (f), (g) and (h) above and below apply to all processes mentioned in this paragraph.

[0355] The following specific examples refer to steps (a), (b), (c), (d), (e), (f), (g) and (h) of the process of the present invention for the preparation of polyethyleneimine and alkoxylated polyethyleneimine, as well as specific examples for additional steps for the preparation of alkoxylated polyethyleneimine.

[0356] Preferred energy resources

[0357] In a preferred embodiment of the process of the present invention, the energy (electricity) from non-fossil resources used in the process according to the present invention (e.g. electrolysis) can be generated at least partially by nuclear energy. Nuclear energy can be obtained by fission.

[0358] Fission occurs when a neutron enters a larger nucleus, forcing it to become excited and split into two smaller atoms - also known as fission products. Additional neutrons are also released, which can initiate a chain reaction. When each atom splits, a tremendous amount of energy is released. Uranium and plutonium isotopes are most commonly used for fission reactions in nuclear power reactors because they are easy to initiate and control. The energy released by fission in these reactors heats water into steam. The steam is used to spin a turbine to produce carbon-free electricity.

[0359] The electricity from non-fossil resources used in the water electrolysis according to the present invention is preferably generated by wind, solar, biomass, hydro and geothermal energy.

[0360] In a preferred embodiment of the process of the present invention, the energy (electricity) used in the process according to the present invention (e.g. electrolysis) is generated at least partially by wind. Wind can be used to run wind turbines. The power rating of modern utility-scale wind turbines ranges from about 600 kW to 9 MW. The power that can be generated from the wind is a function of the cube of the wind speed, so as the wind speed increases, the power output increases until the maximum output of a particular turbine. Areas where the wind is stronger and more constant, such as offshore and high-altitude sites, are preferred locations for wind farms.

[0361] In a further preferred embodiment of the process of the present invention, the energy (electricity) used in the process according to the present invention (e.g. electrolysis) is generated at least partially by solar energy, particularly preferably by photovoltaic systems. Photovoltaic systems convert light into direct current (DC) electricity by exploiting the photovoltaic effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus large areas of sunlight into a small beam. CSP-Stirling currently has the highest efficiency of all solar technologies to date.

[0362] In a preferred embodiment of the method of the application, the energy (electricity) used in the method according to the application (e.g. in the electrolysis) is at least partially generated by hydroelectric power. Hydroelectric power comes in many forms. Traditionally, hydroelectric power comes from the construction of large hydroelectric dams and reservoirs. Small hydro power systems are hydroelectric power installations that typically produce up to 50 MW of power. They are often used on small streams, or with low-impact development projects on large rivers. Run-of-the-river hydroelectric stations take energy from rivers without creating large reservoirs. Water is typically carried along the sides of valleys (using channels, pipes and / or tunnels) until the water is higher than the valley floor, at which point the water can be allowed to fall through a penstock to drive a turbine.

[0363] Wave energy, which captures wave energy at sea, and tidal energy, which converts tidal energy, are two forms of hydroelectric power that have future potential.

[0364] In a further preferred embodiment of the method of the application, the energy (electricity) used in the method according to the application (e.g. in the electrolysis) is at least partially generated by geothermal energy. Geothermal energy is heat from beneath the Earth's surface. It is contained in rocks and fluids beneath the Earth's crust and can be found as far down as the Earth's fiery molten rock, magma.

[0365] To generate electricity by geothermal energy, wells are dug a mile deep into underground reservoirs to access the steam and hot water there, which can then be used to drive turbines connected to generators. There are three types of geothermal power plants: dry steam, flash, and binary.

[0366] Dry steam is the oldest form of geothermal technology and brings steam from underground to directly drive turbines. Flash plants use high-pressure hot water into cold, low-pressure water, while binary plants pass hot water through a secondary liquid with a lower boiling point, which turns to vapor to drive the turbines.

[0367] In a further preferred embodiment of the method of the application, the energy (electricity) used in the method according to the application (e.g. in the electrolysis) is at least partially generated from biomass. Biomass is biological material derived from living, or recently living organisms. It most often refers to plant or plant-based material, which is specifically termed lignocellulosic biomass. As an energy source, biomass can be used directly via combustion to produce heat (e.g. heat from a fermentation process) or electricity, or indirectly to produce forms of biofuel and gas. The conversion of biomass to biofuels can be achieved by different methods, which are broadly classified as: thermal, chemical and bio-chemical methods. As of 2012, wood is the largest biomass energy source; examples include forest residues (such as dead trees, branches, and stumps), yard trimmings, wood chips, and even municipal solid waste. Industrial biomass can be grown from numerous types of plants, including miscanthus, switchgrass, corn, poplar, willow, sorghum, sugarcane, bamboo, and a variety of tree species ranging from eucalyptus to oil palm (palm oil).

[0368] Plant energy is produced from crops specifically grown for fuel, which provide high biomass yields per hectare with low input energy. Grains can be used for liquid transportation fuels, while stalks can be burned to produce heat or electricity. Biomass can be converted into other useful energy forms, such as methane gas or transportation fuels, such as ethanol and biodiesel. Rotting garbage, as well as agricultural and human waste, all release methane gas - also known as landfill gas or biogas. Crops such as corn and sugarcane can be fermented to produce transportation fuel ethanol. Biodiesel (another transportation fuel) can be produced from leftover food such as vegetable oil and animal fats.

[0369] Bioenergy technologies use processes like those used with fossil fuels to convert renewable biomass fuels into heat or electricity. There are three ways to access the energy stored in biomass to produce bioenergy: burning, bacterial decay, and conversion into gaseous or liquid fuels. Bioenergy can offset the need for carbon-fueled burning in power plants, thereby reducing the carbon intensity of electricity generation. Unlike some forms of intermittent renewable energy, bioenergy can increase the flexibility of electricity generation and enhance the reliability of the electrical grid.

[0370] Preparation (generation) of hydrogen gas:

[0371] Hydrogen can generally be obtained by any method known in the art. Hydrogen can be produced using a variety of different methods. Thermochemical methods use heat and chemical reactions to release hydrogen from organic materials such as fossil fuels and biomass or from materials like water. Water (H2O) can also be split into hydrogen (H2) and oxygen (O2) using electrolysis or solar energy. Microorganisms such as bacteria and algae can produce hydrogen by biological methods. The methods are known in the art (see for example https: / / en.wikipedia.org / wiki / Hydrogen_production and https: / / www.energy.gov / eere / fuelcells / hydrogen-production-processes).

[0372] As of 2020, most hydrogen (about 95%) is produced from fossil fuels by steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

[0373] Preferably, the hydrogen in step (a) and / or (b) is obtained using energy, in particular electricity, generated at least partially from non-fossil resources.

[0374] More preferably, the hydrogen in step (a) and / or (b) in the process of the present application for the preparation of ethylene oxide or propylene oxide, ethanolamines, polyethyleneimines and alkoxylated compounds is obtained at least partially by water splitting, preferably by electrolysis. Most preferably, the water splitting, preferably the electrolysis, uses energy generated at least partially from non-fossil resources.

[0375] The term “at least partially by water splitting” means that a part of the hydrogen can still be produced by other methods, typically by steam reforming of natural gas and / or other light hydrocarbons, partial oxidation of heavier hydrocarbons and coal gasification, preferably by steam reforming of natural gas and / or other light hydrocarbons. However, the part of the hydrogen produced in step (a) and / or (b) by other methods than by water splitting should be as low as possible.

[0376] Preferably, in step (a) and / or (b) of the process of the present application for the preparation of ethylene oxide or propylene oxide, ethanolamines, polyethyleneimines and alkoxylated compounds, < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10% of the hydrogen is produced by other methods than by water splitting. In one embodiment, the hydrogen in step (a) is produced only by water splitting, preferably by electrolysis.

[0377] Preferably, the hydrogen gas in step (a) and / or (b) of the process of the present application for the preparation of ethylene oxide or propylene oxide, ethanolamine, polyethyleneimine and alkoxylated compounds has a total cradle-to-gate product carbon footprint of < 5 kg CO2e / kg hydrogen gas, preferably < 4.6 kg CO2e / kg hydrogen gas, more preferably < 3.5 kg CO2e / kg hydrogen gas, most preferably < 2.5 kg CO2e / kg hydrogen gas, further most preferably < 2 kg CO2e / kg hydrogen gas.

[0378] More preferably, the hydrogen gas in step (a) and / or (b) of the process of the present application for the preparation of alkoxylated diamines, oligo- and polyamines, alkoxylated polyethyleneimines and surfactants is obtained by electrolysis based on electricity generated at least partially from non-fossil energy sources,

[0379] The term “at least partially from non-fossil resources” is explained above.

[0380] Categories of hydrogen gas:

[0381] Hydrogen gas can be defined according to the energy source from which it is produced and is typically categorized using color codes. For example, hydrogen gas produced using renewable energy sources can be referred to as renewable hydrogen gas or green hydrogen gas. Hydrogen gas produced from coal can be referred to as brown hydrogen gas and hydrogen gas produced from natural gas or oil can be referred to as grey hydrogen gas. Brown or grey hydrogen gas production combined with carbon capture and storage / sequestration can be referred to as blue hydrogen gas. Hydrogen gas produced with nuclear energy can be referred to as pink hydrogen gas or clean hydrogen gas.

[0382] The hydrogen gas used in step (a) and / or (b) in the process of the present application which is not obtained by water decomposition, preferably by electrolysis, using energy generated at least partially from non-fossil resources can typically be obtained using any suitable energy by any method known in the art, i.e. the hydrogen gas can have any of the colors mentioned above. In one embodiment, the hydrogen gas which is not obtained by water decomposition, preferably by electrolysis, using energy generated at least partially from non-fossil resources is blue hydrogen gas obtained by steam methane reforming (SMR) with carbon capture and storage (CCS), i.e. a process for the production of hydrogen gas from natural gas with the simultaneous capture and storage of resulting carbon dioxide emissions.

[0383] The hydrogen gas used in steps (a) and / or (b) in the process of the present application, which is obtained by water splitting, preferably by electrolysis but using energy generated from fossil resources, can generally be obtained by using any energy generated from fossil resources known in the art. The preferred fossil resource is natural gas, as the combustion of natural gas leads to much lower carbon dioxide emissions per megajoule of energy produced than, for example, the combustion of coal. However, in the process of the present application, the portion of energy generated from fossil fuels should be as low as possible. Most preferably, where the hydrogen gas in steps (a) and / or (b) is obtained by water splitting, preferably by electrolysis, the energy is generated completely from non-fossil resources.

[0384] Water splitting, preferably electrolysis of water, is an environmentally friendly method for the production of hydrogen gas, as it uses renewable H2O and only produces pure oxygen as a by-product. Water splitting can generally be carried out by known methods, such as electrolysis; photocatalytic water splitting, also known as photoelectrochemical (PEC) water splitting; chemical-assisted electrolysis, for example carbon / hydrocarbon-assisted water electrolysis (CAWE); radiolysis; ultrasound; thermal splitting, especially via solar energy, for example involving the use of a solar concentrator to directly collect solar energy to heat water; pyrolysis of biomass; nuclear-assisted thermal splitting, for example in a high-temperature gas-cooled reactor (HTGR); thermo-chemical cycles that simply combine a heat source (thermo) with a chemical reaction to split water into its hydrogen and oxygen components, for example the sulphur-iodine cycle (S-I cycle); the silicon-iron process; photo-biological water splitting; and mixtures thereof.

[0385] Generally, any water source can be used in water splitting.

[0386] Preferably, the water splitting in the process of the present application for the preparation of ethylene oxide or propylene oxide, ethanolamine, polyethyleneimine and alkoxylated compounds is carried out by electrolysis and / or photocatalytic water splitting, more preferably by electrolysis.

[0387] In photocatalysis (photoelectrochemical (PEC)), hydrogen gas is produced from water using sunlight and one or more photocatalysts (specialized semiconductors, often called photoelectrochemical materials, which use light energy to directly dissociate water molecules into hydrogen and oxygen).

[0388] The photocatalysts (semiconductor materials) used in photocatalytic (PEC) processes are similar to those used in photovoltaic solar power generation, but for photocatalytic (PEC) applications, the photocatalysts (semiconductors) are typically immersed in a water-based electrolyte, where sunlight provides the energy for the water splitting process.

[0389] PEC reactors can be configured, for example, in the form of panels (similar to photovoltaic panels) as electrode systems or slurry-based particulate systems.

[0390] Most preferred water electrolysis typically utilizes direct current (DC) as electrical power at least partially from non-fossil energy sources.

[0391] It is now observed as a key observation of the present application (especially with regard to the alkoxylated diamines, oligo- and polyamines, alkoxylated polyethyleneimines and surfactants of the present invention) that by electrolysis of water, the deuterium atom content of the hydrogen gas is lower than in petrochemically generated hydrogen gas (e.g. as contained in fossil-based syngas), i.e. based on the total hydrogen content < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm. The deuterium atom content in electrolytically produced hydrogen gas can be as low as 10 ppm. The remaining deuterium is mainly present in the form of D-H rather than D2.

[0392] A suitable water electrolysis method is alkaline water electrolysis. The production of hydrogen gas by alkaline water electrolysis is a well-established technology up to commercial scale in the megawatt range. In alkaline water electrolysis, two water molecules of an alkaline solution (KOH / NaOH) are initially reduced at the cathode side to one hydrogen gas molecule (H2) and two hydroxide ions (OH - ). The produced H2 is emitted from the cathode surface in gaseous form and the hydroxide ions (OH - ) migrate through a porous separator to the anode under the influence of the electric field between cathode and anode, where they are discharged to half oxygen molecules (O2) and one molecule of water (H2O). Alkaline electrolysis operates at lower temperatures such as 30°C - 100°C, preferably 30°C - 80°C, with an alkaline aqueous solution (KOH / NaOH) as electrolyte, the concentration of which is about 20% to 30%. The separator in the center of the electrolysis cell separates the cathode and anode and also the produced gases from their corresponding electrode, avoiding mixing of the produced gases. However, alkaline electrolysis has negative aspects such as limited current density (below 400 mA / cm 2 ), low operating pressure and low energy efficiency.

[0393] An overview of the production of hydrogen gas by alkaline water electrolysis powered by renewable energy sources is given in J. Brauns and T. Turek, Processes, 8(2) (2020), p. 248.

[0394] In a further embodiment of the process of the present application, the hydrogen gas is provided by polymer electrolyte membrane water electrolysis. Variants of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).

[0395] PEM water electrolysis technology is similar to PEM fuel cell technology, where a solid polysulfonated membrane (Nafion®, fumapem®) is used as electrolyte (proton conductor). These proton exchange membranes have many advantages, such as low gas permeability, high proton conductivity (0.1 ± 0.02 S cm -1 ), low thickness (20-300 pm), and allow high pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most favorable methods for converting renewable energy into high-purity hydrogen. PEM water electrolysis has great advantages, such as compact design, high current density (higher than 2 A cm -2 ), high efficiency, fast response, operation at low temperatures (20°C-90°C), and production of ultrapure hydrogen. State-of-the-art electrocatalysts for PEM water electrolysis are highly active noble metals, such as Pt / Pd for the hydrogen evolution reaction (HER) at the cathode and Ir02 / Ru02 for the oxygen evolution reaction (OER) at the anode.

[0396] One of the biggest advantages of PEM water electrolysis is its ability to operate at high current densities. This can result in reduced operating costs, especially for systems combined with very dynamic energy sources, such as wind and solar energy, where otherwise sudden surges in energy output would otherwise result in uncaught energy. Polymer electrolytes allow PEM water electrolysis cells to operate with very thin membranes (approximately 100-200 pm), while still allowing high operating pressures, resulting in low ohmic losses primarily caused by the conduction of protons through the membrane (0.1 S / cm), and compressed hydrogen output.

[0397] PEM water electrolysis cells utilize a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while electrically insulating the electrodes. Under standard conditions, the enthalpy required to form water is 285.9 kJ / mol. Part of the required energy to sustain the electrolysis reaction is supplied by thermal energy, and the remainder is supplied by electrical energy.

[0398] The half-reaction that occurs on the anode side of a PEM water electrolysis cell is commonly referred to as the oxygen evolution reaction (OER). Here, a liquid water reactant is supplied to a catalyst, where it is oxidized into oxygen, protons, and electrons.

[0399] The half-reaction that occurs on the cathode side of a PEM water electrolysis cell is commonly referred to as the hydrogen evolution reaction (HER). Here, protons that have moved through the membrane are reduced into gaseous hydrogen.

[0400] PEMs can be made from either pure polymer films or composite films, where other materials are embedded in a polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA (e.g. Nafion®, DuPont product). While Nafion® is an ionomer like Teflon with a perfluorinated backbone, there are many other structural motifs for ionomers used to make proton exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

[0401] An overview on the production of hydrogen by PEM water electrolysis is given in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442-4454.

[0402] An overview on the production of hydrogen by anion exchange membrane water electrolysis is given in H. A. Miller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0403] K. Harada et al., International Journal of Hydrogen Energy 45 (2020), pp. 31389-31395, report a deuteration depletion of 2 to 3 times in polymer electrolyte membrane water electrolysis. With a stoichiometric number λ corresponding to a given water mass flow in the anode between 4 and 9, a separation factor β -2

[0404] β = ([H] / [D]) 气体 / ([H] / [D]) 液体

[0405] is found to be between 2 and 3, where “gas” is the evolved gas and “liquid” is the water before electrolysis. The stoichiometric number λ is defined as follows:

[0406] λ = V x p / (J / 2F x 60 x M H2O )

[0407] where V (mL min -1 ) is the water mass flow in the anode, F is the Faraday constant, J is the electrolysis current (A), p is the density of water (g mL -1 ) and M H2O (g mol -1 ​) is the molar weight of water. A stoichiometric number of 10 means that the amount of fresh water supplied to the anode can be 10 times the amount theoretically consumed by electrolysis at a given electrolysis current.

[0408] H. Sato et al., International Journal of Hydrogen Energy 46 (2021), pages 33 689-33 695, report for anion exchange membrane water electrolysis that the deuterium concentration in the escaping hydrogen gas is diluted by about 1 / 5 relative to the feed water at a = 4.

[0409] Thus, the deuterium in the escaping hydrogen gas can be easily depleted by a factor of 2 to 5 with respect to the feed water in polymer electrolyte membrane water electrolysis. Depending on the electrolysis conditions (water flow, current density), even higher depletion factors are possible. Since the average deuterium content of water is about 150 ppm based on the total hydrogen content, the hydrogen gas provided in step (a) of the inventive process can have a deuterium content of 30 to 75 ppm, or even lower, based on the total hydrogen content.

[0410] AEM water electrolysis technology employs low-cost catalytic materials (as in alkaline electrolysis) and solid polymer electrolyte structures (as in PEM electrolysis technology). AEM electrolysis technology operates in an alkaline environment (pH of about 10) enabling the use of appropriate non-precious metal electrocatalysts (i.e. catalysts not containing platinum group metals = catalysts not containing PGMs) while accommodating zero-gap structures. The membrane used in this type of electrolysis is a polymer membrane containing quaternary ammonium salts. It is relatively inexpensive and has a low interaction with atmospheric CO2.

[0411] Catalysts:

[0412] As an example of a hydrogen evolution reaction (HER) catalyst, a catalyst based on a Ni-Mo alloyed material is suitable.

[0413] As an example of an oxygen evolution reaction (OER) catalyst, highly active transition metal mixed oxides are suitable. Specific examples are CuxCo3_xO4 on a Ni foam support, NiCo2O4:Fe and Ni-Fe alloys, for example catalysts not containing PGMs (Ni-Fe, Ni-Mo, Ni / (CeO2-La2O3) / C and CuxCo3_xO4).

[0414] Membranes and ionomers:

[0415] Due to the development of stable functional groups on the polymer backbone, the chemical stability of AEMs under alkaline conditions has been significantly improved. This allows the use of such membranes in AEM electrolysis at higher temperatures for long periods of time. Suitable membranes and ionomers are known to the person skilled in the art and are described, for example, in the reviews mentioned below. One example is the commercial membrane Tokuyama A201.

[0416] Membrane electrode assembly preparation and cell performance:

[0417] The physical and electrochemical characterization of membrane electrode assemblies prepared by catalyst-coated substrate (CCS) or catalyst-coated membrane (CCM) methods indicates that CCMs are preferred, as the improvement in ionic conductivity far exceeds any improvement in electronic conductivity.

