Environmentally friendly ethylene oxide, propylene oxide, and downstream products

Abstract

The present invention relates to a method for preparing ethylene oxide or propylene oxide, comprising the steps of (b) reacting hydrogen with carbon oxides to form methanol, (c) converting the methanol from step (b) to ethene and / or propene, and (d) reacting the ethene and / or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, wherein at least part of the carbon dioxide in step (b) is recovered from industrial exhaust gas or 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 at least part of the hydrogen in step (b) is obtained by water splitting, preferably by water splitting using energy produced at least partly from non-fossil resources; a method for preparing ethanolamines, a method for preparing alkoxylated compounds, a method for producing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, a method for producing alkoxylated polyethyleneimines, and a method for producing surfactants. This relates to methods, each of which is based on the method for preparing ethylene oxide or propylene oxide; polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines that are available by the above-described methods; the use of polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines; compositions that are laundry detergents, cleaning compositions or fabric and home care products containing at least alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, or surfactants; and polyethyleneimines, ethanolamines, alkoxylated surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines that have a reduced fossil hydrogen content, and consequently a reduced overall product carbon footprint from cradle to gate.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing ethylene oxide or propylene oxide, comprising the following steps: (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting methanol in step (b) to ethene and / or propene, (d) A step of reacting the ethene and / or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide. Includes, The carbon dioxide in process (b) is at least partially recovered from industrial exhaust gases, air, ocean water, or other natural water sources, or obtained from biological processes, such as fermentation processes from waste or biomass. and / or The hydrogen in step (b) is obtained, at least in part, by hydrosplitting, preferably by electrolysis, and the method uses energy that is preferably at least in part from non-fossil resources; A method for preparing ethanolamines, comprising steps (b), (c), and (d) of a method for preparing ethylene oxide or propylene oxide, plus the following step: (a) A step of forming ammonia by reacting hydrogen with nitrogen, a step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, and (e) A process of converting the ammonia from step (a) into ethanolamines together with ethylene oxide from step (d) in one or more steps. Includes, A method wherein the hydrogen of step (a) and / or step (b) is obtained, at least in part, by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably by electrolysis, uses energy that is at least in part derived from non-fossil resources; A method for preparing polyethyleneimine, comprising steps (a), (b), (c), (d), and (e) of the method for preparing ethanolamines, plus the following step: (f) Step of separating monoethanolamine from ethanolamines obtained in step (e); (g) Step of converting the monoethanolamine in step (f) into ethyleneimine, preferably by catalytic gas-phase synthesis, and (h) Step of polymerizing the ethyleneimine obtained in step (g) into polyethyleneimine comprising Method in which the hydrogen in step (a) and / or step (b) is obtained at least in part by hydrolysis, preferably by electrolysis, and the hydrolysis, preferably electrolysis, uses energy at least in part generated from non-fossil resources; 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 and propylene oxide units, iii) >0 wt% to 80 wt% of at least one initiator unit having a Zerewitinoff active hydrogen atom (where the sum of the units listed in i), ii) and iii) is 100 wt%) A method for preparing an alkoxylated compound comprising Steps (b), (c) and (d) of the method for preparing ethylene oxide or propylene oxide, in addition to the following steps: (e0) Step of forming an alkoxylated compound by reacting ethylene oxide and / or propylene oxide obtained in step (d) and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide with at least one initiator unit having a Zerewitinoff active hydrogen atom in one or more steps comprising Method in which at least part of the carbon dioxide in step (b) is recovered from industrial exhaust gas or air or seawater or other natural water, or obtained from a biological process, for example a fermentation process from waste or biomass; A method for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines (any of these individually or in combination as "compounds"), comprising steps (a), (b), (c), and (d) of a method relating to the preparation of ethanolamines, and in addition, the following steps: e1) A step of converting the ethylene oxide and / or propylene oxide from step (d), and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide, to alkoxylated diamines, oligoamines, and polyamines or alkoxylated polyethyleneimines, respectively, in one or more steps using known methods. Includes, A method wherein the hydrogen from steps (a) and (b) is electrolyzed based on electricity generated at least partially from non-fossil energy, resulting in a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, relative to the total hydrogen content; A method for preparing alkoxylated polyethyleneimine ("compound"), comprising steps (a), (b), (c), (d), (e), (f), (g), and (h) of a method for preparing polyethyleneimine, and in addition, the following steps: (i) A step to obtain alkoxylated polyethyleneimines by alkoxyling the polyethyleneimine from step (g) with ethylene oxide and / or propylene oxide, and optionally other alkylene oxides and / or lactones. Includes, The hydrogen from steps (a) and (b) is subjected to electrolysis based on electricity generated at least partially from non-fossil energy, resulting in a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, relative to the total hydrogen content. Preferably, step (g) is carried out in the gas phase or the liquid phase; A method for producing a surfactant, wherein such surfactant comprises at least one structural unit derived from ethylene oxide, methanol, ammonia, or ethanolamine, or is produced with hydrogen, and the method comprises the following steps: (a) A process of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) and (d) A step in which methanol in step (b) is converted to ethylene, and further converted to ethylene oxide with oxygen, (e) A step of converting the ammonia from step (a) together with the ethylene oxide from step (d) into ethanolamines in one or more steps, and (f) A step of separating monoethanolamine, diethanolamine, and triethanolamine from the ethanolamines obtained in step (e), (g0) A step of converting any of the products of steps a), b), c), d), and e) into a surfactant containing at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or hydrogen, by at least one known method step. This process includes obtaining a surfactant that contains less deuterium in total hydrogen content compared to chemically identical surfactants obtained solely from fossil-derived sources. A method wherein the hydrogen from steps (a) and (b) is electrolyzed based on electricity generated at least partially from non-fossil energy, resulting in a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, relative to the total hydrogen content; Polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which can be obtained by the methods described above; Use of polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines; A composition that is a laundry detergent, cleaning composition or fabric home care product containing at least an alkoxylated diamine, oligoamine and polyamine or alkoxylated polyethyleneimine (any of these individually or in combination as “compound”), or a surfactant, wherein at least one compound is contained in a concentration of preferably about 0.1% to about 20% by weight relative to the total weight of such composition or product, or, if the composition contains a surfactant, at least one compound is contained in a concentration of about 0.1% to about 50% by weight relative to the total weight of such composition or product; Polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which have a reduced fossil hydrogen content and, consequently, have 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 available or obtained by methods using exclusively fossil hydrogen; and The present invention relates to polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which are available or obtainable through the use of carbon dioxide that is recovered from industrial exhaust gases, air, seawater or other natural waters, or obtained from biological processes, and which have an overall reduced product carbon footprint from cradle to gate compared to polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which are.

[0002] Furthermore, the present invention relates to a method for preparing polyethyleneimine in good yield having a low product carbon footprint (PCF) based on energy at least partially derived from non-fossil resources, a method for preparing ethanolamines in good yield having a low product carbon footprint (PCF) based on energy at least partially derived from non-fossil resources, polyethyleneimine and ethanolamines obtained by the method of the present invention, preferably having a low product carbon footprint (PCT), and polyethyleneimine that is particularly stable when used in carbon recovery, and the use of the polyethyleneimine and ethanolamines of the present invention as CO2 absorbents in CO2 recovery methods. [Background technology]

[0003] Human-induced carbon dioxide and other greenhouse gases warm the Earth's atmosphere, leading to climate change. Global warming has various negative effects, including rising sea levels, increased risk of flooding, droughts, and other extreme weather events.

[0004] Therefore, at the 2015 Paris Climate Summit, the international community agreed to limit the rise in global temperature from pre-industrial levels to "well below" 2°C, and to strive to limit it to 1.5°C. The 1.5°C target was reaffirmed at COP27, the UN Climate Change Conference, in November 2022. This can only be achieved if greenhouse gas emissions decrease rapidly.

[0005] In addition to carbon dioxide (CO2), the most important anthropogenic greenhouse gas (GHG), other gases defined as greenhouse gases by the Intergovernmental Panel on Climate Change (IPCC) include CH4, SF6, N2O, hydrofluorocarbons (HFCs), and perfluorocarbons (PFCs). These various gases do not contribute equally to the greenhouse effect and differ in how long they remain in the atmosphere. To allow for comparison of the effects of these different greenhouse gases, the IPCC defined the so-called "global warming potential." This index represents the warming effect that a given amount of greenhouse gas has over a set period (usually 100 years) compared to CO2. For example, methane has a climate effect 28 times more severe than CO2, but methane does not remain in the atmosphere for nearly as long. The environmental impact of nitrous oxide is also almost 300 times greater than that of CO2. Thus, highly related greenhouse gases can be combined and calculated as a CO2 equivalent. The CO2 equivalent is abbreviated as "CO2e."

[0006] According to the Greenhouse Gas Protocol (WBCSD, WRI, 2011), greenhouse gas emissions are classified into so-called Scope 1, Scope 2, and Scope 3 parts.

[0007] Scope 1 refers to direct CO2e emissions arising from production processes at plants owned or controlled by the reporting company. This includes, for example, • Emissions from chemical reactions, • Emissions resulting from waste treatment that does not involve energy use (e.g., flares), • Emissions from fuel and residue incineration at our own process plants It originates from.

[0008] Scope 2 refers to indirect CO2e emissions resulting from the generation of purchased energy used as utilities by the company's own plants, such as electricity, steam, and heat and cooling, which are available through grid connections, for example.

[0009] Scope 3 upstream CO2e emissions are the sum of all indirect emissions resulting from the use of raw materials purchased from other suppliers, including, for example, indirect emissions from the transportation of fuel to the cradle, its generation, and extraction, consumed at all product manufacturing plants throughout the value chain. It is important to note that this can encompass the emissions of many companies far beyond one, as it must include the total emissions from the raw materials to the cradle. This sum of indirect emissions is also called backpack emissions.

[0010] Scope 3 downstream CO2e emissions include indirect greenhouse gas emissions that occur within a company's value chain, related to goods and services sold, and released after they leave the company's ownership or control. This includes, for example, emissions related to additional transport and conversion, as well as emissions related to final disposal waste at the end of the life cycle of the final product.

[0011] However, in the case of alkoxylated compounds and methods for preparing them, in this application, "material carbon" in polymer products is considered only in terms of additional CO2 emissions for Scope 3 downstream (end-of-life "graveyard") emissions; all other emissions, such as those related to transportation and use at the product end-user and consumer use stages, are outside the scope.

[0012] The product carbon footprint (PCF) summarizes the total greenhouse gas (GHG) emissions generated by a product at different stages of its lifecycle. For example, the cradle-to-gate (partial) PCF considers every stage from resource extraction, through the production of precursors and the creation of the final product itself, to its departure from the company's gate (including all direct GHG emissions from upstream Scope 1, 2, and 3 sources, including removals). The cradle-to-grave PCF covers the entire product lifecycle, including emissions from the use phase and end of life (including all direct GHG emissions from upstream and downstream Scope 1, 2, and 3 sources, including removals).

[0013] Figure 1 shows the definition of a system boundary that conforms to the GHG protocol.

[0014] Unless otherwise specified, PCF in this application refers to PCF from cradle to gate. In the case of alkoxylated compounds and methods for preparing the same, “total PCF from cradle to gate” means the total PCF from cradle to gate of the corresponding alkoxylated compound. Similarly, for other compounds of the present invention, “total PCF from cradle to gate” means the total PCF from cradle to gate of the corresponding compound.

[0015] However, with respect to the alkoxylated compounds of the present invention, the total PCF from cradle to grave of the alkoxylated compound according to the definition above is given, i.e., the "material carbon" in the polymer product is considered only for the additional CO2 emissions generated for Scope 3 downstream ("graveyard" at the end of life) emissions; all other emissions, such as those related to transportation and use at the product end-user and consumer use stages, are outside the scope.

[0016] One of the key factors in reducing CO2 emissions is quantitative knowledge about the amount of greenhouse gas emissions associated with a product along the production value chain and throughout its lifecycle. Product carbon footprint (PCF) can help find the answer.

[0017] Product carbon footprint (PCF) is the most established method for determining the climate impact of a product, and several methods for calculating PCF are known in the field.

[0018] For example, U.S. Patent Publication No. 2022 / 0107618 A1, U.S. Patent Publication No. 2022 / 0108327 A1, and U.S. Patent Publication No. 2022 / 0108326 A1 relate to a computer implementation method for determining the carbon footprint of products in production processes at manufacturing plants, more specifically, of products in interconnected production processes.

[0019] Product carbon footprints help identify, analyze, and, through appropriate means, eliminate or (ideally) completely avoid climate-related impacts arising in the form of greenhouse gas emissions.

[0020] Growing consumer interest in "green products" is leading numerous companies to manufacture and sell products with environmental attributes. Large retailers are beginning to urge their suppliers to clearly display the carbon footprint of their products.

[0021] The biodegradability of the alkoxylated compounds according to the present invention is determined based on currently valid OECD guidelines.

[0022] The OECD distinguishes six forms of biodegradation 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 / ). (i) Ultimate biodegradation (inorganization): This is the level of degradation achieved when the test compound is completely utilized by microorganisms, resulting in the generation of carbon dioxide, water, inorganic salts, and new microbial cellular components (biomass). (ii) Primary biodegradation (in vivo transformation): Modification of the chemical structure of a substance brought about by biological action, resulting in the loss of the substance's inherent properties. (iii) Easily biodegradable: Any classification of chemical substances that have passed a specified screening test for ultimate biodegradability; these tests are so rigorous that such compounds are expected to decompose easily and completely under aerobic conditions when in an aqueous environment. (iv) Intrinsic biodegradability: A classification of chemical substances for which there is clear evidence of biodegradation (primary or ultimate) in any biodegradation test. (v) Half-life (t0.5): The time it takes for 50% of the test substance to change when the change can be described by a first-order rate law; this is independent of the initial concentration. (vi) Evaporation time 50 (DT50): The time it takes for the initial concentration of the test substance to decrease by 50 percent.

[0023] The alkoxylated compounds according to the present invention are generally tested for their biodegradability in accordance with OECD 301B.

[0024] Test number 301: Ready biodegradability (https: / / www.oecd-ilibrary.org / environment / test-no-301-ready-biodegradability_9789264070349-en) This testing guideline describes six methods that enable screening for the biodegradability of chemicals in aerobic aqueous media. These methods are the DOC Die-Away (301A), CO2 generation (modified Sturm test) (301B), MITI(I) (Ministry of International Trade and Industry, Japan) (301C), closed bottle (301D), modified OECD screening (301E), and manometric respiratory measurement (301F).