[0418] Liquid electrolyte: Pure water feed generally leads to poor current density, while 1% K2CO3 or dilute KOH solution gives good results. Good electrolysis performance is achieved with 1% K2CO3 electrolyte. It is therefore preferred that the water electrolyte comprises 0.1 to 2 wt% K2CO3 or KOH.

[0419] An overview on the production of hydrogen by anion exchange membrane water electrolysis is given in H. A. Miller et al., Sustainable Energy Fuels [Sustainable Energy Fuels], 2020, 4, pp. 2114-2133.

[0420] In addition to alkaline water electrolysis (AEM and PEM), another commercially available electrolysis technology is solid oxide electrolysis (SOE).

[0421] SOEC (solid oxide electrolysis cell) feeds water into the cathode and the water undergoes a water reduction reaction (WRR) that converts the water into hydrogen gas and oxide ions. This hydrogen gas is then brought to a purification module to separate the hydrogen gas from the remaining water. Then, the oxide ions migrate from the cathode to the anode and they via The oxygen evolution reaction (OER) releases electrons to the external circuit to become oxygen gas. Typically, the operating temperature of SOFCs is 800°C to 1,000°C, as high temperatures are needed to thermally activate the migration of oxide ions and to promote the electrochemical reactions on both electrodes. Thus, the overall efficiency is improved. SOECs are described, for example, in K. Kamlungsua et al., FUEL CELLS 20 [Fuel Cells 20], 2020, Issue 6, 644-649.

[0422] Preferably, the electrolysis for obtaining hydrogen (sometimes defined as step (a0) in the present specification) is water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0423] In a further preferred embodiment, the electrolysis for obtaining hydrogen is solid oxide water electrolysis (SOE).

[0424] It is known in the art that with respect to the feed water in water electrolysis, e.g. polymer electrolyte membrane water electrolysis, the deuterium in the evolved hydrogen can be depleted. The depletion factor depends on the electrolysis conditions (water flow, current density). Since the average deuterium content of water (mole fraction of deuterium) is about 150 ppm based on total hydrogen content, the hydrogen provided in step (a) of the inventive method has a mole fraction of deuterium (deuterium content) of < 100 ppm based on total hydrogen content, preferably in the range of 10 to < 95 ppm, more preferably in the range of 10 to < 90 ppm, most preferably in the range of 10 to < 80 ppm, or even lower.

[0425] Generally, any water source can be used in the preferred water electrolysis in step (a). However, since the hydrogen produced in step (a) has a mole fraction of deuterium (deuterium content) of < 100 ppm based on total hydrogen content, preferably in the range of 10 to < 95 ppm, more preferably in the range of 10 to < 90 ppm, most preferably in the range of 10 to < 80 ppm, it is preferred to use water having a mole fraction of deuterium (deuterium content) of < 160 ppm based on total hydrogen content.

[0426] Vienna Standard Mean Ocean Water (VSMOW) is an isotopic water standard defined in 1968 by the International Atomic Energy Agency. Despite the somewhat misleading phrase "ocean water", VSMOW refers to pure water (H2O) and does not include any salts or other substances normally found in seawater. VSMOW serves as a reference standard for comparing hydrogen and oxygen isotope ratios, primarily in water samples. Very pure, distilled VSMOW water is also used for high-precision measurements of water's physical properties and for establishing laboratory standards, as it is considered to be a representative of "average ocean water", in effect representing the Earth's water content.

[0427] The isotopic composition of VSMOW water is specified as the ratio of the mole abundance of the rare isotope in question to the mole abundance of its most common isotope and is expressed as parts per million (ppm). For example, 16 O (the most common isotope of oxygen with eight protons and eight neutrons) is about 2,632 times more abundant than 17 O (which has one extra neutron).

[0428] The isotope ratio of VSMOW water is defined as follows:

[0429] 2 H / 1 H = 155.76 ± 0.1 ppm (1 part / approximately 6420 parts ratio)

[0430] 3 H / 1 H = 1.85 ± 0.36 x 10 -11 ppm (1 part / approximately 5.41 x 10 16 parts ratio, negligible for physical property related effects)

[0431] 18 O / 16 O = 2005.20 ± 0.43 ppm (1 part / approximately 498.7 parts ratio)

[0432] 17 O / 16 O = 379.9 ± 1.6 ppm (1 part / approximately 2632 parts ratio)

[0433] (see: https: / / en-academic.com / dic.nsf / enwiki / 753132)

[0434] More preferably, the water in step (a) has an average deuterium content of 1 ppm (super-light water) to 156 ppm based on total hydrogen content, most preferably 2 ppm to 150 ppm based on total hydrogen content.

[0435] Methods for depleting deuterium in water are known to the person skilled in the art. However, the methods are usually energy-intensive electrolytic methods, as described for example in CN 103848399 A.

[0436] Therefore, in the case of the use of deuterium-depleted water, it is preferred to use deuterium-depleted water obtained from the following sources:

[0437] - by-products of the production of "heavy water" (D2O) (heavy water has applications in organic chemistry, drug development and nuclear reactors); (deuterium content of about 10-120 ppm)

[0438] - high mountain water; (deuterium content of about 120-150 ppm)

[0439] - surface river and lake water; (deuterium content of about 130-150 ppm)

[0440] - any water source with a seasonal low deuterium content, such as water collected at low temperatures (cold winter water contains less deuterium than warm summer water); for example, water obtained during winter time, for example from snow or ice; (deuterium content of about 120-150 ppm)

[0441] - polar and subpolar waters (deuterium content of about 90-150 ppm)

[0442] - low salinity seawater, such as low salinity seawater close to river mouths, desalinated seawater or brackish water and wastewater treatment effluents; (deuterium content of about 130 - 155 ppm)

[0443] Step (a)

[0444] Step (a) involves reacting hydrogen gas with nitrogen gas to form ammonia. The hydrogen gas is obtained at least partly by water splitting, preferably by electrolysis, using energy generated at least partly from non-fossil resources in the processes of the present application for the preparation of ethylene oxide or propylene oxide, ethanolamines, polyethyleneimines and alkoxylated compounds. Suitable and preferred methods for generating hydrogen gas in step (a) are mentioned above.

[0445] The hydrogen gas is obtained by electrolysis based on electricity generated at least partly from non-fossil energy sources in the processes of the present application for the preparation of alkoxylated diamines, oligo- and polyamines, alkoxylated polyethyleneimines and surfactants.

[0446] The reaction of step (a) preferably follows the Haber-Bosch process.

[0447] The catalysts commonly used in the Haber-Bosch process generally belong to one of two categories: the molten iron catalysts and the supported metal catalysts. The molten iron catalysts are derived from iron oxides, where there are three possibilities: Fe2O3, Fe3O4, and FeO, which are known as hematite, magnetite and wustite, respectively. Industrially, these iron catalysts will be promoted with a number of promoters such as K2O, BaO, KOH, CaO, MgO and AI2O3, which are present in small weight percentages. 1-x

[0448] The supported metal catalysts are catalysts composed of a metal catalyst material (typically ruthenium or cobalt for the ammonia synthesis reaction) present on the surface of a support material (typically activated carbon or a metal oxide). Typically, the weight percentage of the metal catalyst is about 2-10%.

[0449] Other catalysts that can be used are nickel, and nitride catalyst systems or electride, hydride, nitride, hydridoxynitride promoted Ru, Fe, Co and Ni catalysts. ​

[0450] The above-mentioned catalysts can be used both for conventional centralized large-scale Haber-Bosch ammonia synthesis plants and for distributed small-scale ammonia production via the same process.

[0451] In one embodiment of the present application, step (a) is carried out at a pressure in the range of from 50 to 350 bar (absolute), preferably 150 to 300 bar (absolute).

[0452] In one embodiment of the present application, step (a) is carried out at a temperature in the range of from 300 °C to 600 °C, preferably 400 °C to 500 °C.

[0453] The overall kinetic isotope effect is cumulative, as it will also exist in all subsequent production steps downstream of the value chain. By carrying out step (a), ammonia is formed. The deuterium content is even lower than the distributed deuterium content corresponding to that obtained by the classical petrochemical route.

[0454] Step (b)

[0455] Step (b) involves reacting hydrogen gas with a carbon oxide, preferably carbon dioxide, to form methanol. In the process of the present application for preparing ethanolamine, in the process of the present application for preparing polyethyleneimine, in the process of the present application for preparing ethylene oxide or propylene oxide, and in the process of the present application for preparing alkoxylated compounds, the hydrogen gas is at least partially obtained by water splitting, preferably by electrolysis, using energy generated at least partially from non-fossil resources. Suitable and preferred methods for generating hydrogen gas in step (b) are mentioned above.

[0456] In the process of the present application for preparing ethylene oxide or propylene oxide, and in the process of the present application for preparing alkoxylated compounds, step (b) typically comprises reacting hydrogen gas with carbon dioxide to form methanol.

[0457] In the process of the present application for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimine, in the process for preparing alkoxylated polyethyleneimine and in the process for preparing surfactants, step (b) preferably involves reacting hydrogen gas with a molar fraction of deuterium based on the total hydrogen content of < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, obtained by electrolysis based on electricity generated at least partially from non-fossil energy sources (e.g. from step (a0) in the processes described in the specification) with a carbon oxide, preferably carbon dioxide, to form methanol.

[0458] Suitable carbon oxides are carbon monoxide, carbon dioxide or a mixture of both, wherein carbon dioxide is preferred.

[0459] In one embodiment of the process of the present application for the preparation of ethylene oxide or propylene oxide and in one embodiment of the process of the present application for the preparation of an alkoxylated compound, it is mandatory that the carbon dioxide in step (b) is captured or obtained from biological processes, such as from fermentation processes of waste or biomass, at least partially or completely from industrial flue gases or from air or from seawater or other natural waters. By the process of the present application, an alkoxylated compound and ethylene oxide or propylene oxide, respectively, with a low cradle to grave (i.e. including range 3 downstream (for details: see above)) product carbon footprint (PCF) is provided and the alkoxylated compound usually at the same time has a good biodegradability.

[0460] The term "captured or obtained from biological processes, such as from fermentation processes of waste or biomass, at least partially or completely from industrial flue gases or from air or from seawater or other natural waters" means that part of the carbon dioxide can still be obtained from other sources. For example, carbon dioxide is technically obtained by burning of coke with excess air or as a by-product of lime burning and subsequent purification and also natural gas sources (mineral water) are used for exploitation. However, the part of the carbon dioxide obtained from other sources than captured from industrial flue gases or from air or from seawater or other natural waters or from biological processes, such as from fermentation processes of waste or biomass, should be as low as possible, preferably < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10% in the process of the present application. In one most preferred embodiment, the carbon dioxide is obtained only from captured from industrial flue gases or from air or from seawater or other natural waters or from biological processes, such as from fermentation processes of waste or biomass.

[0461] All available capture technologies can be used.

[0462] Further preferred, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required carbon dioxide used in step (a) in the process of the present application is captured from industrial flue gases or from air or from seawater or other natural waters or obtained from biological processes, such as from fermentation processes of waste or biomass.

[0463] By carrying out step (b) of the embodiments of the process according to the present invention for the preparation of ethylene oxide or propylene oxide and of the embodiments of the process of the present invention for the preparation of alkoxylated compounds, wherein it is mandatory that the carbon dioxide in step (b) is captured or obtained from industrial flue gases or from air or from seawater or other natural water or from biological processes, for example from fermentation processes from waste or biomass, methanol (CH3OH) is formed by reacting the carbon dioxide captured or obtained from industrial flue gases or from air or from seawater or other natural water or from biological processes, for example from fermentation processes from waste or biomass, at least partially, with hydrogen.

[0464] Process conditions for hydrogenating carbon monoxide or a mixture of carbon monoxide and carbon dioxide per se are known, for example low-pressure synthesis, medium-pressure synthesis and high-pressure synthesis.

[0465] i) Low-pressure synthesis

[0466] Low-pressure synthesis is usually carried out at a pressure of between 50 and 100 bar. The temperature is usually from 220 °C to 300 °C. As catalyst, a catalyst based on Cu, Zn and AI2O3 is usually used (for example CuO / ZnO / Al2O3). Low-pressure synthesis is the most preferred synthesis for the preparation of methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0467] ii) Medium-pressure synthesis

[0468] Medium-pressure synthesis is usually carried out at a pressure of between 100 and 250 bar. The temperature is usually up to 300 °C. As catalyst, a catalyst based on Zn / Cr2O3 or a Zn-Cu catalyst is usually used.

[0469] iii) High-pressure synthesis High-pressure synthesis is usually carried out at a pressure of between 250 and 350 bar. The temperature is usually from 320 °C to 380 °C. As catalyst, a catalyst based on zinc-chromium oxide is usually used. This process is less preferred for the production of methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0470] The world energy system of the chemical industry is still mainly based on the use of fossil fuels and will continue to do so in the medium and short term, despite the increasing use of renewable energies. The use of fossil fuels in industry and transport produces large amounts of CO2 emissions. Since the object of the present invention is to provide environmentally friendly ethanolamines, polyethyleneimines and ammonia and environmentally friendly ethylene oxide, propylene oxide, alkoxylated compounds, alkoxylated diamines, oligo- and polyamines, alkoxylated polyethyleneimines and surfactants and an environmentally friendly process for their manufacture, methanol is prepared by reacting hydrogen gas with carbon dioxide in step (b) in the process according to the invention

[0471] - in the case of ethanolamines, polyethyleneimines, ammonia, ethylene oxide, propylene oxide, alkoxylated compounds, at least partially by water splitting, preferably by electrolysis, hydrogen gas obtained using at least partially non-fossil energy

[0472] and

[0473] - in the case of alkoxylated diamines, oligo- and polyamines, alkoxylated polyethyleneimines, surfactants, hydrogen gas obtained by electrolysis based on at least partially non-fossil energy generated electricity (e.g. from step (a0) in the process described in the description) has a molar share of deuterium based on the total hydrogen content of ≤ 100 ppm, preferably in the range from 10 to ≤ 95 ppm, more preferably in the range from 10 to ≤ 90 ppm, most preferably in the range from 10 to ≤ 80 ppm.

[0474] In a preferred embodiment, the carbon dioxide provided in step (b) is completely or at least partially captured from industrial flue gases or from air, preferably ambient air, or - in the case of ethanolamines, polyethyleneimines, ammonia, ethylene oxide, propylene oxide, alkoxylated compounds - from seawater or other natural waters. All available capture technologies can be used.

[0475] An overview of commercial CO2 capture technologies is given in Koytsoumoa et al., The Journal of Supercritical Fluids, Volume 132, February 2018, pages 3-16 and Nexant ECA, Carbon Capture and Sequestration (CCS) Technologies, TECH2022S7, Christopher Ho, Caleb Chong, Alexander Zoelle, October 2022. Capturing CO2 from seawater and other natural waters is for example described at https: / / arpa-e.energy.gov / technologies / exploratory-topics / direct-ocean-capture.

[0476] Capturing CO2 at point sources, such as large carbon-based energy facilities, industries with more CO2 emissions (e.g. cement production, ammonia synthesis, steel making), natural gas processing, synthetic fuel plants and fossil fuel-based hydrogen production plants, is most cost-effective. Extracting CO2 from air is possible, although the lower concentration of CO2 in air compared to combustion sources complicates the engineering and thus makes the process more expensive.

[0477] In some preferred embodiments, the carbon dioxide provided in step (b) is captured at least in part or entirely from industrial flue gases.

[0478] The main industrial sources of CO2 are fossil fuel-based power plants, oil refineries, biogas desulfurization (e.g. fermentation) and production of chemicals. Related chemical production processes are for example C1-C4 olefins and C6 aromatics and downstream chemicals such as naphtha cracking to especially ammonia (based on steam-reformed natural gas) and other CO2 intensive products. In addition, industrial paper, food, cement, mineral and iron and steel production can be mentioned as examples.

[0479] In post-combustion capture, CO2 is removed after combustion of fossil fuels, which is the approach to be applied to fossil fuel power plants. CO2 is captured from flue gases at the power plant or other point source. Absorption or scrubbing of carbon with amines is the main capture technology. It is the only carbon capture technology used industrially so far. Suitable post-carbon capture methods are for example absorption (chemical absorption, physical absorption), adsorption (chemical adsorption, physical adsorption), membrane processes, biological processes and cryogenic processes.

[0480] Pre-conversion capture means capturing CO2 produced as an unwanted co-product of an intermediate reaction of a conversion process. Some examples include the production of ammonia and the gasification of coal in power plants. In ammonia production, CO2 co-produced with hydrogen gas during steam reforming must be removed before ammonia synthesis can take place - absorption in mono- and / or di-ethanolamine (MEA and / or DEA) is commonly used for these purposes. Similarly, in integrated gasification combined cycle (IGCC) power plants, CO2 must be separated from hydrogen gas. This is typically achieved using physical solvents such as selexol and rectisol. Note that when applied to power plants, pre-conversion capture is also known as pre-combustion capture.

[0481] Oxy-fuel combustion technology involves the combustion of a carbonaceous fuel in a pure oxygen stream rather than air. Since the oxidant (O2) does not contain other components in air (such as nitrogen), the CO2 concentration in the flue gas will be very high, while the water vapour content can be easily removed.

[0482] CO2 is adsorbed to MOFs (metal-organic frameworks) through physisorption or chemisorption based on the porosity and selectivity of the MOF, leaving a CO2-lean gas stream. CO2 is then stripped from the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA) so that the MOF can be reused.

[0483] In some other preferred embodiments, the carbon dioxide provided in step (b) is captured entirely or at least partially from air, preferably ambient air.

[0484] Direct air capture (DAC) is a process that captures carbon dioxide (CO2) directly from ambient air and produces a concentrated stream of CO2 for sequestration or utilization or production of carbon neutral fuels. Carbon dioxide removal is achieved when ambient air is contacted with a chemical medium, typically an aqueous alkaline solvent or a sorbent. These chemical media are subsequently stripped of CO2 by the application of energy (i.e. heat), resulting in a CO2 stream that can be dehydrated and compressed, while regenerating the chemical medium for reuse.

[0485] The main types of sorbents designed to capture CO2 from ambient air are described in Chen, Lackner et al., Angew. Chem. Int. Ed. 2020, 59, 6984 - 7006, “Sorbents for the Direct Capture of CO2 from Ambient Air”, which are classified by the following adsorption mechanisms: physisorption, chemisorption and hydrosorption.

[0486] In Kommalapati et al., Energy Technol. 2017, 5, 822 - 833, the application of polyethyleneimines in carbon dioxide capture and separation is described.

[0487] Dilute CO2 can be effectively separated using an anion exchange polymeric resin called Marathon MSA, which absorbs CO2 from air when dry and releases it when exposed to moisture. Most of the energy used for this process is supplied by the latent heat of phase transition of water. Other substances that can be used are metal organic frameworks (or MOFs). Membrane separation of CO2 relies on semi-permeable membranes.

[0488] In some other preferred embodiments - in the case of ethanolamines, polyethyleneimines, ammonia, ethylene oxide, propylene oxide, alkoxylated compounds - the carbon dioxide provided in step (b) is captured from seawater and other natural waters completely or at least partially (Direct Ocean Capture (DOC)).

[0489] DOC is one of the main ways of carbon dioxide removal (CDR). DOC technologies with non-biological concepts are, for example, electrochemical ocean capture (EOC), mineralization, ocean alkalinity enhancement (OAE), etc. There is a clear and visible interest in EOC. There are different approaches, such as the use of bipolar membrane electrodialysis (BPMED), three-compartment electrolytic cation exchange module (E-CEM) and electrochemical hydrogen chain (EHL) systems (see Jayarathna, Chameera and Maelum, Michel and Karunarathne, Sumudu and Andrenacci, Sara and Haugen, Hans Aksel, Review on direct ocean capture (DOC) technologies (2022-11-21). Proceedings of the 16th Greenhouse Gas Control Technologies Conference (GHGT-16) 2022-10-23-24, available at SSRN: https: / / ssrn.com / abstract=4282969 or http: / / dx.doi.org / 10.2139 / ssrn.4282969).