[0025] A well-defined / described solution or suspension of the test substance is inoculated into an inorganic medium and incubated under aerobic conditions in darkness or diffuse light. The endogenous activity of the inoculum can be determined by running a parallel blank run with the inoculum present but without the test substance. A parallel run with a reference compound (aniline, sodium acetate, or sodium benzoate) is performed to verify that these procedures are working. Typically, this test lasts 28 days. At least two flasks or vessels containing the test substance + inoculum, and at least two flasks or vessels containing only the inoculum, must be used; a single vessel is sufficient for the reference compound. Generally, after degradation, parameters such as DOC, CO2 production, and oxygen consumption are determined. The pass level for easily biodegradable samples is 70% DOC removal and 60% ThOD or ThCO2 production by respiratory measurements. These pass values ​​must be reached within a 10-day window within the 28-day test period.

[0026] The ethylene glycol and propylene glycol parts (i.e., alkylene oxide units) in alkoxylated compounds have a significant impact on the product carbon footprint of the alkoxylated compound. Therefore, this objective is achieved by ethylene glycol and / or propylene glycol-based compounds (referred to as alkoxylated compounds in this invention, as there may be one or more additional alkylene glycols in addition to ethylene glycol and propylene glycol), while the ethylene oxide and / or propylene oxide used in the synthesis of the alkoxylated compound are prepared by the unique method of this invention.

[0027] Furthermore, ethylene oxide and propylene oxide are versatile starting materials for numerous downstream products such as polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines.

[0028] Polyethyleneimine (PEI) is a versatile polymer that can be used for a variety of purposes, including, but not limited to, detergents, adhesives, water treatment agents, and cosmetics. Furthermore, PEI is used in papermaking, flocculation processes, and as a raw material in the biotechnology field.

[0029] Ethanolamines are flammable, corrosive, colorless, viscous liquids produced by the reaction between ammonia and ethylene oxide (EO). Identified many years ago, ethanolamines are key components in numerous important product formulations, including cosmetics and personal hygiene applications, agricultural products, wood preservatives, soaps and detergents, and gas treatments. Ethanolamines can also be used in the production of nonionic detergents, emulsifiers, and soaps, as well as in emulsion paints, polishes, and cleansers. The commercially available types of ethanolamines mainly consist of three types: monoethanolamines (MEAs), diethanolamines (DEAs), and triethanolamines (TEAs). The formation of MEAs, DEAs, or TEAs depends on whether one, two, or three ethylene oxide molecules react with the ammonia molecule, and the product ratio can be adjusted by the raw material supply composition and processing conditions. MEAs, DEAs, and TEAs can be separated after synthesis, for example by distillation, as required by the application, to produce high-purity chemical materials on the order of 99% purity.

[0030] Furthermore, PEI, along with MEA, DEA, and / or TEA, are useful as carbon dioxide (CO2) capture agents. The amino groups of PEI react with CO2, thereby binding and removing CO2 from relevant exhaust gas sources, or even from the ambient air. The bound CO2 can be desorbed to concentrate carbon dioxide, enabling a certain degree of reuse of PEI, MEA, DEA, and / or TEA. Generally, the inherent loss of capture efficiency over time can potentially be compensated for with fresh materials, and efforts are ongoing to optimize overall CO2 capture performance through technological innovations in products and production processes. Scientists say there is high demand for these adsorbent materials because, according to them, several gigatons of CO2 must be removed from the atmosphere each year to meet climate targets.

[0031] However, the preparation process for ethanolamines, particularly polyethyleneimine (PEI), including its precursor ethyleneimine (EI) and the necessary raw materials, requires an extremely large amount of energy.

[0032] Ammonia is a key precursor in the preparation of MEA, and subsequently, it is a key precursor in the preparation of EI and PEI. Since the development of the Haber-Bosch process for ammonia preparation, the majority of ammonia has been produced by direct synthesis from hydrogen and nitrogen in the presence of catalysts, particularly iron-containing catalysts. In modern methods, large quantities of hydrogen are supplied by steam reforming, and therefore from natural gas.

[0033] Therefore, the preparation methods for ethanolamines and polyethyleneimines have adverse effects on their carbon footprint, including the consumption of fossil-derived natural resources and lots of energy from cradle to gate.

[0034] Vargese Anish Mathai et al., International Journal of Greenhouse Gas Control, vol.96, 3 March 2020, is a review of CO2 recovery absorbers functionalized with amine-supported polymers.

[0035] Weissermel Klaus et al., *Industrial Organic Chemistry*, 27 May 2003, pages 145-192, deals with the oxidation products of ethylene. In particular, ethanolamines are disclosed in Chapter 7.2.3 (page 159). It is mentioned that when ethylene oxide is reacted with ammonia, a mixture of three theoretically possible ethanolamines is formed with high selectivity (see also Table 7-5 on page 159).

[0036] U.S. Patent No. 6,495,609 B1 relates to the recovery of carbon dioxide in the process of producing ethylene oxide from ethylene. According to U.S. Patent No. 6,495,609 B1, a method for recovering carbon dioxide from the ethylene oxide production process is disclosed, in which the recovered carbon dioxide is used as a carbon source for ethanol synthesis. This carbon dioxide is used to generate a syngas flow, which is then used to produce methanol.

[0037] The UK Patent Application Publication No. 2,464,691A relates to the production of methanol from cellulosic / lignin materials, which are agricultural by-products. It discloses that cellulosic / lignin material by-products remaining after the harvest of agricultural products are converted to carbon dioxide by exothermic oxidation, and in another section of the synthesis plant, hydrogen gas is produced by electrolysis. The hydrogen gas is then reacted with carbon dioxide to produce methanol. [Overview of the project] [Problems that the invention aims to solve]

[0038] Accordingly, the object of the present invention is to provide environmentally friendly polyethyleneimines and ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, and an environmentally friendly method for producing them in good yield, while the method must use as little fossil-derived energy as possible. The ethanolamines and polyethyleneimines must be particularly useful for carbon recovery.

[0039] Polyethyleneimines and ethanolamines must not be derived from starting materials derived from biomass raw materials or biomass balance raw materials. In the sense of the present invention, carbon oxides such as CO and CO2 are considered biomass raw materials. For more information on biomass balance and biomass balance raw materials, see, for example, https: / / www.basf.com / global / documents / en / sustainability / we-produce-safely-and-efficiently / resources-and-ecosystems / BASFs_biomass-balance-approach.pdf. [Means for solving the problem]

[0040] This objective is achieved by a method for preparing polyethyleneimine, comprising the following steps: (a) A process of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting methanol in step (b) to ethylene, (d) A step of forming ethylene oxide by reacting the ethylene from step (c) with oxygen, (e) A step of converting the ammonia from step (a) into ethanolamines together with ethylene oxide from step (d) in one or more steps, (f) A step of separating monoethanolamine from the ethanolamines obtained in step (e); (g) A step of converting the monoethanolamine from step (f) to ethyleneimine, preferably by catalytic gas-phase synthesis. and (h) A step in which the ethyleneimine obtained in step (g) is polymerized into polyethyleneimine. Here, the hydrogen in step (a) and / or step (b) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably by electrolysis, uses energy that is at least in part derived from non-fossil resources.

[0041] The method of the present invention is not based on starting materials derived from biomass raw materials or biomass balance raw materials. [Brief explanation of the drawing]

[0042] [Figure 1] This shows the definition of a system boundary that conforms to the GHG protocol. [Figure 2] The PCF results for MEA are shown. [Figure 3a] The PCF results for PEI prepared by the liquid-phase method are shown. [Figure 3b] The PCF results for PEI prepared by the gas phase method are shown. [Figure 4] The PCF results for EO are shown below. [Figure 5] The PCF results for PO are shown. [Figure 6] The PCF results for scenario i) of alkoxylated compounds are shown. [Figure 7] The PCF results for scenario ii) of alkoxylated compounds are shown. [Figure 8] The PCF results for scenario iii) of alkoxylated compounds are shown. [Figure 9] Table 21 shows the data plots for alkoxylated compounds, representing the "predicted" PCF values ​​from cradle to grave. Here, "predicted" means that the PCF values ​​were calculated from the PCF correlation equation in Table 22 (Y-axis) and plotted against the PCF values ​​from Table 21. [Figure 10] Table 22 shows a plot of PCF calculation values ​​using the correlation formula, with E (EO content) set to 0 and using an average C (carbon content) of 60 wt%. [Modes for carrying out the invention]

[0043] Surprisingly, polyethyleneimines and ethanolamines prepared by the method of the present invention have been found to have higher overall product yields (described later) compared to conventional methods that start exclusively with hydrogen and carbon from fossil-derived sources, such as fossil-derived syngas and / or hydrocarbon cracking equipment feedstocks.

[0044] To address this objective, the relevant PCFs for polyethyleneimines, ethanolamines, and upstream compounds in the preparation of both were calculated based on the following guideline: “The Product Carbon Footprint Guideline for the Chemical Industry” launched by TfS (Together for Sustainability), Version 2.0, November 2022 (https: / / www.tfs-initiative.com / ) (hereinafter referred to as the “TfS Guideline”). This guideline is “audit-ready,” ISO compliant, GHG protocol approved, and “open source,” making it useful for industries worldwide that use chemical materials.

[0045] The applicant's proprietary Verbund system creates an efficient value chain extending from basic chemicals to consumer products. This enables the collection of reliable data on greenhouse gas (GHG) emissions generated by products within and beyond the Verbund, particularly by polyethyleneimines and ethanolamines, and upstream compounds in their preparation methods, across different stages of their lifecycle, especially from cradle to gate (scope 1, 2, and 3 upstream).

[0046] As described above, the preparation methods for polyethyleneimines, particularly the precursor ethyleneimine and ethanolamines, as well as ammonia and ethylene oxide, require a large amount of energy, and many of the steps (a) to (h) of the polyethyleneimine preparation method can be carried out by several alternative methods. The inventors have found a method for preparing polyethyleneimines, in which each step is optimized to obtain polyethyleneimines with a low carbon footprint, or at least prepared for that purpose.

[0047] Ethyleneimines (aziridines) are industrially produced, for example, from monoethanolamine via two commercial routes. The catalytic gas-phase dehydration method requires an oxide catalyst and extremely high temperatures (350-450°C) to induce dehydration and tri-ring closure. The liquid-phase method, on the other hand, converts monoethanolamine to its sulfate ester, which then undergoes base-induced sulfate elimination under relatively mild conditions. Conventional methods required the amination of 1,2-dichloroethane and the cyclization of 2-chloroethylamine.

[0048] According to the text, Ullmann's Encyclopedia of Industrial Chemistry, “Aziridines”, 2012 Wiley-VCH Verlag GmbH & Co.KGaA Weinheim; DOI:10.100204356007.a03 239.pub2, chapter 4.4, the large energy requirement is considered a disadvantage of catalytic gas-phase synthesis, and therefore this method is not very attractive for the preparation of polyethyleneimines with a low carbon footprint. Furthermore, the relatively low selectivity of “up to 90%” and only “40-80%” for monoethanolamine conversion necessitates the recycling of large amounts of unconverted monoethanolamine with a large energy requirement (heating / cooling / heating), and in addition, it becomes necessary to remove high-boiling-point amine components as waste material. The carbon content of the waste material resulting from the relatively low overall yield adds a large amount of CO2e emissions to the PCF.

[0049] The commercial liquid-phase method for "aziridine," as described in Chapter 4.3 of Ullmann's Encyclopedia of Industrial Chemistry, achieves a yield of 85-90% and therefore produces significantly less waste compared to other methods. The disadvantage of the above liquid-phase method, which is the relatively high cost of raw materials, is not the focus of this invention.

[0050] However, a rigorous analysis of various different methods and processes for obtaining polyethyleneimine, and a comparison with alternative methods, revealed, surprisingly, that the greenhouse gas (GHG) emissions generated by the conversion of monoethanolamine to ethyleneimine by catalytic gas-phase synthesis (step g)) are significantly lower than those generated by the conversion of monoethanolamine to ethyleneimine by other methods. Therefore, the PCF of ethyleneimine, and consequently the polyethyleneimine obtained by catalytic gas-phase synthesis, are significantly lower than those of ethyleneimine and polyethyleneimine obtained by other methods (where only step g) differs in the method for preparing ethyleneimine and polyethyleneimine).

[0051] Furthermore, the inventors have found that when ethyleneimine prepared by catalytic gas-phase synthesis is used as a base, the starting materials for preparing ammonia and ethylene oxide, which are the raw materials for ethanolamines including monoethanolamine necessary for the synthesis of ethyleneimine and polyethyleneimine, can be obtained, at least in part, by water splitting, preferably by electrolysis, based at least in part on electricity generated from non-fossil resources, thereby obtaining polyethyleneimine with particularly low PCF.

[0052] In the sense of the present invention, the Product Carbon Footprint (PCF) summarizes the total greenhouse gas (GHG) emissions generated by a product at different stages of its lifecycle. The Cradle-to-Gate Product Carbon Footprint (PCT) summarizes the total greenhouse gas (GHG) emissions generated by a product across Scope 1, 2, and Scope 3 upstream, as defined in the TfS Guidelines described above and as shown by the relevant boundary conditions in Figure 1.

[0053] Unless otherwise specified, PCF in this application refers to PCF from the cradle to the gate. "Total PCF from the cradle to the gate" means the total PCF from the cradle to the gate of the corresponding compound.

[0054] One of the most relevant factors determining PCF is the input ratio and backpack discharge rate of the starting materials used, as well as the input ratio and backpack discharge rate of the energy required for each production step of a particular product. In the present invention's method for preparing ethanolamines and polyethyleneimines, all steps (a) to (h), and the step of generating hydrogen energy in the form of heating energy (e.g., steam) and / or electricity, are used as contributing factors to PCF.

[0055] In all steps (a) to (h) of the method of the present invention and in the step of hydrogen production, energy in the form of heating energy (e.g., steam) and / or electricity is used. According to the method of the present invention, the energy (electricity) used to produce hydrogen used in step (a) and / or (b), preferably the energy used to produce hydrogen used in step (a) and / or (b) and one or more of the energy used in steps (a) to (h) is generated in part from non-fossil resources.