[0490] In one embodiment of the present application, the ethanolamine and / or the polyethylene imine according to the present application in a mixture of mono-, di- and triethanolamine or each, preferably in a mixture of monoethanolamine (MEA) and diethanolamine (DEA), is employed in a process for capturing CO2. The ethanolamine of the present application in a mixture of mono-, di- and triethanolamine and polyethylene imine each does not increase the CO2 emissions only as little, in preferred embodiments not at all, and does not therefore contribute to the CO2 emissions itself as little, preferably not at all, i.e. the cradle-to-gate PCF value of the polyethylene imine of the present application and the ethanolamine of the present application (mono-, di- and triethanolamine) is as low as possible, wherein the specific cradle-to-gate PCF value is mentioned above.

[0491] Thus, in a further embodiment, the present application relates to the use of the ethanolamine according to the present application selected from mono-, di-, triethanolamine and mixtures thereof, preferably the ethanolamine in a mixture of monoethanolamine (MEA) and diethanolamine (DEA) or the polyethylene imine as (liquid and / or solid) CO2 absorbent in a CO2 capture process.

[0492] Suitable carbon capture methods are mentioned above and are known in the art.

[0493] In step (b), the carbon oxide, preferably carbon dioxide, and hydrogen are reacted to form methanol.

[0494] Method conditions for the hydrogenation of carbon oxides, preferably carbon dioxide per se are known. Different method approaches for the synthesis of methanol by hydrogenation of CO2 are being developed: (1) heterogeneous catalysis, (2) homogeneous catalysis, (3) electrochemistry, and (4) photocatalysis (see R. Guil-Lopez, Materials 2019, 12, 3902; doi:10.3390 / ma12233902). Preferably, the synthesis of methanol by hydrogenation of carbon dioxide is carried out in the presence of a heterogeneous catalyst.

[0495] Generally, the methanol production is carried out in a synthesis converter, e.g. a fixed bed catalytic reactor.

[0496] The average temperature within the reactor is generally in the range of 150 °C to 300 °C. The average pressure within the reactor is generally in the range of 50 to 150 bar (absolute).

[0497] An overview of suitable heterogeneous catalyst systems is given by Kristian Stangeland, Hailong Li and Zhixin Yu, Energy, Ecology and Environment Vol. 5, pp. 272-285 (2020). This process requires a multi-component catalyst system. The interaction between the components is essential for the high activity and selectivity of the catalyst for the methanol synthesis from CO2. This has been demonstrated by a number of catalyst systems consisting of various metals (i.e. Cu, Pd, Ni) and metal oxides (i.e. AI2O3, ZnO, ZrO2, In2O3). These complex systems can contain a mixture of metallic, alloyed and metal oxide phases. The most promising catalyst systems for large-scale industrial processes are currently Cu-based catalysts and In-based catalysts due to their superior catalytic performance. Suitable catalysts are, for example, copper-zinc-alumina.

[0498] By carrying out step (b), methanol (CH3OH) is formed by reacting a carbon oxide, preferably carbon dioxide, with hydrogen obtained at least partially by water splitting, preferably by electrolysis, using energy generated at least partially from non-fossil resources.

[0499] Furthermore, by carrying out step (b), methanol (CH3OH) is formed by reacting a carbon oxide, preferably carbon dioxide, with hydrogen obtained by electrolysis based on electricity generated from non-fossil energy sources (e.g. from step (a0) in the process described in the specification) having a molar fraction of deuterium of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm, based on the total hydrogen content. The deuterium content is even lower than the deuterium content corresponding to the distribution obtained by the classical petroleum chemical route.

[0500] Steps (c) and (d)

[0501] Step (c)

[0502] In step (c), the methanol from step (b) is converted

[0503] - in the process of the application for the preparation of ethanolamine and in the process of the application for the preparation of polyethyleneimine - into ethylene

[0504] - in the process of the invention for the preparation of ethylene oxide or propylene oxide, in the process of the invention for the preparation of alkoxylated compounds, and in the process of the invention for the preparation of alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines - conversion to ethylene and / or propylene, preferably in the process of the invention for the preparation of alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines - conversion to ethylene.

[0505] Preferably, the ethylene and / or propylene in step (c) is obtained by a methanol-to-olefins process (MTO process).

[0506] The methanol-to-olefins (MTO) process is a process in which olefins, in particular ethylene and propylene, are produced from methanol.

[0507] The MTO process is generally known to the person skilled in the art. Examples of the MTO process are generally described in:

[0508] The process can be divided into three main steps.

[0509] First, methanol is fed to a reactor, preferably a fluidized bed reactor. In the reactor, a catalyst is used to produce a gas that is particularly rich in ethylene and propylene. The percentage yield of ethylene and propylene is determined, inter alia, by the choice of catalyst and the control of the temperature and pressure in the reactor, as is known to the person skilled in the art. For example: to achieve the highest possible yield of ethylene. The reactor is operated at a preferred temperature of between 300 °C and 600 °C and a preferred pressure of between 0.1 and 0.3 MPa. More general temperature and pressure ranges are given below. The gas stream leaving the reactor generally contains light olefins (typically ethylene, propylene, butadiene and butene) as well as carbon monoxide (CO) and carbon dioxide (CO2).

[0510] Second, the gas stream leaving the reactor is cooled, preferably to about 95-115 °C. This is preferably done by quenching. This generally also removes water and dust from the gas stream. Dimethyl ether, which can have formed, and methanol remaining in the gas stream are returned to the reactor.

[0511] Third, the individual gas fractions are fractionated. This is generally similar to the fractionation during production via a route with a steam cracker as is known in the art.

[0512] The MTO process is generally an acid-catalyzed reaction. Preferred catalysts are zeolites, such as zeolites containing silicon dioxide and aluminum oxide (e.g. ZSM-5) and silicon alumina phosphate (SAPO) zeolite-catalysts (SAPO) (e.g. SAPO-34).

[0513] The reaction is usually carried out at a temperature of 300°C to 600°C. The pressure is usually 0.1 to 0.3 MPa.

[0514] The process is preferably carried out in a fluidized catalytic reactor (fluidized bed reactor).

[0515] The molar ratio of propylene to ethylene can be adjusted by selecting appropriate process conditions and can vary from 0.77 in an ethylene production mode and 1.33 in a propylene production mode.

[0516] Examples of commercial MTO technology licensors are UOP LLC (e.g. UOP Advanced MTO Process), Energy Technology Co. Ltd. (DMTO Process) and Sinopec (SMTO Process).

[0517] A more detailed description can be found for example in “Ethylene”, TECH [Technology Trends] 2018-1, July 2018, pages 100-109 by Adam Chan of Nexant.

[0518] Steps (c) and (d) are often referred to as CO2 to olefins via methanol to olefins (CO2MTO). The specific conditions for each step are mentioned above.

[0519] The preferred step (c) in the process of the present application for preparing ethanolamines and in the process of the present application for preparing polyethyleneimines and also preferably in the process of the present application for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines is mentioned below:

[0520] Step (c)

[0521] In step (c), the methanol from step (b) is converted into ethylene.

[0522] Preferably, the ethylene in step (c) is obtained by a methanol to olefins process (MTO process).

[0523] The MTO process is an acid catalyzed reaction. Preferred catalysts are zeolites like zeolites containing silica and alumina (e.g. ZSM-5) and silicon alumina phosphate (SAPO) zeolite catalysts (e.g. SAPO-34).

[0524] The reaction is usually carried out at a temperature of 300°C to 600°C. The pressure is usually 0.1 to 0.3 MPa.

[0525] The process is preferably carried out in a fluidized catalytic reactor.

[0526] The ratio of propylene to ethylene can be adjusted by selecting appropriate process conditions and can vary from 0.77 in an ethylene production mode and 1.33 in a propylene production mode.

[0527] Examples of commercial MTO technology licensors are UOP LLC (e.g. UOP Advanced MTO Process), Energy Technology Co. Ltd. (DMTO Process) and Sinopec (SMTO Process).

[0528] A more detailed description can for example be found in “Ethylene”, TECH [Technology Trends] 2018-1, July 2018, pages 100-109 by Adam Chan of Nexant.

[0529] The preferred steps (b) and (c) are generally referred to as CO2 to olefins via methanol to olefins (CO2MTO). The specific conditions for each step are mentioned above.

[0530] Step (d)

[0531] In step (d), the ethylene and / or propylene from step (c) is reacted with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide.

[0532] Ethylene oxide:

[0533] Generally, ethylene oxide can be prepared by any method known in the art. Preferably, the ethylene oxide in step (d) is obtained by oxidation of ethylene (direct oxidation process).

[0534] The direct oxidation process is preferably carried out in the gas phase (e.g. gas phase with oxygen or air), generally in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0535] The direct oxidation process of ethylene is generally carried out at a temperature from 230 °C to 270 °C. The pressure is preferably in the range of 10 to 30 bar.

[0536] In a preferred embodiment, the direct oxidation process of ethylene in step (d) is carried out by gas phase selective ethylene oxidation, which is typically carried out in a fixed bed tubular reactor with a supported Ag / AI2O3 catalyst at 230 °C - 270 °C and 10 - 30 bar.

[0537] The preferred catalyst for the direct oxidation of ethylene in step (d) is a silver-based catalyst, such as...

[0538] - Preferably, a supported Re / Cs / Ag / Al2O3 catalyst operating with excess C2H4 / O2; or

[0539] -Preferred are alkali metal (Na, Cs) supported Ag / Al2O3 catalysts operated with excess O2 / C2H4.

[0540] It has been found that oxides of Mo and S also promote supported Re / Cs / Ag / Al2O3 systems for ethylene oxide (EO) formation. Therefore, supported Re / Cs / Ag / Al2O3 systems can additionally incorporate oxides of Mo and / or S as promoters.

[0541] Alternatively, C2H4Cl2 can be added to deposit Cl onto the catalyst, which acts as a promoter.

[0542] Examples of the description can be found, for instance, in “Ethylene Oxide” by Mia Monconduit and Karen Jobes of IHS Markit, Chemical Economics Handbook, December 22, 2020, pp. 14–16.

[0543] In the method of the present invention for preparing ethanolamine and in the method of the present invention for preparing polyethylidene, and also preferably in the method of the present invention for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethylidene, preferred step (d) is mentioned below:

[0544] Step (d)

[0545] In step (d), the ethylene from step (c) is reacted with oxygen to form ethylene oxide.

[0546] Preferably, the ethylene oxide in step (d) is obtained by oxidation of ethylene (direct oxidation method).

[0547] The direct oxidation method is preferably carried out in the gas phase (e.g., a gas phase containing oxygen or air) in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0548] Step (d) is typically performed at a temperature ranging from 230°C to 270°C. The pressure is preferably in the range of 10 to 30 bar.

[0549] In a preferred embodiment, step (d) is carried out by gas-phase selective ethylene oxidation, which is typically carried out in a fixed-bed tubular reactor with a supported Ag / Al2O3 catalyst at 230°C–270°C and 10–30 bar.

[0550] The preferred catalyst for the method in step (d) is a silver-based catalyst, such as...

[0551] - Preferably, a supported Re / Cs / Ag / Al2O3 catalyst operating with excess C2H4 / O2; or

[0552] - Preferably, it is a supported Ag / Al2O3 catalyst promoted by an alkali metal (Na, Cs) operating with excess O2 / C2H4.

[0553] It has been found that oxides of Mo and S also promote supported Re / Cs / Ag / Al2O3 systems for EO formation. Therefore, supported Re / Cs / Ag / Al2O3 systems can additionally incorporate oxides of Mo and / or S as promoters.

[0554] Alternatively, C2H4Cl2 can be added to deposit Cl onto the catalyst, which acts as a promoter.

[0555] Examples of the description can be found, for instance, in “Ethylene Oxide” by Mia Monconduit and Karen Jobes of IHS Markit, Chemical Economics Handbook, December 22, 2020, pp. 14–16.

[0556] Surprisingly, in the method according to the invention, a measurable increase in epoxide selectivity was found compared to conventional methods using fossil-based raw materials (correspondingly fewer byproducts such as acetaldehyde and CO2 were formed and the catalyst ran for a longer time), especially in the case of ethylene oxide.

[0557] In particular, for propylene oxide (see below) (HPPO process), a significant improvement in catalyst run-time reliability was found. Higher operational reliability has the advantage of improving planning efficiency in industrial production practices, especially for methods with relatively high catalyst regeneration-recycling frequencies (such as HPPO).

[0558] Propylene oxide:

[0559] Generally, propylene oxide can be prepared by any method known in the art. Suitable methods for preparing propylene oxide are mentioned above. Preferably, the propylene oxide in step (d) is obtained by oxidation of propene with hydrogen peroxide as oxidizing agent, typically in the presence of a catalyst, preferably a zeolite catalyst, more preferably in the presence of a Titansilikalit-1 (TS-1).

[0560] The HPPO process is typically carried out at temperatures below 90 °C and pressures below 35 bar. The process can be carried out in a single reactor or a multi reactor system, for example in a tubular reactor, for example in a fixed bed or a trickle bed.

[0561] The HPPO process as well as other industrially relevant processes are for example described in M. Di Serio et al., Ind. Eng. Chem. Res. 2013, 52, 1168-1178.

[0562] The hydrogen peroxide used as oxidizing agent in the HPPO process, preferably carried out for preparing propylene oxide according to the present application, can be obtained by any known method. Typically, the hydrogen peroxide is obtained by the anthraquinone process (Nexant ECA research publication by Jia Lin and Adam Chan, Propylene Oxide, TECH 2022-3, December 2022).

[0563] The anthraquinone process is based on the catalytic hydrogenation of anthraquinone to anthrahydroquinone with hydrogen gas on a catalyst, for example a palladium catalyst. Subsequently, the anthraquinone is reformed in a re-oxidation with oxygen, for example pure oxygen or atmospheric oxygen, under elimination of hydrogen peroxide.

[0564] Generally, the process steps in the anthraquinone process are run under mild reaction conditions, typically at pressures below 1 MPa (i.e. 10 bar), typically at temperatures below 100 °C, and preferably continuously.

[0565] Since the anthraquinone to anthrahydroquinone shall not flocculate during the process, the solubility can be adjusted via the alkyl substituents and the solvent composition. For this purpose, alkylated derivatives such as 2-ethyl-, 2-tert-butyl- or 2-pentyl anthraquinone are employed. To keep the anthraquinone in solution, typically non-polar substances such as C9- / C10-alkylbenzene mixtures are part of the working solution. Polar substances such as tri-(2-ethylhexyl)-phosphate, diisobutyl carbinol, tetrabutyl urea or urea or methylcyclohexyl acetate take over this task for the hydroquinone.

[0566] The preparation of hydrogen peroxide is described, for example, in Anjali A. Ingle et al., Environmental Science and Pollution Research (2022) 29:86468-86484 (anthraquinone method), Shu Hu et al., ACS Appl. Energy Mater. 2019, 2, 11, 7972-7979 (electrochemical synthesis of hydrogen peroxide from oxygen and water), and Sandrine Romand's NexantECA research publication, Hydrogen Peroxide, TECH 2019-8, September 2019.

[0567] In a preferred embodiment of the present invention, the propylene oxide in step (d) is obtained by oxidizing propylene with hydrogen peroxide as an oxidant, preferably in the HPPO process.

[0568] Preferably, the present invention therefore relates to a method for preparing propylene oxide, comprising the following steps:

[0569] (b) React hydrogen with carbon dioxide to form methanol.

[0570] (c) Convert the methanol from step (a) into propylene.

[0571] (d) React the propylene from step (b) with an oxidizing agent to form propylene oxide.

[0572] In step (b), the carbon dioxide is captured at least in part from industrial flue gas, from the air, or from seawater or other natural water, or obtained from a biological process, such as from fermentation processes of waste or biomass.

[0573] and / or

[0574] In step (b) of the method of the present invention, the hydrogen gas is preferably obtained at least partially by water decomposition, and preferably by electrolysis. The byproduct of water decomposition, and preferably electrolysis, is pure oxygen, which is typically released into the environment without further use.

[0575] as well as

[0576] In step (d), propylene oxide is therefore obtained by oxidizing propylene with hydrogen peroxide as an oxidant, preferably in the HPPO process.

[0577] Hydrogen peroxide is preferably obtained via the anthraquinone process.

[0578] More preferably, the present invention therefore relates to a method for preparing propylene oxide, comprising the following steps:

[0579] (e) React hydrogen with carbon dioxide to form methanol.

[0580] (f) Convert the methanol from step (a) into propylene.

[0581] (g) React the propylene from step (b) with an oxidant to form propylene oxide.

[0582] In step (b), the carbon dioxide is at least partially captured from industrial flue gas, air, seawater, or other natural water, or obtained from biological processes, such as fermentation processes from waste or biomass.

[0583] In step (d), propylene oxide is therefore obtained by oxidizing propylene with hydrogen peroxide as an oxidant, preferably in the HPPO process.

[0584] Hydrogen peroxide is preferably obtained via the anthraquinone process.

[0585] As also mentioned above, the hydrogen in step (b) of the method of the present invention is preferably obtained at least partially by water splitting, and preferably by electrolysis. The byproduct of water splitting, and preferably electrolysis, is pure oxygen, which is typically released into the environment without further use.

[0586] In one embodiment of the invention, the oxygen in step (d) is obtained at least partially by water decomposition, preferably by electrolysis, preferably by using energy generated at least partially from non-fossil resources.

[0587] The oxygen in step (d) mentioned above is the same oxygen that can be used in the preparation of ethylene oxide (preferably by direct oxidation) and in the preparation of the oxidant used in the preparation of propylene oxide. The oxidant is preferably hydrogen peroxide, more preferably hydrogen peroxide prepared by the anthraquinone process.

[0588] The ethylene oxide obtained in step (d) of the method of the present invention preferably has a concentration of < 1.7 kg CO2e / kg ethylene oxide, preferably < 1.6 kg CO2e / kg ethylene oxide, more preferably < 1.5 kg CO2e / kg ethylene oxide, even more preferably < 1.4 kg CO2e / kg ethylene oxide, most preferably < 1.3 kg CO2e / kg ethylene oxide, even more preferably < 1.2 kg CO2e / kg ethylene oxide, even more preferably < 1.1 kg CO2e / kg ethylene oxide, even more preferably < 1.0 kg CO2e / kg ethylene oxide, even more preferably < 0.9 kg CO2e / kg ethylene oxide, even more preferably < 0.8 kg CO2e / kg ethylene oxide, even more preferably < 0.7 kg CO2e / kg ethylene oxide, even more preferably < 0.6 kg The total cradle-to-gate product carbon footprint is <0.5 kg CO2e / kg ethylene oxide, <0.4 kg CO2e / kg ethylene oxide, and <0.3 kg CO2e / kg ethylene oxide.

[0589] Therefore, the present invention further relates to ethylene oxide obtained in the method according to the invention and ethylene oxide having the following total cradle-to-gate product carbon footprint: < 1.7 kg CO2e / kg ethylene oxide, preferably < 1.6 kg CO2e / kg ethylene oxide, more preferably < 1.5 kg CO2e / kg ethylene oxide, even more preferably < 1.4 kg CO2e / kg ethylene oxide, most preferably < 1.3 kg CO2e / kg ethylene oxide, even more preferably < 1.2 kg CO2e / kg ethylene oxide, even more preferably < 1.1 kg CO2e / kg ethylene oxide, even more preferably < 1.0 kg CO2e / kg ethylene oxide, even more preferably < 0.9 kg CO2e / kg ethylene oxide, even more preferably < 0.8 kg CO2e / kg ethylene oxide, even more preferably < 0.7 kg CO2e / kg ethylene oxide, even more preferably < 0.6 kg CO2e / kg ethylene oxide, or even more preferably < 0.5 kg CO2e / kg ethylene oxide, or even more preferably < 0.4 kg CO2e / kg ethylene oxide, or even more preferably < 0.3 kg CO2e / kg ethylene oxide.

[0590] The propylene oxide obtained in step (d) of the method of the present invention preferably has < 3.4 kg CO2e / kg propylene oxide, preferably < 3.3 kg CO2e / kg propylene oxide, more preferably < 3.2 kg CO2e / kg propylene oxide, even more preferably < 3.1 kg CO2e / kg propylene oxide, most preferably < 3.0 kg CO2e / kg propylene oxide, even more preferably < 2.9 kg CO2e / kg propylene oxide, even more preferably < 2.8 kg CO2e / kg propylene oxide, even more preferably < 2.7 kg CO2e / kg propylene oxide, even more preferably < 2.6 kg CO2e / kg propylene oxide, even more preferably < 2.5 kg CO2e / kg propylene oxide, even more preferably < 2.4 kg CO2e / kg propylene oxide, even more preferably < 2.3 kg CO2e / kg propylene oxide total cradle-to-gate product carbon footprint.