[0056] A rigorous analysis of the different method steps for obtaining polyethyleneimine according to the present invention has revealed that, in order of energy requirements for the product obtained in the steps, the most relevant energy-requiring steps are step (g, the hydrogen-generating step), as well as steps (a), (b), (c), and (f). Therefore, preferably, the energy used in the hydrogen-generating step and step (g), more preferably the energy used in the hydrogen-generating steps, (g), and (c), most preferably the energy used in the hydrogen-generating steps and steps (g), (c), and (b), even more preferably the energy used in the hydrogen-generating steps and steps (a), (b), (c), (f), and (g), and still most preferably the energy used in the hydrogen-generating steps and steps (a) to (h) is at least partially derived from non-fossil resources in the method of the present invention.

[0057] Surprisingly, it was found that steps (c) and (b), as well as steps (a) and (f), were not the only steps with extremely high energy requirements in the polyethyleneimine preparation method; steps (c) and (b), and steps (a) and (f) were also high. Therefore, polyethyleneimines—and ethanolamines—with particularly low total product carbon footprints from cradle to gate can be achieved only if the energy used in at least step (c), and preferably at least steps (c) and (b), and more preferably at least steps (c), (b), (a) and (f) (in addition to the hydrogen-generating steps and step (g)) is at least partially derived from non-fossil resources.

[0058] According to TfS requirements, the PCF of the final product must take into account all processing steps leading up to the production of the final finished product—and therefore, those skilled in the art would not expect highly processed products such as ethanolamines and polyethyleneimines to achieve a low cradle-to-gate total product carbon footprint, as will be discussed later. Clearly, these products require energy-intensive starting materials and numerous subsequent energy-intensive processing steps.

[0059] However, the use of at least some energy derived from non-fossil resources should be considered insufficient to obtain particularly low cradle-to-gate PCF of polyethyleneimine. In addition, minimizing the yield at each step of the method and, consequently, the generation of waste, is a strong leverage. Another important factor is the conversion of monoethanolamine to ethyleneimine by catalytic gas-phase synthesis, as claimed in step (g) of the method of the present invention.

[0060] The term "at least part from non-fossil resources" means that, in further embodiments of the present invention, particularly with respect to the method for preparing polyethyleneimine, the method for preparing ethanolamines, and all of the methods of the present invention, some of the energy may still be generated from fossil fuels, preferably natural gas, because the carbon dioxide emissions per megajoule of energy produced by the combustion of natural gas are far less than those from the combustion of coal. However, the amount of energy produced from fossil fuels in the methods of the present invention must be as small as possible, preferably 50% or less, preferably 30% or less, most preferably 20% or less, and even more preferably 10% or less. In one embodiment, the energy is generated exclusively from non-fossil resources.

[0061] More preferably, at least a portion of the energy used in the method of the present invention is utilized from exothermic chemical methods other than the method steps of the present invention (typical examples: production of acrylic acid, formaldehyde, or ethylene oxide), for example, from excess energy generated in a chemical "Verbund" production setup that distributes excess energy, such as steam, to endothermic treatment consumers. The excess steam can replace steam generated by fossil fuels and can be allocated CO2e credits as an exothermic treatment source, thus enabling the CO2 balance to be tightened as described in the "TfS PCF Guidelines". Such a Verbund plant is preferably supplied with additional energy generated from non-fossil resources.

[0062] Various methods for certifying and transporting "energy source mixtures" are set up in accordance with local legislation. Certificates such as "non-fossil fuel certificate agreements" are a common practice for the proportion of non-fossil energy used in industrial production and the transport of related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / ).

[0063] More preferably, in further embodiments of the present invention, particularly with respect to the method for preparing polyethyleneimine, the method for preparing ethanolamines, and all of the methods of the present invention, at least 50%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90%, and most preferably 100% of the total energy input required for use in the methods of the present invention is derived from non-fossil resources.

[0064] Preferably, the energy is generated at least in part from non-fossil resources selected from solar energy (heat, photovoltaic and concentrated solar thermal power), wind power, hydropower (tidal, wave, hydroelectric dams, in-river hydrokinetics), geothermal energy, heat recovered by heat pumps, bioenergy (biofuels, biomass), a renewable portion of waste energy sources, nuclear energy, and mixtures thereof.

[0065] In further embodiments, the energy is generated at least in part from non-fossil resources selected from renewable resources, preferably solar energy (heat, photovoltaic and concentrated solar thermal power), wind power, hydropower (tidal, wave, hydroelectric dams, river fluid dynamics), geothermal energy, heat recovered by heat pumps, bioenergy (biofuels, biomass), renewable portions of waste, and mixtures thereof.

[0066] The types of energy resources described above are generally known to those skilled in the art. Preferred energy resources will be discussed later.

[0067] The polyethyleneimine preparation method of the present invention reduces greenhouse gas (GHG) emissions generated by polyethyleneimine across Scope 1, 2, and Scope 3 upstream (from cradle to gate), i.e., the total product carbon footprint (PCF) of polyethyleneimine from cradle to gate, by preferably 50% or more compared to the product carbon footprint of typically prepared polyethyleneimine.

[0068] In the sense of the present invention, polyethyleneimine prepared typically or by conventional methods preferably means that hydrogen and syngas are provided by steam reforming of natural gas, and the conversion from monoethanolamine to ethyleneimine in step (g) of the present invention is carried out by a liquid-phase method, and therefore, non-fossil energy is not mainly used in the conventional method.

[0069] A preferred method for preparing polyethyleneimine of the present invention, wherein polyethyleneimine is obtained in step (h) having a total product carbon footprint from cradle to gate of generally <8.0 kg CO2e / polyethyleneimine 1 kg, preferably <7.0 kg CO2e / polyethyleneimine 1 kg, more preferably <6 kg CO2e / polyethyleneimine 1 kg, even more preferably <5 kg CO2e / polyethyleneimine 1 kg, most preferably <4.0 kg CO2e / polyethyleneimine 1 kg, even more preferably <3.0 kg CO2e / polyethyleneimine 1 kg, still more preferably <2.0 kg CO2e / polyethyleneimine 1 kg, and most preferably <1.5 kg CO2e / polyethyleneimine 1 kg. This means that the greenhouse gas (GHG) emissions generated by polyethyleneimine according to the method of the present invention across Scope 1, 2 and Scope 3 upstream (from cradle to gate) are generally <8.0 kg CO2e / 1 kg polyethyleneimine, preferably <7.0 kg CO2e / 1 kg polyethyleneimine, more preferably <6 kg CO2e / 1 kg polyethyleneimine, even more preferably <5 kg CO2e / 1 kg polyethyleneimine, most preferably <4.0 kg CO2e / 1 kg polyethyleneimine, even more preferably <3.0 kg CO2e / 1 kg polyethyleneimine, still more preferably <2.0 kg CO2e / 1 kg polyethyleneimine, and most preferably <1.5 kg CO2e / 1 kg polyethyleneimine.

[0070] In this invention, the product carbon footprint given per kgCO2e / kg of product refers to the active product (100% product). For example, when preparing a 50 wt.% aqueous PEI solution, the total product carbon footprint from cradle to gate considers only the active product, which does not contain water or other impurities.

[0071] The present invention further relates to polyethyleneimines obtainable by the polyethyleneimine preparation method according to the present invention.

[0072] (i) Hydrogen obtained at least in part by hydrolysis, preferably by electrolysis, and (ii) based on energy produced at least in part from non-fossil resources, preferably enters twice into the value chain process according to the present invention for the production of ethanolamines and polyethyleneimine, namely in step (a) (production of ammonia) and in step (b) (production of methanol, which is necessary as a supply source for producing ethylene). Furthermore, the carbon source for the production of ethanolamines and polyethyleneimine, namely in step (b) (production of methanol), is also carbon oxide, preferably carbon dioxide. Accordingly, the byproduct spectra of ammonia and methanol used in the method for preparing ethanolamines and polyethyleneimine according to the present invention differ from the byproduct spectra of ammonia and methanol obtained by conventional methods (i.e., using synthesis gas "singas," which is a combination of various amounts of H2, CO, and CO2 often derived from gasified coal or natural gas). For example, methanol obtained by conventional methods generally contains more methylformiate, acetone, and higher alcohols (≧C3) than methanol and ammonia obtained by the method according to the present invention, and ammonia obtained by conventional methods generally contains more sulfur compounds and unsaturated hydrocarbon impurities. Therefore, the by-product spectrum of ethylene produced by cracking fossil hydrocarbon raw materials such as naphtha or natural gas used in conventional ethylene oxide is even more different from that of ethylene oxide according to the present invention.

[0073] The different product ranges of ethylene, both ammonia and methanol, are also reflected in the downstream products, namely the ethanolamines and polyethyleneimines obtained by this invention.

[0074] Surprisingly, it was found that polyethyleneimines obtained by the method of the present invention are further characterized by a different ratio of primary, secondary, and tertiary amino groups compared to polyethyleneimines obtained by conventional methods. In the polyethyleneimines prepared by the present invention, the ratio of secondary amino groups is increased at the expense of the ratio of primary amino groups. The aforementioned ratio of primary, secondary, and tertiary amino groups in the polyethyleneimines of the present invention is beneficial to the stability of polyethyleneimines during carbon recovery (under conditions that appear during exposure cycles up to, for example, 110°C during the CO2 desorption stage, primary amino groups generally decompose faster than secondary amino groups).

[0075] The present invention further relates to polyethyleneimine having a total product carbon footprint from cradle to gate of <8.0 kg CO2e / polyethyleneimine per kg, preferably <7.0 kg CO2e / polyethyleneimine per kg, more preferably <6 kg CO2e / polyethyleneimine per kg, even more preferably <5 kg CO2e / polyethyleneimine per kg, most preferably <4.0 kg CO2e / polyethyleneimine per kg, even more preferably <3.0 kg CO2e / polyethyleneimine per kg, still more preferably <2.0 kg CO2e / polyethyleneimine per kg, and most preferably <1.5 kg CO2e / polyethyleneimine per kg. This application teaches all the steps necessary to obtain polyethyleneimine having the specific total product carbon footprint from cradle to gate mentioned.

[0076] Several carbon labels are known that display the PCF of a given product. The Carbon Reduction Label, the world's first carbon label, shows the carbon footprint embodied in a product and was first introduced in the UK by the Carbon Trust in 2006. The guideline used in this application as the basis for calculating the total PCF from cradle to gate: “The Product Carbon Footprint Guideline for the Chemical Industry” launched by TfS (Together for Sustainability), Version 2.0, November 2022 (TfS Guideline) is “open source,” meaning it is available to anyone. Therefore, a person skilled in the art can calculate the specific product carbon footprint of polyethyleneimine prepared by different methods using raw materials and energy sources available at a particular location, and polyethyleneimine prepared by different methods with different material and energy inputs can be clearly distinguished by their different product carbon footprints from cradle to gate.

[0077] Preferably, the polyethyleneimine preparation method of the present invention provides ammonia obtained in step (a) having a total cradle-to-gate product carbon footprint of generally <0.6 kg CO2e / 1 kg ammonia, preferably <0.4 kg CO2e / 1 kg ammonia, and more preferably <0.15 kg CO2e / 1 kg ammonia. This means that the greenhouse gas (GHG) emissions generated by the ammonia according to the method of the present invention across Scope 1, 2 and Scope 3 upstream (cradle-to-gate) are generally <0.6 kg CO2e / 1 kg ammonia, preferably <0.4 kg CO2e / 1 kg ammonia, and more preferably <0.15 kg CO2e / 1 kg ammonia.

[0078] The present invention further relates to ammonia having a total cradle-to-gate product carbon footprint of <0.6 kg CO2e / 1 kg of ammonia, preferably <0.4 kg CO2e / 1 kg of ammonia, and more preferably <0.15 kg CO2e / 1 kg of ammonia. This application teaches all the steps necessary to obtain ammonia having the specific cradle-to-gate total product carbon footprint mentioned.

[0079] More preferably, the polyethyleneimine preparation method of the present invention, wherein the ethylene oxide obtained in step (d) has a total product carbon footprint from cradle to gate of generally <1.2 kg CO2e / 1 kg of ethylene oxide, preferably <0.8 kg CO2e / 1 kg of ethylene oxide, and more preferably <0.6 kg CO2e / 1 kg of ethylene oxide. This means that the greenhouse gas (GHG) emissions generated by the ethylene oxide according to the method of the present invention across Scope 1, 2 and Scope 3 upstream (from cradle to gate) are generally <1.2 kg CO2e / 1 kg of ethylene oxide, preferably <0.8 kg CO2e / 1 kg of ethylene oxide, and more preferably <0.6 kg CO2e / 1 kg of ethylene oxide.

[0080] The present invention further relates to ethylene oxide having a total cradle-to-gate product carbon footprint of <1.2 kg CO2e / ethylene oxide 1 kg, preferably <0.8 kg CO2e / ethylene oxide 1 kg, more preferably <0.6 kg CO2e / ethylene oxide 1 kg. This application teaches all the steps necessary to obtain ethylene oxide having the specific cradle-to-gate product carbon footprint mentioned.

[0081] Furthermore, more preferably, in the polyethyleneimine preparation method of the present invention, ethanolamines obtained in step (e) having a total cradle-to-gate product carbon footprint of generally <1.6 kg CO2e / ethanolamines per 1 kg, preferably <1.2 kg CO2e / ethanolamines per 1 kg, more preferably <0.9 kg CO2e / ethanolamines per 1 kg. This means that the greenhouse gas (GHG) emissions generated by the ethanolamines according to the method of the present invention across Scope 1, 2 and Scope 3 upstream (cradle-to-gate) are generally <1.6 kg CO2e / ethanolamines per 1 kg, preferably <1.2 kg CO2e / ethanolamines per 1 kg, more preferably <0.9 kg CO2e / ethanolamines per 1 kg.

[0082] The present invention further relates to ethanolamines having a total cradle-to-gate product carbon footprint of <1.6 kg CO2e / ethanolamines per 1 kg, preferably <1.2 kg CO2e / ethanolamines per 1 kg, and more preferably <0.9 kg CO2e / ethanolamines per 1 kg. This application teaches all the steps necessary to obtain ethanolamines having the specific cradle-to-gate product carbon footprints mentioned.