[0591] Therefore, the present invention further relates to propylene oxide obtained in the method according to the invention and propylene oxide having the following total cradle-to-gate product carbon footprint: < 3.4 kg CO2e / kg propylene oxide, preferably < 3.3 kg CO2e / kg propylene oxide, more preferably < 3.2 kg CO2e / kg propylene oxide, even more preferably < 3.1 kg CO2e / kg propylene oxide, most preferably < 3.0 kg CO2e / kg propylene oxide, even more preferably < 2.9 kg CO2e / kg propylene oxide, even more preferably < 2.8 kg CO2e / kg propylene oxide, even more preferably < 2.7 kg CO2e / kg propylene oxide, even more preferably < 2.6 kg CO2e / kg propylene oxide, even more preferably < 2.5 kg CO2e / kg propylene oxide, even more preferably < 2.4 kg CO2e / kg propylene oxide, even more preferably < 3 ...5 kg CO2e / kg propylene oxide, even more preferably < 3.3 kg CO2e / kg propylene oxide, even more preferably < 3.2 kg CO2e / kg propylene oxide, even more preferably < 3.1 kg CO2e / kg propylene oxide, even more preferably < 3.0 kg CO2e / kg propylene oxide, even more preferably < 2.9 kg CO2e / kg propylene oxide, even more preferably < 2.8 kg CO2e / kg propylene oxide, even more preferably < 2.7 kg CO2e / kg propylene oxide, even more preferably < 2.6 kg CO2e / kg propylene oxide, even more preferably < 2.5 kg CO2e / kg propylene oxide, even more preferably < 2.4 kg CO2e / kg propylene oxide, even more preferably < 3.5 kg CO2e / kg propylene oxide, even more preferably < 3.5 kg CO2e 2.3 kg CO2e / kg propylene oxide.

[0592] In step (b) (methanol production), one carbon source for the production of ethylene oxide and propylene oxide is captured carbon dioxide. Therefore, the byproduct profile of methanol used in the method for preparing ethylene oxide and propylene oxide according to the invention differs from that obtained by conventional methods (i.e., using syngas, which is often derived from a combination of varying amounts of H2, CO, and CO2 from gasified coal or natural gas). For example, conventionally obtained methanol typically contains more methyl formate, acetone, and higher alcohols (≥ C3) than methanol obtained by the method according to the invention. The byproduct profile of ethylene and propylene produced by cracking fossil-based hydrocarbon feedstocks (such as naphtha or natural gas used in conventionally obtained ethylene oxide and propylene oxide) is even more different from that of ethylene oxide and propylene oxide obtained by CO2-to-olefins (CO2MTO) via the methanol-to-olefins route according to the invention, for example, due to the presence of highly undesirable sulfur components, especially in naphtha.

[0593] Different byproduct profiles of methanol (ethylene and propylene, respectively) are also reflected in downstream products, such as in ethylene oxide and propylene oxide, and in alkoxylated compounds obtained according to the present invention.

[0594] Step (e)

[0595] In step (e), the ammonia from step (a) is converted into an ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof in one or more steps using ethylene oxide from step (d).

[0596] The reaction products obtained in step (e) typically include monoethanolamine, diethanolamine, and triethanolamine.

[0597] The preparation in step (e) is preferably carried out in the presence of water, typically in a closed-loop process requiring only a small amount of fresh water feed. However, ethanolamine can also be prepared by reacting ammonia and ethylene oxide in an anhydrous process. The anhydrous process preferably employs a fixed-bed catalyst, such as an organic ion exchange resin or a thermally more stable acidic inorganic clay or zeolite.

[0598] In the preferred process, the reaction occurs in the aqueous phase, and the reactor pressure is typically high enough to prevent ammonia and ethylene oxide from vaporizing at the reaction temperature.

[0599] The ammonia concentration in the water is preferably between 50% and 100%.

[0600] The reaction pressure in the aqueous phase reaction is typically up to 160 bar, preferably 90 to 130 bar (absolute value).

[0601] The reaction temperature in the aqueous phase reaction is typically up to 150°C, preferably 40°C to 130°C.

[0602] Typically, in aqueous phase reactions, an excess of up to 40 mol of ammonia is used per mole of ethylene oxide.

[0603] Unconsumed ammonia and water are typically separated from the product and recycled in a distillation line downstream of the reactor.

[0604] The product distribution of the three ethanolamines can be controlled by appropriately selecting the ammonia:ethylene oxide ratio.

[0605] Although the above reaction can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, in order to obtain monoethanolamine, post-treatment by distillation is usually required to remove diethanolamine and triethanolamine.

[0606] In the preparation of polyethyleneimine described in steps (f), (g) and (h), monoethanolamine is required, which is usually separated from ethanolamine, which is usually obtained by distillation as a mixture of monoethanolamine, diethanolamine and triethanolamine in steps (a) to (e) of the method according to the invention (see step (f)).

[0607] In the method of the present invention for preparing surfactants, monoethanolamine, diethanolamine and triethanolamine can be separated from ethanolamines, which are typically obtained as a mixture of monoethanolamine, diethanolamine and triethanolamine by distillation in steps (a) to (e) of the method according to the present invention (see step (f)).

[0608] In the method of the present invention for preparing alkoxylated polyethylimide, as described in steps (h) and (i), monoethanolamine is required, which is typically separated from ethanolamine, and these ethanolamines are typically obtained in steps (a) to (e) of the method according to the present invention as a mixture of monoethanolamine, diethanolamine and triethanolamine (see step (f)).

[0609] However, in cases where the ethanolamine according to the invention is used for applications different from the preparation of polyethyleneimine, the separation of monoethanolamine may not be necessary. In carbon capture, for example, a mixture of monoethanolamine and diethanolamine can be used, and only triethanolamine must be separated (usually by distillation).

[0610] Ethanolamine is a family of chemicals that are used as ingredients in personal care products, cleaning products, and industrial applications.

[0611] Further applications of ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof according to the present invention are, for example:

[0612] Personal care products

[0613] Ethanolamines, such as MEA and especially TEA, are used as ingredients in personal care and cosmetic products. In these types of products, ethanolamines help remove dirt and oil from the skin by dissolving grease and blending with other essential ingredients. Because ethanolamines do not impart a strong odor, they are often found in products like hair dyes. Ethanolamines (like MEA) help regulate the pH of a product to prevent it from degrading while stored in its container, thus extending its shelf life.

[0614] Home care and industrial cleaning products

[0615] Ethanolamines, such as MEA, are common ingredients in cleaning products (like floor and tile cleaners) and laundry detergents.

[0616] DEA is a common ingredient in industrial cleaning products such as engine degreasers and industrial-strength detergents due to its ability to break down oils and greases.

[0617] Industrial applications

[0618] MEA acts as a plasticizer to help make plastics flexible and soft. Chemical manufacturing plants use MEA in the production of synthetic ammonia to remove carbon dioxide from ammonia gas.

[0619] As a chemical intermediate, DEA is used in agricultural chemicals to manufacture pesticides, where it helps improve the pesticides' solubility in water. In the production of waxes, polishes, and coating products, DEA acts as an emulsifier to help the ingredients mix and helps prevent the corrosion of other materials.

[0620] MEA and DEA can also be used in industrial applications such as chemical manufacturing and gas processing. In gas processing methods used in oil refineries and natural gas streams, MEA and DEA help remove contaminants from gasoline.

[0621] TEA is used in agricultural chemicals to help disperse pest control agents into crops, which in turn helps repel insects from the crops. As a petroleum demulsifier, TEA helps separate oil from water and other substances. In cement additives, TEA helps promote the curing and / or hardening of cement. It is also a corrosion inhibitor in steel and zinc materials used in construction and building.

[0622] Examples of the description can be found, for instance, in “Ethanolamines” by Mia Monconduit and Tison Keel of IHS Markit, Chemical Economics Handbook, February 14, 2020, pp. 19-20.

[0623] Step (e0): Preparation of the alkoxylated compounds of the present invention

[0624] In the preparation of the alkoxylated compounds of the present invention, step (e0) is usually performed after step (d) mentioned above.

[0625] In step (e0), in one or more steps, the ethylene oxide and / or propylene oxide obtained in step (d), and optionally at least one alkyl oxide different from ethylene oxide and propylene oxide, are reacted with at least one starting unit having a Zelevitinov active hydrogen atom to form an alkoxylated compound.

[0626] The alkoxylated compound prepared in the method of the present invention comprises

[0627] i) 20 wt% to < 100 wt%, preferably 30 wt% to < 99.3 wt% of ethylene oxide units and / or propylene oxide units,

[0628] ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of at least one epoxide unit different from ethylene oxide and propylene oxide units.

[0629] iii) > 0 wt% to 80 wt%, preferably 0.2 wt% to 70 wt% of at least one starting unit having a Zelevitinov active hydrogen atom,

[0630] The sum of the units mentioned under i), ii) and iii) is 100 wt%.

[0631] i) Ethylene oxide units and / or propylene oxide units:

[0632] The alkoxylated compounds according to the present invention comprise ethylene oxide (EO), propylene oxide (PO), or both.

[0633] EO and PO can be present in various weight ratios. Typically, alkoxylated compounds have EO:PO weight ratios ranging from 100:0 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.

[0634] ii) At least one alkylene oxide unit that is different from the ethylene oxide unit and the propylene oxide unit:

[0635] The alkoxylated compounds according to the present invention may contain at least one alkylene oxide unit different from the ethylene oxide unit and the propylene oxide unit.

[0636] Examples of epoxide units other than ethylene oxide and propylene oxide units are based on 1,2-epoxide butane, 2,3-epoxide butane, styrene oxide, 1,3-epoxide propane or tetrahydrofuran, preferably 1,2-epoxide butane or 2,3-epoxide butane, more preferably 1,2-epoxide butane (BuO).

[0637] Preferably, there are no alkyl oxide units different from ethylene oxide units and propylene oxide units, that is, the alkoxylated compound prepared in the method of the present invention contains 0 wt-% of alkyl oxide units different from ethylene oxide units and propylene oxide units.

[0638] The epoxide unit can be in the form of only one type of epoxide unit (i.e., only ethylene oxide unit or only propylene oxide unit), for example, in the case of epoxide units polymerized in the form of homopolymers, or in the form of two or more different epoxide units (e.g., ethylene oxide units and propylene oxide units in the ratios mentioned above, or ethylene oxide units and / or propylene oxide units and 1,2-butyryloxy units). For example, in the case of epoxide units polymerized in the form of random copolymers or block copolymers.

[0639] In some embodiments, the polymer is EO-terminated. In other embodiments, the polymer is PO-terminated. This termination can be referred to as a small block, such as a small block of EO acting as the terminator. If the polymer is terminated, it can be referred to in the art as a block copolymer. In some embodiments, the polymer is a block PAG. Such a block PAG can comprise blocks of all EO or PO, blocks of random EO / PO monomers having at least two blocks with different EO / PO ratios, or a combination of all EO or PO blocks and random EO / PO blocks.

[0640] Preferred ethylene oxide units and / or propylene oxide units according to the present invention are characterized by the following formula:

[0641] ia) (Ia)

[0642] ib) (Ib)

[0643] ic) (Ic),

[0644] in

[0645] n, m, n' and m' are each independently 1 to 500, preferably 1 to 100, more preferably 2 to 50;

[0646] and groups

[0647] and In formula (Ic), they are in the form of two or more, preferably two or three blocks, and / or arranged randomly.

[0648] The total molecular weight of the ethylene oxide units is in the range of 88 to 22,000 Da, preferably 88 to 4,400 Da, and more preferably 88 to 2,200 Da, and the total molecular weight of the propylene oxide units is in the range of 116 to 29,000 Da, preferably 116 to 5,800 Da, and more preferably 116 to 2,900 Da. The average molecular weight of the ethylene oxide units and / or propylene oxide units can be calculated based on their monomer structure.

[0649] iii) At least one starting unit having a Zelevitinov active hydrogen atom

[0650] Zelevitinov active hydrogen is reactive, as determined by the Zelevitinov method as described in Analyst 1963, 88, 782-790. The quantitative determination of active hydrogen in a chemical substance by adding methyl magnesium iodide in pentyl ether to the substrate solution and quantitatively measuring the volume of escaping gaseous methane is commonly referred to as the Zelevitinov determination.

[0651] Preferably, the starting unit having a Zelevithinov active hydrogen atom is selected from the group consisting of: water, at least one of: monofunctional alcohols, difunctional alcohols or polyfunctional alcohols, monofunctional amines, difunctional amines or polyfunctional amines, and monofunctional, difunctional or polyfunctional thio compounds. More preferably, the starting unit is water, a monofunctional alcohol, a difunctional alcohol or polyfunctional alcohol and / or a monofunctional amine, a difunctional amine or polyfunctional amine.

[0652] The starting unit preferably contains 1 to 100, more preferably 2 to 50, most preferably 2 or 8, and even more preferably 2 or 3 Zelevitinov active hydrogen atoms.

[0653] When polyalkylene imide is used as the starting unit, the preferred polyalkylene imide starting unit has an amine value of 3 to 30 mmol / g, preferably 5 to 25 mmol / g, and more preferably 10 to 22 mmol / g.

[0654] The amine value refers to the proportion of amines present in an element. The amine value is determined according to DIN 53176 (version 2000-12).

[0655] Examples of suitable monofunctional, difunctional, or polyfunctional alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetrahydric alcohols, or higher alcohols, which may also be referred to in the art as polyhydric alcohols. In some embodiments, the alcohol is a monohydric alcohol. Examples of suitable monohydric alcohols include C1- to C1-C ... 20 Alcohols, such as n-butanol, isobutanol, 2-ethylhexanol, 2-propylheptanol, butanediol, butyl diethylene glycol, butyl triethylene glycol, butyl propylene glycol, butyl dipropylene glycol, butyl tripropylene glycol, methyl diethylene glycol, methyl triethylene glycol, methyl dipropylene glycol, methanol, ethanol, hexanol, isononol, decanol, 2-butyloctanol, oleyl alcohol, octadecanol (C 18 Alcohols (e.g., stearyl alcohol), isononadecanol, C 12 alcohols, C 13 alcohols, C 14 alcohols, C 15 alcohols, C 16 alcohols, C 17 Alcohols, 2-ethylhexanol, 2-propylheptanol, 2-butyloctanol, 2-pentylnonol, 2-hexyldecanol, and alcohols such as C 13 -C 15 alcohols, C 12 -C 18 alcohols, C 16 -C 18 alcohol, or C 12 -C 14 A mixture of alcohols. In other embodiments, the alcohol is a diol. Examples of suitable diols include ethylene glycol, 1,2-propanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. In yet another embodiment, the alcohol is a polyol. Examples of suitable polyols include glycerol, trimethylolpropane, and pentaerythritol.

[0656] Various types of amines can be used to form alkoxylated compounds. Examples of suitable amines include monoamines, diamines, triamines, or higher amines, which may also be referred to in the art as polyamines. Specific examples of suitable amines include alkanolamines, ethylenediamines, diethylenetriamines, and polyethyleneimines.

[0657] In the context of this invention, the term "polyethylimide" refers not only to polyethylimide homopolymers but also to polyalkylimides containing NH-CH2-CH2-NH structural units and other alkylene diamine structural units such as NH-CH2-CH2-CH2-NH, NH-CH2-CH(CH3)-NH, NH-(CH2)4-NH, NH-(CH2)6-NH, or (NH-(CH2)8-NH structural units, but with the NH-CH2-CH2-NH structural units being the majority in molar fraction. Preferred polyethylimides contain the majority of NH-CH2-CH2-NH structural units in molar fraction, for example, 60 mol-% or more, more preferably at least 70 mol-% relative to all alkylene imide structural units. In specific embodiments, polyethylimide refers to those polyalkylene imides that have one or zero alkylene imide structural units per molecule that are different from NH-CH2-CH2-NH.

[0658] In the context of this invention, "polyethyleneimine" can be linear or branched. The degree of branching can be determined by a person skilled in the art using 13C NMR based on the specific application.

[0659] Polyalkylimides (including polyethylimides) can be characterized by their degree of branching (DB). For a definition of branching degree, refer to H. Frey et al., Acata Polym. [Acta Polymerica Sinica] 1997, 48, 30. The branching degree DB is defined therein as...

[0660] DB (%) = (T+Z) / (T+Z+L) x 100, where

[0661] T is the average number of terminally bound monomer units (primary amino groups).

[0662] Z is the average number of branched monomer units (tertiary amines).

[0663] L is the average number of linearly linked monomer units (secondary amines). T, Z, and L can be determined in D2O by 13C-NMR.

[0664] The degree of branching (DB) of the polyalkylene imine, especially the polyethylene imine, according to the invention is preferably in the range of 55% to 95%, more preferably in the range of 57% to 90%, and even more preferably in the range of 60% to 80%.

[0665] The polyalkylene imide, preferably polyethylene imide, used in the reaction mixture may preferably have a weight-average molecular weight (MW) of 300 to 20,000, for example 300 to 15,000, suitably 300 to 10,000, more suitably 300 to 5,000, preferably 500 to 1,500, and more preferably 500 to 1,000 g / mol. The weight-average molecular weight (Mw) can be determined by gel permeation chromatography (GPC), wherein hexafluoroisopropanol and 0.05 w% ammonium acetate are used as eluents and a narrowly distributed polyethylene glycol standard is used as the stationary phase.

[0666] preparation:

[0667] There are no specific requirements for the method used to obtain the alkoxylated compounds of the present invention, and the preparation of the alkoxylated compounds of the present invention is generally known to those skilled in the art.

[0668] Alkoxylation can generally be carried out in three ways: (i) anionic (base-initiated) polymerization, (ii) acid-initiated polymerization, and (iii) through coordination polymerization.

[0669] Anionic polymerization of epoxides represents a "classic" technique for synthesizing corresponding polymers / compounds comprising ethylene oxide and / or propylene oxide units. Anionic polymerization is typically carried out by catalytic addition of ethylene oxide and / or propylene oxide, and optionally at least one alkyl oxide other than ethylene oxide and propylene oxide, to at least one starting unit having a Zelevitinov active hydrogen atom.

[0670] As catalysts, highly nucleophilic metal compounds, preferably alkali metals (especially sodium, potassium, or cesium) compounds, can be used. Examples are alkali metal hydroxides, alkali metal salts, alkali metal hydrides, or alkali metal amides. In practice, potassium hydroxide is of the greatest significance (see, for example, US 6156720 A).

[0671] Other suitable classes of catalysts are polymetallic cyanide compounds, preferably bimetallic cyanide compounds, and especially zinc hexacyanometalates. These catalysts are also often referred to as DMC catalysts. Polyether alcohols prepared using polymetallic cyanide compounds are characterized by very low contents of unsaturated components. Another advantage of using polymetallic cyanide compounds as catalysts is the significantly increased space-time yield upon the addition of alkyl epoxides. Alkoxylation in the presence of DMC catalysts is described, for example, in DD 203 735, DD 203 734, WO 97 / 29146, WO 98 / 03571, WO 00 / 14143, WO 99 / 44739 and US 2008 / 0161509 A1.

[0672] Solvents used for the anionic polymerization of epoxides are typically polar and aprotic; therefore, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO), and hexamethylphosphoramide (HMPA) are commonly used. Furthermore, polymerization in bulk monomers is possible and is the preferred method.

[0673] Alkoxides containing sodium, potassium, or cesium counterions in THF or other polar aprotic solvents represent commonly used initiator systems.

[0674] Adding complexing agents (such as crown ethers suitable for the corresponding cations) can strongly accelerate the anionic polymerization of epoxides.

[0675] The temperature during alkoxylation is typically between 80°C and 200°C, preferably between 90°C and 180°C.

[0676] The alkoxylated compounds of the present invention can be prepared by batch, semi-batch, or continuous methods.

[0677] In semi-intermittent alkoxylation, for example, a catalyst and at least one starting material are initially loaded, and an epoxide (ethylene oxide or propylene oxide) is added simultaneously during the reaction process. This particular synthetic strategy is due to the high reactivity of the alkoxide and the high heat involved in the alkoxylation reaction.