[0083] Most preferably, the polyethyleneimine obtained in step (g) of the polyethyleneimine preparation method of the present invention having a total product carbon footprint from cradle to gate of generally <7.5 kg CO2e / 1 kg of ethyleneimine, more preferably <6.5 kg CO2e / 1 kg of ethyleneimine, and most preferably 4.5 kg CO2e / 1 kg of ethyleneimine. This means that the greenhouse gas (GHG) emissions generated by the ethyleneimine according to the method of the present invention across Scope 1, 2 and Scope 3 upstream (from cradle to gate) are preferably <7.5 kg CO2e / 1 kg of ethyleneimine, more preferably <6.5 kg CO2e / 1 kg of ethyleneimine, and most preferably 4.5 kg CO2e / 1 kg of ethyleneimine.

[0084] The present invention further relates to ethyleneimine having a cradle-to-gate total product carbon footprint of <7.5 kg CO2e / ethyleneimine per kg, more preferably <6.5 kg CO2e / ethyleneimine per kg, and most preferably 4.5 kg CO2e / ethyleneimine per kg. This application teaches all the steps necessary to obtain ethyleneimine having the specific cradle-to-gate total product carbon footprint mentioned.

[0085] Those skilled in the art know that products in the “ammonia value chain” (such as ethanolamines, ethyleneimine, and polyethyleneimine) are generally highly correlated with emissions right at the beginning of this crucial value chain. Therefore, when you add up the emissions from the various energy-intensive process steps required to obtain the downstream end products that are reflected in the PCF of ethanolamines, ethyleneimine, and polyethyleneimine, the final PCF figures for these highly processed products in the ammonia value chain should be extremely high. Consequently, it was entirely unexpected that ethanolamines, ethyleneimine, and polyethyleneimine, products far down the “ammonia value chain,” could provide such a low cradle-to-gate total product carbon footprint as described above.

[0086] The present invention preferably relates to a method for preparing polyethyleneimine, wherein the method comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, wherein the ammonia obtained in step (a) has a total product carbon footprint from cradle to gate of preferably <0.6 kg CO2e / 1 kg of ammonia, preferably <0.4 kg CO2e / 1 kg of ammonia, and more preferably <0.15 kg CO2e / 1 kg of ammonia. (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting methanol in step (b) to ethylene, (d) A step of forming ethylene oxide by reacting the ethylene from step (c) with oxygen, and a step of having a total product carbon footprint from cradle to gate of the ethylene oxide obtained in step (e) having a carbon footprint of <1.2 kg CO2e / 1 kg of ethylene oxide, preferably <0.8 kg CO2e / 1 kg of ethylene oxide, more preferably <0.6 kg CO2e / 1 kg of ethylene oxide. (e) A step of converting the ammonia from step (a) together with the ethylene oxide from step (d) to ethanolamines in one or more steps, wherein the ethanolamines obtained in step (e) preferably have a total product carbon footprint from cradle to gate of <1.6 kg CO2e / 1 kg of ethanolamines, preferably <1.2 kg CO2e / 1 kg of ethanolamines, and more preferably <0.9 kg CO2e / 1 kg of ethanolamines. (f) A step of separating monoethanolamine from the ethanolamines obtained in step (e); (g) A step of converting the monoethanolamine from step (f) to ethyleneimine by catalytic gas-phase synthesis, wherein the ethyleneimine obtained in step (g) preferably has a total product carbon footprint from cradle to gate of <7.5 kg CO2e / ethyleneimine 1 kg, more preferably <6.5 kg CO2e / ethyleneimine 1 kg, and most preferably 4.5 kg CO2e / ethyleneimine 1 kg. and (h) A step of polymerizing the ethyleneimine obtained in step (g) into polyethyleneimine, wherein the polyethyleneimine obtained in step (i) preferably has a total product carbon footprint from cradle to gate of <8.0 kg CO2e / polyethyleneimine 1 kg, preferably <7.0 kg CO2e / polyethyleneimine 1 kg, more preferably <6 kg CO2e / polyethyleneimine 1 kg, even more preferably <5 kg CO2e / polyethyleneimine 1 kg, most preferably <4.0 kg CO2e / polyethyleneimine 1 kg, even more preferably <3.0 kg CO2e / polyethyleneimine 1 kg, still more preferably <2.0 kg CO2e / polyethyleneimine 1 kg, and most preferably <1.5 kg CO2e / polyethyleneimine 1 kg. Includes, The hydrogen in process (a) and / or process (b) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably by electrolysis, uses energy that is at least in part derived from non-fossil resources, and the hydrogen in process (a) and / or process (b) has a cradle-to-gate total product carbon footprint of preferably <5 kg CO2e / 1 kg of hydrogen, preferably <4.6 kg CO2e / 1 kg of hydrogen, more preferably <3.5 kg CO2e / 1 kg of hydrogen, most preferably <2.5 kg CO2e / 1 kg of hydrogen, and even more preferably <2 kg CO2e / 1 kg of hydrogen, and more preferably the hydrogen in process (a) and process (b) has a cradle-to-gate total product carbon footprint of preferably <5 kg CO2e / 1 kg of hydrogen, preferably <4.6 kg CO2e / 1 kg of hydrogen, more preferably <3.5 kg CO2e / 1 kg of hydrogen, most preferably <2.5 kg CO2e / 1 kg of hydrogen, and even more preferably <2 kg This relates to a method having a total product carbon footprint from cradle to gate for 1 kg of CO2e / hydrogen.

[0087] A preferred method for preparing polyethyleneimine, wherein the ammonia is obtained in step (a) having a total product carbon footprint from cradle to gate of <0.6 kg CO2e / 1 kg ammonia, preferably <0.4 kg CO2e / 1 kg ammonia, and more preferably <0.15 kg CO2e / 1 kg ammonia.

[0088] A more preferable method for preparing polyethyleneimine, wherein ammonia is obtained in step (a) having a total product carbon footprint from cradle to gate of <0.6 kg CO2e / ammonia 1 kg, preferably <0.4 kg CO2e / ammonia 1 kg, more preferably <0.15 kg CO2e / ammonia 1 kg, and ethanolamines are obtained in step (e) having a total product carbon footprint from cradle to gate of <1.6 kg CO2e / ethanolamines 1 kg, preferably <1.2 kg CO2e / ethanolamines 1 kg, more preferably <0.9 kg CO2e / ethanolamines 1 kg.

[0089] The most preferred method for preparing polyethyleneimine is to obtain ammonia obtained in step (a) having a total product carbon footprint from cradle to gate of <0.4 kg CO2e / 1 kg of ammonia, more preferably <0.15 kg CO2e / 1 kg of ammonia, ethanolamines obtained in step (e) having a total product carbon footprint from cradle to gate of <1.6 kg CO2e / 1 kg of ethanolamines, more preferably <1.2 kg CO2e / 1 kg of ethanolamines, more preferably <0.9 kg CO2e / 1 kg of ethanolamines, and ethyleneimine obtained in step (g) having a total product carbon footprint from cradle to gate of <7.5 kg CO2e / 1 kg of ethyleneimine, more preferably <6.5 kg CO2e / 1 kg of ethyleneimine, most preferably 4.5 kg CO2e / 1 kg of ethyleneimine.