[0678] The polymerization rate of EO is significantly faster than that of PO, which plays an important role in the commonly used anionic copolymerization of EO and PO. Generally, the reactivity of alkyl oxides decreases with increasing length and size of the alkyl substituent at the epoxide moiety.

[0679] The alkoxylated polyethylimide of the present invention can be obtained by alkoxylation of polyethylimide using methods known in the art. The alkoxylation of polyethylimide using ethylene oxide, propylene oxide, and butane is described, for example, in Houben-Weyl, Methoden der organischen Chemie, 4th edition, Vol. 14 / 2, p. 440 and subsequent pages (1963) and Vol. E 20, p. 1367 and subsequent pages (1987). The alkoxylated polyethylimide of the present invention can be obtained, for example, as described in US 5445765 and DE-A 2227546.

[0680] In cases where at least one starting unit is a monofunctional, difunctional, or polyfunctional alcohol, the resulting alcohol alkoxide component (alkoxylated alcohol) can be converted to an alkyl ether sulfate by sulfation with sulfuric acid or a sulfuric acid derivative in a manner known per se to give an acid alkyl ether sulfate (see, for example, US 2008 / 0207939 A1). Sulfation reactions of alcohols have been described, for example, in US 3,462,525, US 3,420,875, and US 3,524,864. Details regarding the conduct of this reaction are given in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A25 (1994), pp. 779-783, and in the references given therein.

[0681] If sulfuric acid itself is used for esterification, it is convenient to typically use an acid with a concentration of 75% to 100% by weight, preferably 85% to 98% by weight (referred to as "concentrated sulfuric acid" or "monohydrate"). If it is desirable to control the reaction, such as through thermal development, the esterification can be performed in a solvent or diluent.

[0682] Typically, the alcohol reactant is introduced first, and the sulfating agent is added gradually with continuous mixing. If complete esterification of the alcohol alkoxide component is desired, the sulfating agent and the alcohol alkoxide component are usually used in a molar ratio of 1:1 to 1:1.5, preferably from 1:1 to 1:1.2. If a mixture of alcohol alkoxides is used, a smaller amount of sulfating agent may be advantageous. Esterification is typically carried out at temperatures ranging from 25°C to 85°C, preferably from 45°C to 75°C. If appropriate, it may be advantageous to carry out esterification at its boiling point in a low-boiling, water-immiscible solvent and diluent, where the water formed during esterification is azeotropically distilled off.

[0683] Instead of the sulfuric acid of the above concentration, for the sulfation of the alcohol alkoxide components of the present invention, sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (“fuming sulfuric acid”), chlorosulfonic acid, thioyl chloride, or other aminosulfonic acids can also be used. The reaction conditions must then be appropriately modified as known to those skilled in the art.

[0684] If sulfur trioxide is used as the sulfation reagent, the reaction can also advantageously be carried out in a falling film reactor in countercurrent or cocurrent flow, and, if appropriate, continuously. After esterification, these batches are neutralized by adding alkali, and, if appropriate, post-processed after removing excess alkali metal sulfates and any solvents present.

[0685] If chlorosulfonic acid is used as the sulfation reagent, the corresponding alcohol alkoxide component is loaded into a stirred apparatus under inert conditions. The appropriate amount of chlorosulfonic acid is added dropwise under vigorous stirring. The molar ratio between the alcohol component and chlorosulfonic acid is generally from 0.5:1 to 1:0.5, preferably from 0.75:1 to 1:0.75. Very particularly preferably, the molar ratio of the alcohol alkoxide component to chlorosulfonic acid is 1:1. After removing HCl gas, the reaction batch is adjusted to a slightly alkaline pH using a sodium hydroxide solution.

[0686] The alkoxylated compound obtained in step (e0) is characterized by a lower cradle-to-grave product carbon footprint compared to the same alkoxylated compound obtained by conventional methods (i.e., without CO2 to olefins (CO2MTO) via the methanol-to-olefins route, without carbon capture, etc.) (see explanation above). Therefore, the present invention addresses the aforementioned challenges and provides an alkoxylated compound with a low cradle-to-grave (i.e., including downstream products in scope 3 (see explanation above)) carbon footprint and good overall biodegradability.

[0687] Despite the various industrially relevant PCF values ​​(total cradle to grave) of alkoxylated compounds The carbon footprint of a product varies considerably, but due to different starting chemical compositions, the content of starting materials, ethylene oxide, propylene oxide, butane oxide, and higher epoxides, as well as different alkoxylation method conditions, the inventors of this invention have unexpectedly discovered that a single mathematical formula for scenarios i), ii), and iii) described in the Examples section allows for the description of all the different alkoxylated compounds covered by this invention.

[0688] This new mathematical formula enables those skilled in the art to predict the cradle-to-grave outcomes of specific alkoxylated compounds prepared through specific scenarios i), ii), or iii). PCF. Through this mathematical formula, the total cradle-to-grave ratio of alkoxylated compounds... Comparison of product carbon footprint (PCF) is possible.

[0689] In this application, “material carbon” in polymer products is considered the only additional CO2 emission at the end of the product lifecycle, the “grave” emission; all other emissions during the product’s use by customers and consumers (such as emissions related to transportation and use) are outside the scope.

[0690] These three scenarios i), ii), or iii) are as follows:

[0691] i) Conventional fossil fuels: Ethylene oxide and / or propylene oxide are not prepared via steps b) and c), but are directly used in step d) using fossil-based ethylene and / or propylene, for example, obtained through naphtha cracking. Additionally, steps d) and e) are based on fossil fuels (comparative example).

[0692] ii) According to the invention: the carbon dioxide used in step b) is; additionally, the hydrogen in step (b) is obtained by electrolysis based on electricity generated from non-fossil resources, and steps c) and d) are based on CO2MTO (CO2 to olefins via the methanol-to-olefins route); the hydrogen from SMR in the case of CCS (carbon capture and storage) is used only to prepare the oxidant (hydrogen peroxide) required for the preparation of propylene oxide via HPPO in step d).

[0693] iii) According to the best case of the invention: all steps b) to d) and the production of hydrogen and oxygen are mainly based on non-fossil energy.

[0694] The mathematical formulas for scenarios i), ii), or iii) are as follows:

[0695] Scenario i): 8.88 C - 0.253 E + 1.33 P - 0.940

[0696] Scene ii): 6.90 C - 0.560 E + 0.464 P - 0.495

[0697] Scene iii): 5.21 C - 0.276 E - 0.436 P - 0.259

[0698] in

[0699] C = Carbon content [mass ratio] in alkoxylated compounds

[0700] E = EO- content [mass ratio] in alkoxylated compounds

[0701] P = the total content [mass ratio] of PO and higher epoxides in alkoxylated compounds.

[0702] Here, each mass ratio ranges from 0 … 1 (equal to 0 … 100 wt%).

[0703] Furthermore, the total mass balance must be settled, which means C+E+P = 1 (100%).

[0704] Therefore, the present invention relates to alkoxylated compounds having a typical < 8.88 C - 0.253 E + 1.33 P -0.940, preferably < 8.38 C - 0.330 E + 1.12 P - 0.829, more preferably < 7.89 C - 0.406 E +0.898 P - 0.718, optimal value < 7.40 C - 0.483 E + 0.681 P - 0.606, further optimally < 6.90 C - 0.560 E + 0.464 P - 0.495, further optimal value < 6.48 C - 0.489 E + 0.239 P - 0.436, further optimal value < 6.06 C - 0.418 E - 0.014 P - 0.377, further optimal value < 5.64 C - 0.347 E - 0.211 P - 0.318, or even more preferably < 5.21 C - 0.276 E - 0.436 P - Total cradle-to-grave carbon footprint (see explanation above) of products. C, E, and P are as defined above.

[0705] In a preferred embodiment of the invention, the weight fraction of the alkyl oxide unit, which is different from the ethylene oxide unit and the propylene oxide unit, is 0 wt%. In this case, P = PO- content [mass ratio] in the alkoxylated compound.

[0706] The present invention further relates to alkoxylated compounds obtainable by the method of the present invention. Preferably, the alkoxylated compounds have a typical pH < 8.88. C - 0.253 E + 1.33 P - 0.940, preferably < 8.38 C -0.330 E + 1.12 P - 0.829, more preferably < 7.89 C - 0.406 E + 0.898 P - 0.718, optimal value < 7.40 C - 0.483 E + 0.681 P - 0.606, further optimally < 6.90 C - 0.560 E +0.464 P - 0.495, further optimal value < 6.48 C - 0.489 E + 0.239 P - 0.436, further optimal value < 6.06 C - 0.418 E - 0.014 P - 0.377, further optimal value < 5.64 C - 0.347 E- 0.211 P - 0.318, or even more preferably < 5.21 C - 0.276 E - 0.436 P - Cradle-to-grave carbon footprint (see explanation above) of products. C, E, and P are as defined above.

[0707] As discussed above, the different byproduct profiles of methanol, ethylene, and propylene, as well as ethylene oxide and propylene oxide, are also reflected in the downstream products, namely the alkoxylated compounds obtained according to the present invention.

[0708] The inventors of this application have unexpectedly discovered that, compared with conventionally prepared ethylene oxide and / or propylene oxide, the use of ethylene oxide and / or propylene oxide according to the invention generates lower levels of polymeric byproducts during the alkoxylation process.

[0709] In the preparation of polyurethane (from polyether polyols), it is desirable to reduce these polymeric byproducts because very high molecular weight byproduct fractions are known to be effective surfactants that cause polyurethane foam collapse or have negative effects on other applications (e.g., causing turbidity or precipitation in blends).

[0710] Preferably, the alkoxylated compounds according to the present invention meet the biodegradability requirements set forth in OECD 301B (as mentioned above).

[0711] Both the alkoxylated compounds and methods of the present invention achieve low cradle-to-grave (see explanation above) product carbon footprint and generally good biodegradability.

[0712] The alkoxylated compounds of the present invention comprise

[0713] i) 20 wt% to < 100 wt%, preferably 30 wt% to 99.3 wt% of ethylene oxide units and / or propylene oxide units,

[0714] ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of at least one epoxide unit different from ethylene oxide and propylene oxide units.

[0715] iii) > 0 wt% to 80 wt% and 0.2 wt% to 70 wt% of at least one starting unit having a Zelevitinov active hydrogen atom.

[0716] The sum of the units mentioned under i), ii) and iii) is 100 wt%

[0717] The ethylene oxide unit and / or propylene oxide unit, alkyl oxide units different from ethylene oxide and propylene oxide units, and starting unit units having Zelevitinov active hydrogen atoms are defined above.

[0718] In one embodiment, the alkoxylated compound of the present invention comprises an EO:PO weight ratio ranging from 100:1 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.

[0719] Ethylene oxide units and / or propylene oxide units, alkyl oxide units other than ethylene oxide units and propylene oxide units, and starting units having Zelevithinov active hydrogen atoms are defined above.

[0720] The alkoxylated compounds of the present invention typically have a number average molecular weight of 100 to 50,000 Da, preferably 200 to 30,000 Da, and more preferably 300 to 20,000 Da, as determined by GPC in THF using PEG standards.

[0721] The alkoxylated compounds of this invention have a wide range of applications in various industries. Some of these applications are:

[0722] - Lubricants: Alkoxylated compounds can be used as lubricants in various industries such as automotive, aerospace, and industrial machinery. They offer excellent lubrication properties, high thermal stability, and oxidation resistance.

[0723] - Personal care products: Alkoxylated compounds can be used in the formulation of personal care products such as lotions, creams, and shampoos. They provide skin and hair with properties such as moisturizing and conditioning.

[0724] - Household care products: Alkoxylated products can be used as surfactants in laundry detergents, hard surface cleaners, and rinsing aids. They provide excellent wetting, cleaning, and emulsifying properties.

[0725] - Pharmaceutical Industry: Alkoxylated compounds can be used as excipients in the pharmaceutical industry to improve drug solubility, stability, and bioavailability. They are also used in formulations of ointments, creams, and gels.

[0726] - Textile Industry: Alkoxylated compounds can be used as softeners and antistatic agents in the textile industry. They can improve the texture and feel of fabrics and reduce static electricity.

[0727] -Food Industry: Alkoxylated compounds can be used as emulsifiers, thickeners, and stabilizers in the food industry. They can be used in the production of ice cream, dairy products, and baked goods.

[0728] - Oil and Gas Industry: Alkoxylated compounds can be used as hydraulic fluids, oil shut-off agents, and heat transfer fluids in the oil and gas industry. They offer, for example, excellent lubrication properties and high thermal stability.

[0729] -Agricultural / Agrochemicals: Alkoxylated compounds can be used as adjuvants in the agricultural industry, for example, to improve the effectiveness of herbicides and pest control agents.

[0730] - Chemical Industry: Alkoxylated compounds can be used as reaction media, surfactants, and dispersants in the chemical industry. They can be used in the production of polymers, resins, and coatings.

[0731] - Building materials: Alkoxylated compounds can be used in the construction industry as additives in cement, concrete and mortar to improve, for example, their workability, strength and durability.

[0732] - Polyurethane production: Alkoxylated compounds can be used as starting materials for the production of products such as polyurethane foams, adhesives, and coatings. They can act as chain extenders and crosslinking agents in the polymerization process.

[0733] - Metalworking fluids: Alkoxylated compounds can be used as coolants and lubricants in metalworking processes such as cutting, grinding, and drilling. They offer, for example, excellent thermal stability, low volatility, and high lubricity.

[0734] - Electronics: Alkoxylated compounds can be used as heat transfer fluids in electronic cooling systems. They offer advantages such as high thermal conductivity, low viscosity, and compatibility with a wide range of materials.

[0735] - Fuels and Energy: Alkoxylated compounds can be used as additives in fuels and lubricants (such as fuel performance packs) to improve their performance and reduce emissions. They can also be used as heat transfer fluids in solar and geothermal energy systems.

[0736] - Water treatment: Alkoxylated compounds can be used as flocculants and coagulants in water treatment processes. They can help remove suspended particles and impurities from water.

[0737] - Adhesives and sealants: Alkoxylated compounds can be used as adhesives and thickeners in the formulation of adhesives and sealants. They can provide improved adhesion, flexibility, and moisture resistance.

[0738] Therefore, the present invention further relates to the use of the alkoxylated compounds of the present invention in any of the applications mentioned above.

[0739] Therefore, preferably, the present invention further relates to the application of alkoxylated compounds according to the invention or obtained by the method according to the invention in home care products, cosmetic products, pharmaceutical products, the food industry, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agrochemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages, and poly(urethane) applications. Uses of [the product], including home care products, cosmetic products, pharmaceutical products, products in the food industry, building materials, lubricants such as engine oil, bearing oil, gear oil, compressor oil, grease, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agrochemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages, and poly(urethane) applications.

[0740] Step (f):

[0741] Step (f) involves separating the monoethanolamine from the ethanolamine obtained in step (e).

[0742] Although reaction step (e) can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, separation is usually required to remove diethanolamine and triethanolamine in order to obtain monoethanolamine. This post-treatment is generally known in the art and is typically carried out by distillation, preferably under reduced pressure, such as vacuum distillation.

[0743] Examples of methods for producing monoethanolamine can be found, for instance, in “Ethanolamines and Propanolamines” by Martin Ernst, Johann-Peter Melder, Franz Ingo Berger, and Christian Koch, Ullmann’s Encyclopedia of Industrial Chemistry, 2022, pp. 4–6.

[0744] Step (g):

[0745] In step (g), the monoethanolamine from step (f) is preferably converted into ethylimine (aziridine) by catalytic gas-phase synthesis.

[0746] One object of the present invention is to provide an environmentally friendly polyethyleneimine. The inventors have unexpectedly discovered that greenhouse gas (GHG) emissions generated by the conversion of monoethanolamine to ethyleneimine via catalytic gas-phase synthesis are significantly lower than those generated by the conversion of monoethanolamine to ethyleneimine via other methods.

[0747] Therefore, the PCF of ethyleneimine obtained by catalytic gas-phase synthesis and thus polyethyleneimine is significantly lower than that of ethyleneimine and polyethyleneimine obtained by other methods (where only step (g) differs in the methods for preparing ethyleneimine and polyethyleneimine).

[0748] The inventors of this invention have further and unexpectedly discovered that by using monoethanolamine from step (f), i.e., based on hydrogen obtained at least partially by water splitting, preferably by electrolysis, using energy generated at least partially from non-fossil resources, the catalyst lifespan in step (g) of the method of the invention is improved.

[0749] Suitable methods for preparing ethyleneimine from monoethanolamine are generally known in the art.

[0750] Suitable catalytic gas-phase methods for preparing ethyleneimine from monoethanolamine are generally known in the art. For suitable examples of catalyst compositions, see, for example, US 4,841,061, and for the corresponding ethyleneimine gas-phase method conditions, see US 4,966,980.

[0751] In this method, ethyleneimine is prepared by dehydrating monoethanolamine at a temperature typically between 350°C and 450°C, typically under reduced pressure of 30 to 500 mbar (absolute value).

[0752] This method is typically carried out in the presence of catalysts with weakly basic and acidic sites, such as Si-Cs-P or Si-Rb-P based catalysts. An overview of the production technique and optimal catalyst composition with high yields (e.g., up to 80 mol%), selectivity, and activity can be found in: Applied Catalysis A: General 221 (2001) 209-217; Acid-base catalysis: On the example of ethylenimine production; Hideaki Tsuneki; Nippon Shokubai Co. Ltd., Functions and Materials Research Laboratory, Suita Electric Co., Ltd. 564-8512, Japan. This method is prone to catalyst deactivation through coking and sintering, and despite short contact times, due to the loss of active components at high processing temperatures. To improve catalyst lifetime, catalyst regeneration cycles with, for example, trimethyl phosphate treatment can be employed, as described in: Applied Catalysis A: General 331 (2007) 95-99; Deactivation and regeneration of ethylenimine production catalyst; Hideaki Tsuneki, Kimio Ariyoshi; Nippon Shokubai Co. Ltd., Functions and Materials Research Laboratory, Suita Electric Co., Ltd. 564-8512, Japan. Other examples of suitable catalyst preparation methods include the regeneration methods described in WO 2015090084 and CN 104475144.

[0753] Catalytic gas-phase dehydration methods are typically carried out in the gas phase in a tube reactor, preferably a fixed-bed tube reactor. Alternatively, fluidized-bed reactors used for the dehydration of monoethanolamine can be used for more efficient catalytic contact and heat transfer.

[0754] The resulting product mixture is typically separated by quenching followed by multi-stage distillation to give high-purity ethyleneimine, while unreacted monoethanolamine is fed back into the reactor.

[0755] Another preferred commercial method is via liquid-phase dehydration as originally described in the Wenker method, as described in H. Wenker, J. Am. Chem. Soc. [Journal of the American Chemical Society] 57 (1935) 2328. This technique is typically a two-step process that usually involves reacting monoethanolamine with sulfuric acid to produce 2-aminoethyl hydrogen sulfate as an intermediate. Dehydration is usually achieved under pressure and elevated temperature by the subsequent addition of sodium hydroxide, as described in H. Kindler, W. Sanne, R. Sinn, A. Wittwer, Chem. Ing. Tech. [Chemical Engineering Technology] 37 (1965) 400 and DE 1302658, 1971 (R. Sinn, W. Sanne, H. Kindler; BASF Aktiengesellschaft)).

[0756] The liquid-phase ethyleneimine method can typically be carried out in batch or continuous mode, usually at a very high yield of 85-90 mol%, yielding high-purity ethyleneimine after distillation, which has the excellent properties required for, for example, high molecular weight polyethyleneimine and other derivatives.

[0757] Step (h)

[0758] In step (h), the ethyleneimine from step (g) is polymerized into polyethyleneimine.

[0759] Suitable methods for preparing polyethyleneimine by polymerizing ethyleneimine (aziridine) are known to those skilled in the art.

[0760] Polyethylene imide is preferably prepared by cationic ring-opening polymerization of ethylene imide in the presence of Brønsted acid, Lewis acid, haloalkanes, or carbon dioxide. Examples are given in US 2,182,306, US 3,203,910, and US 2001 / 0039318.

[0761] As another example of the synthesis of polyethyleneimine, it is referred to as “Aziridines and azetidines: building blocks for polyamines by anionic and cationic ring-opening polymerization”, Gleede, T.; Reisman, L.; Rieger, E.; Mbarushimana, PC; Rupar, PA; Wurm, FR; Polymer Chemistry, 2019, 10, 3257.

[0762] The polymerization can be carried out, for example, in a batch process in which water and 1,2-dichloroethane, as catalysts, are placed in a reaction vessel, the mixture is heated to a temperature of 70°C to 100°C, and ethyleneimine is continuously added under stirring of the reaction mixture.

[0763] The obtained polyethylene imine is usually a branched or hyperbranched polyethylene imine.

[0764] The obtained polyethylene imine preferably has a weight-average molecular weight M in the range of 500 to 2,000,000 g / mol, more preferably in the range of 500 to 100,000 g / mol. w .

[0765] The degree of branching of polyethylene imide is preferably in the range of 0.45 to 0.75, more preferably 0.5 to 0.7, and most preferably 0.55 to 0.7. 13 Determined by C10 NMR spectroscopy in D2O. Branching degree calculated as ( D + T ) / ( D + T + L In this formula, D It refers to dendritic (or tertiary) amine groups. L (Linear chain) refers to secondary amine group, and L (Straight-chain) refers to the primary amine group.

[0766] The inventors have unexpectedly discovered that, compared to conventionally prepared polyethylidene imide, the proportion of secondary amines increases in the polyethylidene imide obtained by the method of the present invention at the expense of the proportion of primary amines. The stated ratio of primary, secondary, and tertiary amines in the polyethylidene imide of the present invention is beneficial to the stability of the polyethylidene imide during carbon capture.

[0767] The present invention provides environmentally friendly ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine, ethyleneimine, ethylene oxide and ammonia, and an environmentally friendly method for preparing them, wherein the method uses as little fossil energy as possible.

[0768] In another embodiment of the invention, the polyethylene imine of the invention is characterized by a low molar fraction of deuterium, which is based on a total hydrogen content of ≤ 110 ppm, preferably in the range of 10 to ≤ 105 ppm, more preferably in the range of 10 to ≤ 95 ppm, and most preferably in the range of 10 to ≤ 92 ppm.

[0769] The present invention further relates to polyethyleneimine, wherein the molar fraction of deuterium is based on a total hydrogen content of ≤ 110 ppm, preferably in the range of 10 to ≤ 105 ppm, more preferably in the range of 10 to ≤ 95 ppm, and most preferably in the range of 10 to ≤ 92 ppm.

[0770] The polyethylidene is preferably prepared by a method including at least step (a) according to the invention. More preferably, the polyethylidene is prepared by a method according to the invention including steps (a) to (h).

[0771] The polyethyleneimines according to the invention are characterized by a low molar deuterium content. They exhibit a different deuterium content than polymers produced petrochemically and ethanolamines produced by petrochemical methods (i.e., based on fossil fuels).

[0772] Another key feature of the present invention, selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and polyethyleneimine, is a low molar deuterium content. This low molar deuterium content is primarily introduced by the hydrogen gas used in the method according to the invention. Therefore, ammonia prepared by reacting said hydrogen gas with nitrogen gas is also characterized by a low molar deuterium content.

[0773] Steps (e1) and (i) – alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide

[0774] Step (i) and step (e1)

[0775] In this step, the polyethylene imine is further reacted in a known alkoxylation reaction with at least ethylene oxide and / or propylene oxide, preferably at least ethylene oxide, obtained from step (d) to obtain ethoxylated and / or propoxylated, preferably ethoxylated polyethylene imine. Such compounds are well known and are available by the present invention as compounds from non-fossil-based sources.

[0776] Steps (i) and (e1) are of the same type; in step (i), PEI is alkoxylated, while in step (e2), a diamine, oligoamine, polyamine, or PEI is alkoxylated. These methods are otherwise identical.

[0777] When other alkyl esters are used for the alkoxylation reaction, other typical alkoxylated polyethylimides are obtained; typical alkyl esters known for this purpose are butane epoxides (especially n-butane epoxide, nBuO) and higher alkyl esters. nBuO is the most commonly used. Such products are known, for example, Sokalan® PG617 from BASF, which is a polyethylimide typically alkoxylated with about 7 EO and 5 PO in a block structure of PEI-10EO-7PO, and Sokalan® HP20, also from BASF, which is a polyethylimide typically alkoxylated with about 20 EO-units / NH ethoxylated, wherein the polyethylimide has a reported molecular weight of about 600 or 800 g / mol, depending on the source.

[0778] Therefore, by means of the present invention, those Sokalan® products—Sokalan® PG617 and Sokalan® HP20 and all similar products that use polyethylene imine and use EO for alkoxylation—can be obtained in a known manner, as well as optional additional ingredients such as the mentioned lactones and other epoxides besides EO, but such products have a fossil-based share with a much lower molar weight based on these products.

[0779] Further disclosures of such alkoxylated PEI products (particularly in the detergent field) can be found, for example, in EP 2 014 753 A1 and EP 2 925 848 B1; in addition, alkoxylated PEI and alkoxylated diamines / oligoamines / polyamines – sometimes containing additional alkylene oxides and / or lactones (typically contained within the alkoxylation reaction or as separate “polylactone-block” or inserting a single lactone or no more than two or possibly three lactones into an alkylene oxide chain, wherein such alkylene oxide chain is derived solely from EO or from EO and other epoxides, wherein such multiple alkylene oxides are in any form, such as random, block arrangement, depending on the process steps) – can also be found in WO 2021 / 165468 A, WO2021 / 165493, WO 2022 / 136408 A, WO 2022 / 136409 A, WO WO 2023 / 021104 A, WO 2023 / 021105A, WO 2023 / 021103 A, WO 2023 / 021101 A, WO 2022 / 136389 A and WO 2023 / 117494 A, EP3665209 and WO 2023017794 are just a few examples. When the invention is applied to those disclosures, it can also be used to prepare all of those compounds disclosed therein. Further disclosures using PEI or then at least EO-alkoxylated diamines / oligoamines / polyamines are available under this invention. Therefore, by employing EO and / or PEI prepared according to the invention and otherwise following the methods and disclosures of those prior art documents, the invention covers all of those compounds and methods disclosed in the disclosures expressly mentioned in this paragraph.

[0780] This invention provides environmentally friendly alkoxylated diamines, oligoamines and polyamines, as well as alkoxylated polyethylimide, and an environmentally friendly method for preparing them, wherein the method uses as little fossil energy as possible.

[0781] It has been found that the environmentally friendly compounds, namely alkoxylated diamines, oligoamines and polyamines, as well as alkoxylated polyethylimide, are characterized by particularly low molar deuterium content.

[0782] As mentioned above, it is important to be able to reliably track the source of hydrogen and downstream compounds obtained through clean energy.

[0783] Today, most hydrogen is produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

[0784] However, to date, it has been impossible to distinguish hydrogen obtained through steam reforming, partial oxidation, and coal gasification (i.e., from fossil resources) from hydrogen obtained through electrolysis. As discussed above, hydrogen obtained through electrolysis is preferably obtained using non-fossil energy sources. It is anticipated that the electrification (power generation) of fossil resources will be completely replaced by power generation from non-fossil resources in the near future.

[0785] Therefore, the inventors have discovered a method for tracing the source of hydrogen and its downstream products (preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide) via the deuterium molar fraction of the compound. These downstream products of hydrogen (obtained by electrolysis) and hydrogen itself can be distinguished by their deuterium molar fraction from, in principle, chemically identical compounds prepared by fossil fuel-based methods (i.e., by petrochemical methods).

[0786] Furthermore, by using carbon oxides (such as carbon monoxide and preferably carbon dioxide) along with hydrogen instead of petrochemical synthesis gases in subsequent synthetic routes of alkoxylated diamines, oligoamines and polyamines, as well as alkoxylated polyethylimide, it was found that these compounds have a uniquely low molar fraction of deuterium and excellent traceability.

[0787] Therefore, the present invention relates to the use of the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds for tracing the source, particularly the energy source, of hydrogen and hydrogen-based downstream compounds, wherein these compounds are preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide.

[0788] The present invention further relates to a method for tracking the source, particularly the energy source, of hydrogen and said hydrogen-based downstream compounds by determining the molar fraction of deuterium in hydrogen and said hydrogen-based downstream compounds, wherein these compounds are preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide.

[0789] Hydrogen-based downstream products are typically products prepared using hydrogen, preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimides. The preparation of downstream products, as well as other hydrogen-based downstream products, is known in the art.

[0790] Within the meaning of this invention, tracking and tracing are synonymous.

[0791] In the context of this invention, the source refers to the method of hydrogen production employed, particularly electrolysis and / or the energy source, i.e., non-fossil energy. As mentioned above, it is anticipated that the electrification (power generation) of fossil fuel sources will be completely replaced by power generation from non-fossil resources in the near future. Hydrogen produced by electrolysis in this case is non-fossil hydrogen. Examples of non-fossil power sources have been mentioned above.

[0792] The method of the present invention for tracing the source, especially the energy source, of hydrogen and the aforementioned downstream compounds can be used as a single tracing method or in combination with other tracing methods.

[0793] Suitable molar fractions of deuterium are mentioned in this application for: hydrogen-based compounds obtained by electrolysis of hydrogen, especially by the method of the present invention, particularly alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide, as well as hydrogen itself.

[0794] When produced using the present invention by substituting at least one element with elements of the present invention (e.g., replacing standard fossil-based PEI, EO, and / or PO, amines, etc. with PEI and / or EO and / or PO and / or amines that are producible or preferably produced by the methods of the present invention), the compounds of the present invention obtainable by the present invention cover any and all such alkoxylated diamines, oligomeric amines and polyamines, and alkoxylated polyethylimides; such compounds are well known, namely alkoxylated diamines, oligomeric amines and polyamines, and alkoxylated polyethylimides obtainable by the present invention, and especially those as detailed above herein, and more specifically those disclosed in the following prior art disclosures, such as those very preferably disclosed by their structure and / or their production methods as disclosed below: EP 2 014 753 A1, EP 2 925848 B1, WO 2021 / 165468 A, WO 2021 / 165493, WO 2022 / 136408 A, WO 2022 / 136409 A, WO2023 / 021104 A, WO 2023 / 021105 A, WO 2023 / 021103 A, WO 2023 / 021101 A, WO 2022 / 136389 A and WO 2023 / 117494 A, EP 3665209 and WO 2023017794, and specifically also commercially known products of BASF named Sokalan® PG617, Sokalan® HP20 and Sokalan HP 96 (which are ethoxylated hexamethylenediamine).

[0795] Typically, such products are sometimes also referred to as "multifunctional polyethyleneimines" (e.g., BASF's Sokalan® HP20 and Sokalan PG617, which are preferred structures of the compounds of the present invention) and "multifunctional diamines" (e.g., BASF's Sokalan® HP96, which is a preferred structure of the compounds of the present invention). These multifunctional polyethyleneimines—which are the compounds of the present invention according to the present invention—are typically ethoxylated polyethyleneimines having a weight-average molecular weight Mw in the range of 3,000 to 250,000, preferably 5,000 to 200,000, more preferably 8,000 to 100,000, more preferably 8,000 to 50,000, more preferably 10,000 to 30,000, and most preferably 10,000 to 20,000 g / mol. Suitable multifunctional polyethyleneimines have 80 wt.% to 99 wt.%, preferably 85 wt.% to 99 wt.%, more preferably 90 wt.% to 98 wt.%, and most preferably 93 wt.% to 97 wt.% or 94 wt.% to 96 wt.% of ethylene oxide side chains based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. A suitable polyethyleneimine core molecule is a polyethyleneimine with a weight-average molecular weight Mw in the range of 500 to 5000 g / mol. Preferably, a molecular weight of 500 to 1000 g / mol is used, and even more preferably, a Mw of 600 to 800 g / mol is used. The ethoxylated polymer then has an average of 5 to 50, preferably 10 to 35, and even more preferably 20 to 35 ethylene oxide (EO) units / NH-functional groups. The present invention also covers such polyfunctional diamines, typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamines, which may be further quaternized and / or optionally sulfated. Typical polyfunctional diamines have a weight-average molecular weight (Mw) in the range of 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g / mol. In preferred embodiments of the invention, quaternized and sulfated ethoxylated hexamethylene diamines are preferred compounds, which contain an average of 10 to 50, preferably 15 to 40, and even more preferably 20 to 30 ethylene oxide (EO) groups / NH-functional groups, and preferably have two cationic ammonium groups and two anionic sulfate groups.

[0796] When the present invention is used to produce by replacing at least one element of the prior art method / starting material with an element of the present invention (e.g., replacing standard fossil-based PEI, EO and / or PO, amines, etc. with PEI and / or EO and / or PO and / or amines that can be produced by the method of the present invention or preferably produced by the method of the present invention), the present invention covers all the compounds mentioned above.

[0797] The uses of such compounds of the present invention as disclosed and defined in the preceding paragraphs and the products / formulations / compositions containing them are the same as those known in the art; such uses and products / formulations / compositions containing such compounds of the present invention are especially those disclosed in any of the following disclosures:

[0798] EP 2 014 753 A1, EP 2 925 848 B1, WO 2021 / 165468 A, WO 2021 / 165493, WO2022 / 136408 A, WO 2022 / 136409 A, WO 2023 / 021104 A, WO 2023 / 021105 A, WO 2023 / 021103 A, WO 2023 / 021101 A, WO 2022 / 136389 A and WO 2023 / 117494 A, EP 3665209 and WO2023017794, and also include uses and products / preparations / compositions known in the prior art, comprising Sokalan® PG617, Sokalan® HP20 and Sokalan® HP 96. In all those disclosures, prior art compounds may be partially or completely replaced by compounds of the present invention that have the same or closely similar chemical structures but are produced using at least one element of the present invention (e.g., replacing standard fossil-based PEI, EO and / or PO and / or amines with PEI and / or EO and / or PO and / or amines produced as can be produced by the method of the present invention or preferably produced by the method of the present invention).

[0799] Step (g0) - Surfactant

[0800] In step (g0), any product from steps a), b), c), d), and / or e) is converted in at least one known method step into a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or hydrogen, to obtain a surfactant comprising deuterium with a lower total hydrogen content compared to a surfactant obtained solely from a chemically identical surfactant based on a fossil source.

[0801] As mentioned above, it is important that the source of hydrogen obtained through clean energy and thus downstream compounds (such as the surfactants of this invention) can be traced in a reliable manner.

[0802] Today, most hydrogen is produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

[0803] However, to date, it has been impossible to distinguish hydrogen obtained through steam reforming, partial oxidation, and coal gasification (i.e., from fossil resources) from hydrogen obtained through electrolysis. As discussed above, hydrogen obtained through electrolysis is preferably obtained using non-fossil energy sources. It is anticipated that the electrification (power generation) of fossil resources will be completely replaced by power generation from non-fossil resources in the near future.

[0804] Therefore, the inventors have discovered a method for tracing the source of hydrogen and its downstream products, preferably the surfactants of the present invention, via the deuterium molar fraction of the said compound. These downstream products of hydrogen (i.e., the surfactants as detailed herein) (of which hydrogen is obtained through electrolysis) and hydrogen itself can be distinguished by their deuterium molar fraction from, in principle, chemically identical compounds prepared by fossil fuel-based methods (i.e., by petrochemical methods).

[0805] Furthermore, by using carbon oxides (such as carbon monoxide and preferably carbon dioxide) along with hydrogen instead of petrochemical synthesis gas in subsequent synthetic routes of surfactants, it was found that these compounds have a uniquely low molar fraction of deuterium and excellent traceability.

[0806] Therefore, the present invention relates to the use of the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds for tracing the source, particularly the energy source, of hydrogen and hydrogen-based downstream compounds, wherein these compounds are preferably surfactants as detailed herein.

[0807] The present invention further relates to a method for tracking the source, particularly the energy source, of hydrogen and said hydrogen-based downstream compounds by determining the molar fraction of deuterium in hydrogen and said downstream compounds, wherein these compounds are surfactants as detailed herein.

[0808] Within the meaning of this invention, "tracking" and "following" are synonymous.

[0809] In the context of this invention, the source refers to the method of hydrogen production employed, particularly electrolysis and / or the energy source, i.e., non-fossil energy. As mentioned above, it is anticipated that the electrification (power generation) of fossil fuel sources will be completely replaced by power generation from non-fossil resources in the near future. Hydrogen produced by electrolysis in this case is non-fossil hydrogen. Examples of non-fossil power sources have been mentioned above.

[0810] The method of the present invention for tracing the source, especially the energy source, of hydrogen and the aforementioned downstream compounds can be used as a single tracing method or in combination with other tracing methods.

[0811] The compounds of the present invention available through this invention cover any and all such surfactants that follow the outline given herein, especially those as detailed in more particular.

[0812] Such surfactants are known from the prior art to date, and some of them are commercially available.

[0813] When using the present invention for production, i.e., by replacing at least one element of the prior art method / starting material with an element of the present invention (e.g., replacing standard fossil-based ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, triethanolamine, or hydrogen, as can be produced by the method of the present invention or preferably produced by the method of the present invention), all those surfactants that can be derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen are covered by the present invention.

[0814] Such surfactants are structurally known. Many of them are listed in the following sections; those that are specifically listed and known to be produced by using at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen are particularly covered by this invention.

[0815] Since the methods for producing such surfactants are well known and well documented and are therefore generally known to those skilled in the art, it would be inappropriate to mention any and all of them and to refer to or refer to the various methods of their production.

[0816] Furthermore, the method of the present invention can be used to produce any of the surfactants listed in the following sections, provided that, for such synthetic route, at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen is used in the method for producing such surfactant.

[0817] Surfactants obtainable through this invention

[0818] The surfactant that can be produced by this invention is, in principle, any one of the following: ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen is used in the method for producing the surfactant for this synthetic route.

[0819] Specifically, such surfactants are disclosed in any of the following disclosures: US 2019 / 390142, WO2020 / 264077, WO 2020 / 005476, WO 2023017061 A1, WO 03 / 042262, Publications 800542 and 800500, WO 99 / 05242, US Patents 5,576,282, 6,306,812 B1, and 6,326,348 B1.

[0820] Surfactants include nonionic, anionic, and amphoteric surfactants, which are defined in more detail below:

[0821] Nonionic cleaning surfactants

[0822] Nonionic surfactants (NIS) are surfactants that contain neither positively nor negatively charged functional groups. Unlike anionic and cationic surfactants, nonionic surfactants do not ionize in solution.

[0823] NIS1

[0824] In one embodiment, the nonionic surfactant is selected from compounds of general formulas (NIS1a) and (NIS1b):

[0825]

[0826]

[0827] The variables in general formulas (NIS1a) and (NIS1b) are defined as follows:

[0828] R1 is selected from C1-C23 alkyl and C2-C23 alkenyl groups, wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched; examples are n-C7H15, n-C8H17, n-C9H19, n-C11H23, n-C13H27, n-C15H31, n-C17H35, i-C9H19, i-C12H25.

[0829] R2 is selected from H, C1-C20 alkyl and C2-C20 alkenyl, wherein the alkyl and / or alkenyl are straight-chain (straight-chain; n-) or branched.

[0830] R3 and R4 are each independently selected from C1-C16 alkyl groups, wherein the alkyl group is straight-chain (straight-chain; n-) or branched; examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, isodecyl.

[0831] R5 is selected from H and C1-C18 alkyl groups, wherein the alkyl group is straight-chain (straight-chain; n-) or branched. The integer definitions of general formulas (NIS1a) and (NIS1b) are as follows:

[0832] m is in the range of 0 to 200, preferably 1 to 80, more preferably 3 to 20; n and o are each independently in the range of 0 to 100; n is preferably in the range of 1 to 10, more preferably 1 to 6; o is preferably in the range of 1 to 50, more preferably 4 to 25. The sum of m, n and o is at least one, preferably in the range of 5 to 100, more preferably in the range of 9 to 50.

[0833] Nonionic surfactants of general formulas (NIS1a) and (NIS1b) can have any structure, whether block or random, and are not limited to the sequences of formulas (NIS1a) and (NIS1b) shown.

[0834] Compounds according to formula (NIS1a) may be referred to herein as alkyl polyethylene glycol ethers (AEO). Compounds according to formula (NIS1b) may be referred to herein as alkylphenol polyethylene glycol ethers (APEO).

[0835] In one embodiment, the compound has the general formula (NIS1a), wherein R1 is n-C13H27, R2 and R5 are H, m is 3-20, and n and o are 0.

[0836] In one embodiment, the compound has the general formula (NIS1a), wherein R1 is a straight-chain or branched C10 alkyl group, R2 and R5 are H, m is 3-14, and n and o are 0.

[0837] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), wherein the nonionic cleaning surfactant is characterized in that R1 is n-C15H31, R2 and R5 are H, m is 9-80, and n and o are 0, or the cleaning surfactant is characterized in that R1 is n-C17H35, R2 and R5 are H, m is 9-80, and n and o are 0.

[0838] In one embodiment, m in the two nonionic cleaning surfactants is 25-80, preferably m is 25 or 80. The NIS may be referred to herein as NIS1a1.

[0839] In one embodiment, the nonionic cleaning surfactant is selected from general formula (NIS1a), wherein m is in the range of 3 to 11, preferably not exceeding 10, more preferably not exceeding 7; n and o are 0, R1 is a straight-chain C9-C17 alkyl group, and R2 and R5 are H.

[0840] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), wherein the nonionic cleaning surfactant is characterized in that R1 is n-C12H25, R2 and R5 are H, m is 3-30, preferably 7, and n and o are 0; or the cleaning surfactant is characterized in that R1 is n-C14H29, R2 and R5 are H, m is 3-30, preferably 7, and n and o are 0. The NIS may be referred to herein as NIS1a2.

[0841] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), wherein the nonionic cleaning surfactant is characterized in that R1 is n-C11H23, R2 and R5 are H, m is 4-10, and n and o are 0; or the cleaning surfactant is characterized in that R1 is selected from n-C11H23 and n-C17H35, R2 and R5 are H, m is 4-10, and n and o = 0.

[0842] The NIS may be referred to as NIS1a3 in this document.

[0843] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), wherein one of the nonionic surfactants is characterized in that R1 is n-C9H19, R2 and R5 are H, m is 5-7, and n and o = 0, or the cleaning surfactant is characterized in that R1 is n-C17H35, R2 and R5 are H, m is 5-7, and n and o = 0. The NIS may be referred to herein as NIS1a4.

[0844] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), wherein the nonionic cleaning surfactant is characterized in that R1 is n-C11H23, R5 is H, m is 7, and n and o = 0, or the cleaning surfactant is characterized in that R1 is C13H27, R5 is H, m is 7, and n and o = 0. The NIS may be referred to herein as NIS1a5.

[0845] In one embodiment, the nonionic cleaning surfactant is selected according to the general formula (NIS1a), wherein R1 is a C3 to C18 straight-chain alkyl group, R2 is H, and R3 and R4 are each independently selected from...

[0846] -Methyl, where n or o is 2-25, or

[0847] -Ethyl, and n or o is 1-3, or

[0848] -propyl, and n or o is 1-3,

[0849] And where m+n+o equals 5-50. In one embodiment, R5 is H. In one embodiment, R5 is selected from methyl, butyl, benzyl, and tert-butyl. The NIS may be referred to herein as NIS1a6.

[0850] In one embodiment, the compound is according to the general formula (NIS1a), wherein R2 is H, m is 10-50, R3 is a straight-chain or branched C8-C12 alkyl group, n is 1 or 2, wherein 1 is preferred, o is 0 or 1 and R5 is H.

[0851] In one embodiment, the compound is according to the general formula (NIS1a), wherein R2 is H, m is 10-50, R3 is a straight-chain or branched C8-C12 alkyl group, n is 1 or 2, wherein 1 is preferred, o is 0 or 1 and R5 is H.

[0852] In one embodiment, the nonionic cleaning surfactant is selected from compounds according to formula (NIS1a), wherein R1 is an n-C8 alkyl, R2 is H, R3 is a branched C11 alkyl, R5 is H, m is 22, n is 1 and o is 0. The NIS may be referred to herein as NIS1a7.

[0853] In one embodiment, the nonionic cleaning surfactant is selected from compounds according to formula (NIS1a), wherein R1 is an n-C8 alkyl, R2 is H, R3 is a branched C11 alkyl, R5 is H, m is 19, n is 1 and o is 0. The NIS may be referred to herein as NIS1a8.

[0854] In one embodiment, the nonionic cleaning surfactant is selected from compounds according to formula (NIS1a), wherein R1 is an n-C8 alkyl, R2 is H, R3 is an n-C8-C10 alkyl, R5 is H, m is 40, n is 1 and o is 0. The NIS may be referred to herein as NIS1a9.

[0855] In one embodiment, the nonionic cleaning surfactant is selected from compounds according to formula (NIS1a), wherein R1 is an n-C8 alkyl, R2 is H, R3 is methyl, R4 is an n-C10 alkyl, R5 is H, m is 22, n is 1 and o is 1. The NIS may be referred to herein as NIS1a10.

[0856] NIS2

[0857] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS2), which may be referred to herein as alkyl-polysaccharide (APG):

[0858]

[0859] In general formula (NIS2), R1 is selected from C1-C17 alkyl and C2-C17 alkenyl groups, wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched; examples are n-C7H15, n-C9H19, n-C11H23, n-C13H27, n-C15H31, n-C17H35, i-C9H19, i-C12H25.

[0860] In general formula (NIS2), R2 is selected from H, C1-C17 alkyl and C2-C17 alkenyl, wherein the alkyl and / or alkenyl are straight-chain (straight-chain; n-) or branched.

[0861] In the general formula (NIS2), G1 is selected from monosaccharides with 4 to 6 carbon atoms, such as glucose and xylose.

[0862] In the general formula (NIS2), the integer w is in the range of 1.1 to 4, and w is the mean.

[0863] In one embodiment, NIS2 is an octanoyl glucoside, which is a compound according to formula (NIS2), wherein R1 is n-C6H13, R2 is H, G1 is glucose and w is about 1.

[0864] In one embodiment, NIS2 is lauryl glucoside, which is a compound according to formula (NIS2), wherein R1 is n-C10H21, R2 is H, G1 is glucose and w is about 1.

[0865] NIS3

[0866] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS3):

[0867]

[0868] The variables in the general formula (NIS3) are defined as follows:

[0869] AO is selected from ethylene oxide (EO), propylene oxide (PO), butane oxide (BO), and mixtures thereof.

[0870] R6 is selected from C5-C17 alkyl and C5-C17 alkenyl groups, wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched.

[0871] R7 is selected from H, C1-C18-alkyl, wherein the alkyl group is straight-chain (straight-chain; n-) or branched.

[0872] The integer y in the general formula (NIS3) is a number in the range of 1 to 70, preferably 7 to 15.

[0873] NIS4

[0874] In one embodiment, the nonionic cleaning surfactant is NIS4, which includes sorbitol esters (NIS4a) and / or ethoxylated (NIS4b) or propoxylated (NIS4c) sorbitol esters. Non-limiting examples include products sold under the trademarks SPAN and TWEEN.

[0875] NIS5

[0876] In one embodiment, the nonionic cleaning surfactant NIS5 is selected from nonionic surfactants of alkoxylated monoalkylamines or dialkylamines (NIS5a), fatty acid monoethanolamides (FAMA, NIS5b), fatty acid diethanolamides (FADA, NIS5c), ethoxylated fatty acid monoethanolamides (EFAM, NIS5d), propoxylated fatty acid monoethanolamides (PFAM, NIS5e), polyhydroxyalkyl fatty acid amides (NIS5f), or N-acyl N-alkyl derivatives of glucosamine (NIS5g) (such as glucosamide (GA), fatty acid glucosamide (FAGA)) and combinations thereof.

[0877] Anionic cleaning surfactants

[0878] Anionic surfactants (AS) refer to surfactants that have negatively charged ionic groups. Anionic surfactants include, but are not limited to, surfactant compounds containing hydrophobic groups and at least one water-soluble anionic group (typically selected from sulfate, sulfonate, and carboxyl groups to form water-soluble compounds).

[0879] AS1

[0880] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS1a) or (AS1b):

[0881]

[0882]

[0883] The variables in the general formulas (AS1a and AS1b) are defined as follows:

[0884] R1 is selected from C1-C23-alkyl (such as 1-, 2-, 3-, 4-C1-C23-alkyl) and C2-C23-alkenyl, wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched, and wherein the 2-, 3-, or 4-alkyl groups are examples of n-C7H15, n-C9H19, n-C11H23, n-C13H27, n-C15H31, n-C17H35, i-C9H19, i-C12H25.

[0885] R2 is selected from H, C1-C20-alkyl or C2-C20-alkenyl, wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched.

[0886] R3 and R4 are each independently selected from C1-C16-alkyl groups, wherein the alkyl group is straight-chain (straight-chain; n-) or branched; examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, isodecyl.

[0887] Selected from -RCOO-, -SO3-, and -RSO3-, where R is selected from straight-chain (straight-chain; n-) or branched C1-C8-alkyl and C1-C4 hydroxyalkyl. When A- is -SO3-, the compound can be called (aliphatic) alcohol / alkyl (ethoxy / ether) sulfate [(F)A] [S], when A- is -RCOO-, the compound can be called a (aliphatic) alcohol / alkyl (ethoxy / ether) carboxylate [(F)A] C).

[0888] M+ is selected from H and the salt-forming cation. The salt-forming cation can be monovalent or polyvalent; therefore, M+ equals 1 / vMv+. Examples include, but are not limited to, sodium, potassium, magnesium, calcium, ammonium, and ammonium salts of mono-, di-, and triethanolamine.

[0889] The integer definitions of general formulas (AS1a) and (AS1b) are as follows:

[0890] m is in the range of 0 to 200, preferably 1 to 80, more preferably 3 to 20; n and o are each independently in the range of 0 to 100; n is preferably in the range of 1 to 10, more preferably 1 to 6; o is preferably in the range of 1 to 50, more preferably 4 to 25. The sum of m, n, and o is in the range of 0 to 100. In one embodiment, the sum of m, n, and o is 0. In another embodiment, the sum of m, n, and o is at least one, preferably in the range of 9 to 50.

[0891] Anionic cleaning surfactants of general formulas (AS1a) and (AS1b) can have any structure, block copolymer or random copolymer.

[0892] In one embodiment, the anionic cleaning surfactant according to formula (AS1a) is a compound in which R1 is n-C11H23, R2 is H, A- is -SO3-, and m, n, and o are O. M+ is preferably Na+. Such a compound may be referred to as sodium lauryl sulfate.

[0893] In one embodiment, the anionic cleaning surfactant according to formula (AS1a) is a compound characterized in that R1 is n-C11H23, R2 is H, A- is -SO3-, and m, n, and o are 0; M+ is preferably Na+. Alternatively, AS1a is characterized in that R1 is n-C18H37, R2 is H, A- is -SO3-, and m, n, and o are 0; M+ is preferably Na+. Such compounds may be referred to herein as AS1a1.

[0894] In one embodiment, the anionic cleaning surfactant according to formula (AS1a) is a compound in which R1 is n-C11H23, R2 is selected from H, A- is -SO3-, m is 2-5, preferably 3, and n and o are 0. M+ is preferably Na+. Such compounds may be referred to herein as lauryl ether sulfate (LES) or sodium lauryl ether sulfate (SLES) or AS1a2.

[0895] Other suitable anionic cleaning surfactants include salts (M+) of C12-C18 sulfonyl fatty acid alkyl esters (such as C12-C18 sulfonyl fatty acid methyl esters), C10-C18-alkylaryl sulfonic acids (such as n-C10-C18-alkylbenzene sulfonic acid), and C10-C18 alkylalkoxycarboxylic acid esters.

[0896] M+ is selected from salt-forming cations in all cases. Salt-forming cations can be monovalent or polyvalent; therefore, M+ equals 1 / v Mv+. Examples include, but are not limited to, sodium, potassium, magnesium, calcium, ammonium, and ammonium salts of mono-, di-, and triethanolamine.

[0897] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS1a), wherein the anionic surfactant is characterized in that R1 is C11, R2 is H, m is 2, n and o are 0, A- is -SO3-, and M+ is Na+, or the surfactant is characterized in that R1 is C13, R2 is H, m is 2, n and o are 0, A- is -SO3-, and M+ is Na+. The AS may be referred to herein as AS1a3.

[0898] AS2

[0899] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS2a) or (AS2b):

[0900] (AS2a)

[0901] In formula (AS2a), R1 is a straight-chain or branched C10-C13 alkyl group; M+ is preferably Na+.

[0902] (AS2b)

[0903] In formula (AS2b), R1 is a straight-chain or branched C10-C13 alkyl group; n is 1 or 2; and M+ is preferably Na+.

[0904] Compounds of formula (AS2a) having a branched R1 may be referred to herein as BABS (branched alkylbenzene sulfonates). Compounds of formula (AS2a) (where R1 is an n-C10-C13 alkyl group) may be referred herein as LAS (linear alkylbenzene sulfonates).

[0905] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS2a), wherein the anionic cleaning surfactant is characterized in that R1 is n-C10H21, and the other surfactant is characterized in that R1 is n-C13H27. Both anionic cleaning surfactants may be sodium salts and may be referred to herein as AS2a.

[0906] In one embodiment, the compound according to formula (AS2b) is a compound in which R1 is n-C14H29 to n-C17H35, preferably n-C12H29 to n-C15H31. The compound may be referred to herein as α-olefin sulfonate (AOS). Typically, AOS is a mixture of olefin sulfonate (60%-65%) and hydroxyalkane sulfonate (35%-40%).

[0907] AS3

[0908] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS3), which may be referred to as an N-acyl amino acid surfactant:

[0909]

[0910] The variables in the general formula (AS3) are defined as follows:

[0911] R6 is selected from straight-chain (straight-chain; n-) or branched C6-C22-alkyl and straight-chain (straight-chain; n-) or branched C6-C22-alkenyl, such as oleylene.

[0912] R7 is selected from H and C1-C4-alkyl.

[0913] R8 is selected from H, methyl, -(CH2)3NHC(NH)NH2, -CH2C(O)NH2, -CH2C(O)OH, -(CH2)2C(O)NH2, -(CH2)2C(O)OH, (imidazol-4-yl)-methyl, -CH(CH3)C2H5, -CH2CH(CH3)2, -(CH2)4NH2, benzyl, hydroxymethyl, -CH(OH)CH3, (indole-3-yl)-methyl, (4-hydroxy-phenyl)-methyl, isopropyl, -(CH2)2SCH3 and -CH2SH.

[0914] R9 is selected from -COOX and -CH2SO3X, where X is selected from Li+, Na+ and K+.

[0915] In one embodiment, AS3 is selected from monocarboxylate and dicarboxylate salts of N-acylated glutamate (e.g., sodium, potassium, ammonium, and ammonium salts of mono-, di-, and triethanolamine), such as sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoyl glutamate, disodium stearoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, and potassium myristoyl glutamate; carboxylate salts of N-acylated alanine (e.g., sodium, potassium, ... Ammonium salts of ammonium and mono-, di-, and triethanolamines, such as sodium cocoyl alanine and triethanolamine lauroyl alanine; carboxylates of N-acylated glycine (e.g., sodium, potassium, ammonium, and mono-, di-, and triethanolamines), such as sodium cocoyl glycine and potassium cocoyl glycine; carboxylates of N-acylated sarcosine (e.g., sodium, potassium, ammonium, and mono-, di-, and triethanolamines), such as sodium lauroyl sarcosine, sodium myristoyl sarcosine, sodium oleoyl sarcosine, and ammonium lauroyl sarcosine.

[0916] AS4

[0917] In one embodiment, the anionic cleaning surfactant is selected from the group consisting of soaps (AS4). In one embodiment, AS4 is selected from salts (M+) of saturated and unsaturated C12-C18 fatty acids (AS4a) such as lauric acid, myristic acid, palmitic acid, stearic acid, benzolic acid, oleic acid, and (hydrated) erucic acid. M+ is selected from salt-forming cations. Salt-forming cations can be monovalent or polyvalent; therefore, M+ equals 1 / v Mv+.

[0918] Examples include, but are not limited to, sodium, potassium, magnesium, calcium, ammonium, and ammonium salts of mono-, di-, and triethanolamine.

[0919] In one embodiment, AS4 is a salt (M+) of a sulfate, sulfonate, or carboxylate derived from natural fatty acids (AS4b) such as tallow (primarily C14-C18), coconut oil (primarily C12-C14), palm kernel oil (primarily C8-C18), olive oil (primarily C16-C18), or canola oil (primarily C18). Depending on the natural fatty acids from which the soap is derived, such anionic surfactants contain varying amounts of sulfate, sulfonate, or carboxylates of lauric acid and / or myristic acid and / or palmitic acid and / or stearic acid and / or oleic acid and / or linoleic acid.

[0920] AS5

[0921] In one embodiment, the anionic cleaning surfactant is selected from sulfonated fatty acid methyl esters according to formula (AS5):

[0922] (AS5)

[0923] in

[0924] R1 is a fatty acid C6 to C16 or -CH2COOH and M+ is preferably Na+.

[0925] In one embodiment, AS5 is a fatty acid methyl ester sulfonate (MES). In one embodiment, the MES is derived from natural fatty acids such as tallow (primarily C14-C18), coconut oil (primarily C12-C14), palm kernel oil (primarily C8-C18), olive oil (primarily C16-C18), or canola oil (primarily C18). The MES may be referred to herein as AS5a.

[0926] In one embodiment, AS5a is a C12-C18 fatty acid methyl ester sulfonate. Preferably, AS5a is a coconut oil methyl ester sulfonate.

[0927] In one embodiment, the anionic cleaning surfactant is a monoester of sulfosuccinic acid (which may be referred to herein as AS5b) or a diester of sulfosuccinic acid (which may be referred to herein as AS5c).

[0928] Amphoteric cleaning surfactants

[0929] Amphoteric cleaning surfactants refer to surfactants that, depending on pH, can be any of the following: cationic, amphoteric, or anionic.

[0930] AMS1

[0931] In one embodiment, the amphoteric cleaning surfactant is selected from compounds of general formula (AMS1), which may be referred to as amino acids (both proteogenetic and non-proteogenetic):

[0932]

[0933] The variables in the general formula (AMS1) are defined as follows:

[0934] R8 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, wherein the alkyl group is and / or is straight-chain (straight-chain; n-) or branched.

[0935] R9 is selected from C1-C22-alkyl, C2-C22-alkenyl, C10-C22-alkylcarbonyl, and C10-C22-alkenylcarbonyl.

[0936] R10 is selected from H, methyl, -(CH2)3NHC(NH)NH2, -CH2C(O)NH2, -CH2C(O)OH, -(CH2)2C(O)NH2, -(CH2)2C(O)OH, (imidazol-4-yl)-methyl, -CH(CH3)C2H5, -CH2CH(CH3)2, -(CH2)4NH2, benzyl, hydroxymethyl, -CH(OH)CH3, (indole-3-yl)-methyl, (4-hydroxy-phenyl)-methyl, isopropyl, -(CH2)2SCH3 and -CH2SH.

[0937] Rx is selected from H and C1-C4-alkyl groups.

[0938] AMS2

[0939] In one embodiment, the amphoteric cleaning surfactant is selected from compounds of general formula (AMS2a), (AMS2b), or (AMS2c), which may be referred to as betaine and / or sulfobetaine (AMS2):

[0940]

[0941] The variables in the general formulas (AMS2a), (AMS2b), and (AMS2c) are defined as follows:

[0942] R11 is selected from straight-chain (straight-chain; n-) or branched C7-C22 alkyl and straight-chain (straight-chain; n-) or branched C7-C22 alkenyl.

[0943] R12 are each independently selected from straight-chain (straight-chain; n-) C1-C4 alkyl groups.

[0944] R13 is selected from C1-C5 alkyl and hydroxy C1-C5 alkyl; for example, 2-hydroxypropyl.

[0945] It is selected from carboxylate and sulfonate groups.

[0946] The integer r in general formulas (AMS2a), (AMS2b) and (AMS2c) is in the range of 2 to 6.

[0947] In one embodiment, AMS2b is cocamidopropyl betaine.

[0948] AMS3

[0949] In one embodiment, the amphoteric cleaning surfactant is selected from compounds of general formula (AMS3), which may be referred to as alkyl-amphocarboxylic acid esters:

[0950]

[0951] The variables in the general formula (AMS3) are defined as follows:

[0952] R11 is selected from C7-C22 alkyl and C7-C22 alkenyl groups, wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched, preferably straight-chain.

[0953] R14 is selected from -CH2C(O)O-M+, -CH2CH2C(O)O-M+ and -CH2CH(OH)CH2SO3-M+.

[0954] R15 is selected from H and -CH2C(O)O-.

[0955] In the general formula (AMS3), the integer r is in the range of 2 to 6.

[0956] In one embodiment, the alkyl-amphocarboxylate is selected from sodium cocoamphoacetate, sodium lauroylamphoacetate, sodium capryloamphoacetate, disodium cocoamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodiapropionate, disodium lauroylamphodiapropionate, disodium caprylamphodiapropionate, and disodium caprylamphodiapropionate.

[0957] AMS4

[0958] In one embodiment, the amphoteric cleaning surfactant is selected from compounds of general formula (AMS4), which may be referred to as amine oxide (AO):

[0959]

[0960] The variables in the general formula (AMS4) are defined as follows:

[0961] R16 is selected from C8-C18 alkyl, hydroxyC8-C18 alkyl, amamidopropyl and C8-C18 alkylphenyl; wherein the alkyl and / or alkenyl groups are straight-chain (straight-chain; n-) or branched.

[0962] R17 is selected from C2-C3 alkylene, hydroxy-C2-C3 alkylene, and mixtures thereof.

[0963] R18: Each residue can be independently selected from C1-C3 alkyl and hydroxy C1-C3; R15 groups can be attached to each other, for example, by oxygen or nitrogen atoms, to form a ring structure.

[0964] In the general formula (AMS4), the integer x is in the range of 0 to 5, preferably from 0 to 3, and most preferably 0.

[0965] In one embodiment, the amine oxide is selected from C10-C18 alkyldimethylamine oxides and C8-C18 alkoxyethyldihydroxyethylamine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyldimethylamine oxide, cetyldimethylamine oxide, stearyldimethylamine oxide, tallow dimethylamine oxide, and dimethyl-2-hydroxyoctadecylamine oxide.

[0966] In one embodiment, the amine oxide is cocamidopropyl dimethylamine oxide, which is sometimes also referred to as cocamidopropylamine oxide.

[0967] Uses and cleaning compositions, and uses of surfactants and cleaning compositions containing surfactants.

[0968] Alkoxylated diamines, oligoamines and polyamines, as well as alkoxylated polyethylimide, are referred to as "inventive compounds" and may also be referred to as "one or more compounds of the invention" hereinafter.

[0969] The uses of surfactants of this invention as disclosed and defined herein and the products / formulations / compositions comprising them are the same as those known in the art; such uses of surfactants of this invention and the products / formulations / compositions comprising them are particularly those disclosed in any of the following disclosures: US 2019 / 390142, WO2020 / 264077, WO 2020 / 005476, WO 2023017061 A1, WO 03 / 042262, Publications 800542 and 800500WO 99 / 05242, US Patents 5,576,282, 6,306,812 B1 and 6,326,348 B1 - too many to list, only a very few examples - And specifically those listed in the previous chapter; such surfactants have many known uses, all of which are covered by this invention, such as in pharmaceutical applications, in oilfield applications, in detergents, in agricultural chemical formulations, printing, electronic products, for metal processing and production, paints and coatings, automobile production, and any typical uses of such surfactants that are currently in use or have been used in the past.

[0970] In all those disclosures of the prior art and known uses and applications, surfactants may be partially or completely replaced with surfactants of the present invention that have the same or closely similar chemical structures but are produced using at least one element of the present invention (e.g., ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, and / or hydrogen, which are produced as can be produced by the method of the present invention or preferably produced by the method of the present invention, instead of standard fossil-based ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, and / or hydrogen).

[0971] The surfactants of the present invention, as detailed herein and by reference to the various prior art documents cited herein, may also be referred to hereinafter as "one or more inventive compound(s)" and "one or more compound(s) of the invention".

[0972] In cases where "one or more inventive compound(s)" and "one or more compound(s) of the invention" specifically refer to alkoxylated diamines, oligomeric amines, polyamines, and alkoxylated polyethylimide, or specifically surfactants, "one or more inventive compound(s)" and "one or more compound(s) of the invention" are respectively characterized. Otherwise, "one or more inventive compound(s)" and "one or more compound(s) of the invention" encompass alkoxylated diamines, oligomeric amines, polyamines, and alkoxylated polyethylimide, as well as surfactants.

[0973] The terms "at least one compound of the present invention" and "one or more compounds of the present invention" cover one, two, three, four or more compounds of the present invention as a mixture.

[0974] One or more compounds of the present invention, obtained directly from the methods of the present invention, can be advantageously used in cleaning compositions.

[0975] They can be used as at least one compound of the present invention, or a mixture of more than one compound of the present invention.

[0976] Therefore, another subject of the present invention is the use of one or more of the compounds of the present invention described above in cleaning compositions, particularly those prepared by the methods defined herein.

[0977] Of course, any surfactant that can be produced using ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen and therefore using at least one element of the present invention, as mentioned in this and subsequent sections regarding uses and compositions, as well as cleaning additives, may be partially or completely replaced by surfactants of the present invention with the same chemical structure but produced using the present invention.

[0978] One or more compounds of the present invention may be added to the cleaning composition.

[0979] One or more compounds of the present invention are typically present in the formulation at a concentration of about 0.1% to about 50%, preferably from about 0.25% to 15%, more preferably from about 0.5% to about 10%, and even more preferably from about 0.5% to about 5%, and most preferably at an amount of up to 3%, each in weight percent relative to the total weight of such composition / product. Such composition / product optionally further comprises a surfactant system of about 1% to about 70% by weight, wherein—specifically—for liquid manual dishwashing or spray detergent cleaning compositions, such compositions comprise a surfactant system of 0.1% to 50%, preferably from 1% to 35%, more preferably from 3% to 30% by weight of the total composition, and such surfactant system preferably comprises anionic surfactants of 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system. Where one or more compounds of the present invention are one or more surfactants, the surfactants of the present invention may of course be included as more than one or all surfactants in the surfactant system.

[0980] Therefore, another subject of the present invention is the use of one or more compounds of the present invention obtained by the method of the present invention as detailed above in the use of improved removal of oily and greasy stai...

Claims

1. A process for the production of oxirane or propylene oxide comprising the steps of: (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol, (c) converting the methanol from step (b) to ethylene and / or propylene, (d) reacting the ethylene and / or propylene from step (c) with oxygen or an oxidizing agent to form oxirane and / or propylene oxide, wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gas or from air or from seawater or other natural water or obtained from a biological process, for example from a fermentation process from waste or biomass, and / or wherein the hydrogen in step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least partially from non-fossil resources.

2. A process for the preparation of an ethanolamine, wherein, said process comprising steps (b), (c) and (d) of the process according to claim 1 and thus comprising the steps of: (a) reacting hydrogen with nitrogen to form ammonia, (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol, (c) converting the methanol from step (b) to ethylene (d) reacting ethylene from step (c) with oxygen to form ethylene, (e) converting the ammonia from step (a) to ethanolamine in one or more steps with oxirane from step (d), wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least partially from non-fossil resources.

3. A process for the preparation of polyethyleneimine, wherein, said process comprising steps (a), (b), (c), (d) and (e) of the process according to claim 2 and thus comprising the steps of: (a) reacting hydrogen with nitrogen to form ammonia, (b) reacting hydrogen with a carbon oxide, preferably carbon dioxide, to form methanol, (c) converting the methanol from step (b) to ethylene, (d) reacting ethylene from step (c) with oxygen to form oxirane, (e) converting the ammonia from step (a) to ethanolamine in one or more steps with oxirane from step (d), (f) separating monoethanolamine from the ethanolamine obtained in step (e); (g) converting monoethanolamine from step (f) to ethyleneimine, preferably by catalytic gas phase synthesis, and (h) polymerizing the ethyleneimine obtained in step (g) to polyethyleneimine, wherein the hydrogen in step (a) and / or step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least partially from non-fossil resources.

4. The method of any one of claims 1 to 3, wherein, In all steps (a) to (h), energy in the form of thermal energy and / or electrical power is used, and the energy used in steps (a), (b), (c), (f) and (g), preferably the energy used in steps (a) to (h), is at least partially generated from non-fossil resources.

5. The method of any one of claims 1 to 4, wherein, The energy generated from non-fossil resources is selected from the group consisting of solar energy (thermal, photovoltaic and concentrated), wind power, hydro power (tidal energy, wave energy, hydro power dams, riverine hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), renewable parts of waste, nuclear energy and mixtures thereof.

6. The method of any one of claims 1 to 5, wherein, The hydrogen is obtained by water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

7. The method of any one of claims 1 to 6, wherein, Carbon dioxide is employed in step (b), which is preferably at least partially captured from industrial flue gases or from air.

8. The method of any one of claims 1 to 7, wherein, The ethylene in step (c) is obtained by a methanol-to-olefins process, preferably using a zeolite catalyst.

9. The method of any one of claims 1 to 8, wherein, The ethylene oxide in step (d) is obtained by epoxidation of ethylene, preferably using a silver-based catalyst.

10. A process for the preparation of an alkoxylated compound, the alkoxylated compound comprising i) 20 wt-% to < 100 wt-% of ethylene oxide units and / or propylene oxide units, ii) 0 wt-% to 30 wt-% of at least one alkylene oxide unit different from ethylene oxide units and propylene oxide units, iii) > 0 wt-% to 80 wt-% of at least one starter unit having Zel’evitnoff-active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, the process comprising steps (b), (c) and (d) of the process according to claim 1 and thus comprising the following steps: (b) reacting hydrogen with carbon dioxide to form methanol, (c) converting the methanol from step (a) to ethylene and / or propylene, (d) reacting the ethylene and / or propylene from step (b) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and (e0) in one or more steps, reacting the ethylene oxide and / or propylene oxide obtained in step (d) and, optionally, the at least one alkylene oxide different from ethylene oxide and propylene oxide, with the at least one starter unit having Zel’evitnoff-active hydrogen atoms to form the alkoxylated compound, wherein the carbon dioxide in step (b) is at least partially captured from industrial flue gases or from air or from seawater or other natural water, or obtained from a biological process, for example from a fermentation process from waste or biomass.

11. The method of claim 10, wherein, The hydrogen in step (b) is at least partially obtained by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy at least partially generated from non-fossil resources.

12. A process for making alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, any of which individually or together are "the compounds", wherein, the process comprising steps (a), (b), (c) and (d) of the process according to claim 2 and thus comprising the following steps: (a) reacting hydrogen gas with nitrogen gas to form ammonia, (b) reacting hydrogen gas with a carbon oxide, preferably carbon dioxide, to form methanol, (c) and (d) and converting the methanol from step (b) to ethylene and / or propylene, and further to ethylene oxide and / or propylene oxide with oxygen or an oxidizing agent, e1 ) converting the ethylene oxide and / or propylene oxide and optionally the at least one different epoxide alkane than ethylene oxide and propylene oxide from step (d) to alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, respectively, in one or more steps using known methods, wherein the hydrogen gas in steps (a) and (b) is obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium of < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content.

13. A method for preparing an alkoxylated polyethyleneimine ("the compound") wherein, The process comprises the steps (a), (b), (c), (d), (e), (f), (g) and (h) of the process according to claim 3 and thus comprises the following steps: (a) reacting hydrogen gas with nitrogen gas to form ammonia, (b) reacting hydrogen gas with a carbon oxide, preferably carbon dioxide, to form methanol, (c) and (d) converting the methanol from step (b) to ethylene and / or propylene, preferably ethylene, and further to ethylene oxide and / or propylene oxide, preferably ethylene oxide, with oxygen, (e) converting the ammonia from step (a) to ethanolamine with ethylene oxide from step (d) in one or more steps, and (f) separating monoethanolamine from the ethanolamine obtained in step (e), (g) converting monoethanolamine to ethyleneimine, (h) polymerizing ethyleneimine from step (g) to polyethyleneimine; and (i) alkoxylating the polyethyleneimine from step (g) with the ethylene oxide and / or propylene oxide, preferably ethylene oxide, and optionally further ingredients such as other epoxide alkane and / or lactone, to obtain an alkoxylated polyethyleneimine, wherein the hydrogen gas in steps (a) and (b) is obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium of < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, wherein preferably step (g) is carried out in gas phase or in liquid phase.

14. A process for the production of a surfactant comprising at least one structural element derived from ethylene oxide, methanol, ammonia, ethanolamine, or produced with hydrogen, wherein the process comprises the steps (a), (b), (c), (d), (e) and (f) of the process according to claim 3 and thus comprises the following steps: (a) reacting hydrogen with nitrogen to form ammonia, (b) reacting hydrogen with carbon oxide, preferably carbon dioxide, to form methanol, (c) and (d) converting the methanol from step (b) to ethylene and further to ethylene oxide with oxygen, (e) converting the amine from step (a) a) with ethylene oxide from step (d) in one or more steps to ethanolamine, and (f) separating monoethanolamine, diethanolamine and triethanolamine from the ethanolamine obtained in step (e), (g0) converting any products from steps a), b), c), d) and e) to a surfactant comprising at least one structural element derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen in at least one known process step, to obtain a surfactant comprising less deuterium based on the total hydrogen content compared to the same surfactant obtained only from fossil source based chemistry, wherein the hydrogen in steps (a) and (b) is obtained by electrolysis based on electrical power generated at least partially from non-fossil energy sources has a molar share of deuterium of < 100 ppm, preferably in the range from 10 to < 95 ppm, more preferably in the range from 10 to < 90 ppm, most preferably in the range from 10 to < 80 ppm based on the total hydrogen content.

15. A polyethyleneimine obtainable by the process according to any one of claims 3 to 9.

16. An ethanolamine obtainable by the process according to any one of claims 1 to 9.

17. Use of a polyethyleneimine according to claim 15 or obtained by the process according to any one of claims 3 to 9 or an ethanolamine according to claim 16 or obtained by the process according to any one of claims 1 to 9 as a CO2 absorbent in a CO2 capture process.

18. An alkoxylated compound obtainable by the process according to claim 10 or 11.

19. The alkoxylated compound according to claim 18 or obtainable by the method according to claim 10 or 11, wherein, The alkoxylated compound meets the biodegradability requirements set out in OECD 301 B.

20. A surfactant obtainable by the process according to claim 14.

21. Use of the alkoxylated compound according to claim 18 or 19 or obtained by the method according to claim 10 or 11 in household care products, cosmetic products, pharmaceutical products, food industry, construction materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metal working fluids and transmission fluids, antifoams, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metal working fluids, agrochemicals such as pesticides, textile and leather auxiliaries, bio-processing, fuel performance packages and poly(urethane) applications.

22. An alkoxylated diamine, oligoamine and polyamine or alkoxylated polyethyleneimine (any one of the "compounds", individually or collectively), wherein, Such compound is at least partially based on hydrogen from non-fossil based sources, wherein the molar fraction of deuterium in such compound is lower than the molar fraction of deuterium in the same chemical compound when derived from fossil based sources only, and wherein such alkoxylated compound can contain other monomers in the chain derived from alkylene oxides, preferably containing ethylene oxide, such other monomers are preferably selected from lactones and / or other alkylene oxides than ethylene oxide.

23. An alkoxylated polyethylene imine ("the compound"), wherein, The polyethyleneimine has a molar fraction of deuterium of < 110 ppm, preferably in the range of from 10 to < 105 ppm, more preferably in the range of from 10 to < 95 ppm, most preferably in the range of from 10 to < 92 ppm, based on the total hydrogen content.

24. Use of the surfactant according to claim 20 or of the compound according to claim 22 or 23, or of the compound obtainable or preferably obtained by the method according to claim 12 or 13, or of the surfactant obtainable or preferably obtained by the method according to claim 14, preferably in a composition, more preferably a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product.

25. The use of claim 23, wherein, The composition comprises at least one compound in a concentration of from about 0.1 % to about 20% by weight relative to the total weight of such composition or product, or wherein the composition comprises at least one surfactant in a concentration of from about 0.1 % to about 50% by weight relative to the total weight of such composition or product.

26. The use according to claim 23 or 24, wherein, The composition is in liquid or semi-liquid form.

27. The use according to any one of claims 23 to 25, further fulfilling at least one of the following requirements: a. comprising at least one enzyme, b. comprising from about 1 % to about 70% by weight of a surfactant system, c. comprising at least one further cleaning adjunct, preferably at least one polymer, more preferably at least one graft polymer based on a polyalkylene oxide and a polymer side chain attached via radical polymerization, the polymer side chain comprising at least one monomer selected from vinyl esters, vinyl lactams and optionally vinyl amines, or an oligo- or polysaccharide comprising a polymer side chain obtained from radical polymerization of at least one monomer comprising acrylic acid, methacrylic acid and salts thereof, in an effective amount, and d. exhibiting improved wash performance, preferably in primary cleaning, and in case the composition comprises a surfactant obtainable or preferably obtained by the process according to claim 14, e. exhibits primary wash properties, wherein the surfactant can also be partially or completely comprised in the surfactant system.

28. A composition which is a laundry detergent, cleaning composition or fabric and home care product, containing at least one compound according to claim 22 or 23, or obtainable or preferably obtained by the process according to claim 12 or 13, or a surfactant obtainable or preferably obtained by the process according to claim 14, comprising the at least one compound in a concentration of preferably from about 0.1 % to about 20% by weight relative to the total weight of such composition or product, or, and in case the composition comprises a surfactant obtainable or preferably obtained by the process according to claim 14, comprising the at least one compound in a concentration of from about 0.1 % to about 50% by weight relative to the total weight of such composition or product, and optionally further comprising at least one of a) to c) a. at least one enzyme, preferably selected from one or more of lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, deoxyribonuclease, dispersase, pectinase, oxidoreductase, cutinase, lactase and peroxidase, more preferably at least two of the foregoing types, and in case enzymes are comprised, preferably also at least one enzyme stabilizing system, b. from about 1 % to about 70% by weight of a surfactant system, c. at least one additional cleaning adjunct, preferably at least one polymer, more preferably at least one graft polymer based on a polyalkylene oxide and a polymer side chain attached via free radical polymerization, the polymer side chain comprising at least one monomer selected from vinyl ester, vinyl lactam and optionally vinyl amine, or an oligo- or polysaccharide comprising a polymer side chain obtained from free radical polymerization of at least one monomer comprising acrylic acid, methacrylic acid and salts thereof, in an effective amount, and optionally exhibits improved wash performance in primary cleaning (i.e. stain removal), and / or in case the composition comprises a surfactant obtainable or preferably obtained by the process according to claim 14, dye transfer inhibition properties, wherein the surfactant can also be partially or completely comprised in the surfactant system.

29. The composition according to claim 28 in liquid or semi-liquid form, preferably a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid hand dishwash detergent formulation or a solid automatic dishwash formulation, more preferably a liquid laundry detergent formulation, optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2 ppm to 5%, more preferably 0.1 % to 2% by weight of the composition, and 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration optionally comprised from 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6%, each by weight of the composition.

30. The polyethylenimine obtainable or obtained by the process according to any one of claims 3 to 9, the ethanolamine obtainable or obtained by the process according to any one of claims 1 to 9, the alkoxylated compound obtainable or obtained by the process according to claim 10 or 11, the surfactant obtainable or obtained by the process according to claim 14, the alkoxylated diamines, oligoamines and polyamines according to claim 22 and the alkoxylated polyethylenimine according to claim 23, have a reduced amount of fossil-based hydrogen content, and thus a generally reduced cradle-to-gate product carbon footprint, compared to polyethylenimine, ethanolamine, alkoxylated compound, surfactant, alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethylenimine obtainable or obtained by a process using only fossil-based hydrogen.

31. The polyethylenimine obtainable or obtained by the process according to any one of claims 3 to 9, the ethanolamine obtainable or obtained by the process according to any one of claims 1 to 9, the alkoxylated compound obtainable or obtained by the process according to claim 10 or 11, the surfactant obtainable or obtained by the process according to claim 14, the alkoxylated diamines, oligoamines and polyamines according to claim 22 and the alkoxylated polyethylenimine according to claim 23, which are obtainable or obtained by using carbon dioxide at least partially captured from industrial flue gases or from air or from seawater or other natural water or obtained from a biological process, have a generally reduced cradle-to-gate product carbon footprint, compared to polyethylenimine, ethanolamine, alkoxylated compound, surfactant, alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethylenimine not obtainable or obtained by using carbon dioxide at least partially captured from industrial flue gases or from air or from seawater or other natural water or obtained from a biological process.

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