[0090] Furthermore, in the most preferred method for preparing polyethyleneimine, ammonia obtained in step (a) having a total product carbon footprint from cradle to gate of <0.4 kg CO2e / ammonia 1 kg, more preferably <0.15 kg CO2e / ammonia 1 kg, ethanolamines obtained in step (e) having a total product carbon footprint from cradle to gate of <1.6 kg CO2e / ethanolamines 1 kg, preferably <1.2 kg CO2e / ethanolamines 1 kg, more preferably <0.9 kg CO2e / ethanolamines 1 kg, ethyleneimine obtained in step (g) having a total product carbon footprint from cradle to gate of <7.5 kg CO2e / ethyleneimine 1 kg, more preferably <6.5 kg CO2e / ethyleneimine 1 kg, most preferably 4.5 kg CO2e / ethyleneimine 1 kg, and preferably <7.0 kg CO2e / polyethyleneimine 1 kg, more preferably <6 kg CO2e / polyethyleneimine 1 kg, even more preferably <5 kg Polyethyleneimine obtained in process (h) having a total product carbon footprint from cradle to gate of 1 kg of CO2e / polyethyleneimine, most preferably <4.0 kg CO2e / polyethyleneimine, even more preferably <3.0 kg CO2e / polyethyleneimine, still more preferably <2.0 kg CO2e / polyethyleneimine, and most preferably <1.5 kg CO2e / polyethyleneimine.

[0091] The present invention further relates to a method for preparing ethanolamines, wherein the method comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, wherein the ammonia obtained in step (b) has a cradle-to-gate total product carbon footprint of preferably <0.4 kg CO2e / 1 kg of ammonia, more preferably <0.15 kg CO2e / 1 kg of ammonia. (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting methanol in step (b) to ethylene, (d) A step of forming ethylene oxide by reacting the ethylene from step (c) with oxygen, wherein the ethylene oxide obtained in step (d) preferably has a total product carbon footprint from cradle to gate of <1.2 kg CO2e / 1 kg of ethylene oxide, preferably <0.8 kg CO2e / 1 kg of ethylene oxide, and more preferably <0.6 kg CO2e / 1 kg of ethylene oxide. (e) A step of converting the ammonia from step (a) together with the ethylene oxide from step (d) to ethanolamines in one or more steps, wherein the ethanolamines obtained in step (f) preferably have a total product carbon footprint from cradle to gate of <1.6 kg CO2e / 1 kg of ethanolamines, preferably <1.2 kg CO2e / 1 kg of ethanolamines, and more preferably <0.9 kg CO2e / 1 kg of ethanolamines. Includes, The hydrogen in process (a) and / or process (b) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably by electrolysis, uses energy that is at least in part derived from non-fossil resources, and the hydrogen in process (a) and / or process (b) has a cradle-to-gate total product carbon footprint of preferably <5 kg CO2e / 1 kg of hydrogen, preferably <4.6 kg CO2e / 1 kg of hydrogen, more preferably <3.5 kg CO2e / 1 kg of hydrogen, most preferably <2.5 kg CO2e / 1 kg of hydrogen, and even more preferably <2 kg CO2e / 1 kg of hydrogen, and more preferably the hydrogen in process (a) and process (b) has a cradle-to-gate total product carbon footprint of preferably <5 kg CO2e / 1 kg of hydrogen, preferably <4.6 kg CO2e / 1 kg of hydrogen, more preferably <3.5 kg CO2e / 1 kg of hydrogen, most preferably <2.5 kg CO2e / 1 kg of hydrogen, and even more preferably <2 kg This relates to a method having a total product carbon footprint from cradle to gate for 1 kg of CO2e / hydrogen.

[0092] A preferred method for preparing ethanolamines, wherein the ethylene oxide is obtained in step (d) having a total product carbon footprint from cradle to gate of <1.2 kg CO2e / 1 kg of ethylene oxide, more preferably <0.8 kg CO2e / 1 kg of ethylene oxide, and most preferably <0.8 kg CO2e / 1 kg of ethylene oxide.

[0093] A preferred method for preparing ethanolamines, wherein ammonia is obtained in step (a) having a total product carbon footprint from cradle to gate of <0.4 kg CO2e / 1 kg of ammonia, more preferably <0.15 kg CO2e / 1 kg of ammonia.

[0094] A preferred method for preparing ethanolamines, wherein ammonia is obtained in step (a) having a total product carbon footprint from cradle to gate of <0.4 kg CO2e / 1 kg ammonia, more preferably <0.15 kg CO2e / 1 kg ammonia, and ethylene oxide is obtained in step (d) having a total product carbon footprint from cradle to gate of <1.2 kg CO2e / 1 kg ethylene oxide, more preferably <0.8 kg CO2e / 1 kg ethylene oxide, more preferably <0.6 kg CO2e / 1 kg ethylene oxide.

[0095] The most preferred method for preparing ethanolamines is ammonia obtained in step (a) having a total product carbon footprint from cradle to gate of <0.4 kg CO2e / 1 kg ammonia, more preferably <0.15 kg CO2e / 1 kg ammonia, ethylene oxide obtained in step (d) having a total product carbon footprint from cradle to gate of <1.2 kg CO2e / 1 kg ethylene oxide, preferably <0.8 kg CO2e / 1 kg ethylene oxide, more preferably <0.6 kg CO2e / 1 kg ethylene oxide, and ethanolamines obtained in step (e) having a total product carbon footprint from cradle to gate of <1.6 kg CO2e / 1 kg ethanolamines, more preferably <1.2 kg CO2e / 1 kg ethanolamines, more preferably <0.9 kg CO2e / 1 kg ethanolamines.

[0096] The method for preparing ethanolamines according to the present invention reduces greenhouse gas (GHG) emissions generated by ethanolamines across Scope 1, 2, and Scope 3 upstream (from cradle to gate), i.e., the total product carbon footprint (PCF) of ethanolamines from cradle to gate, by preferably 50% or more compared to the product carbon footprint of ethanolamines prepared in the present invention.

[0097] In the sense of the present invention, ethanolamines prepared typically or by conventional methods preferably mean that hydrogen and syngas are provided by steam reforming of natural gas.

[0098] The present invention further relates to ethanolamines obtainable by the preparation method for ethanolamines according to the present invention. The total product carbon footprint from cradle to gate of ethanolamines obtainable by the method according to the present invention is described above.

[0099] As described above, the different by-product spectra of ammonia and methanol obtained by the method of the present invention, compared with the by-product spectra of fossil-derived ammonia and fossil-derived syngas and / or hydrocarbon cracking equipment sources obtained by conventional methods, are also reflected in the ethanolamines (downstream products) according to the present invention.

[0100] The method for preparing polyethyleneimine includes steps (a) to (h) and the generation of hydrogen, as described above.

[0101] Preparation (generation) of hydrogen: The hydrogen of steps (a) and / or (b), preferably steps (a) and (b), is obtained at least in part by hydrospraying, preferably by electrolysis, which uses energy that is at least in part derived from non-fossil resources: This process relates to the provision of hydrogen, at least in part, by water splitting, preferably by electrolysis, which uses energy that is at least partly derived from non-fossil resources.

[0102] The term "at least part by water splitting" means that some of the hydrogen may still be produced by other means, generally by steam reforming of natural gas and / or other light hydrocarbons, partial oxidation of heavy hydrocarbons, and coal gasification, preferably by steam reforming of natural gas and / or other light hydrocarbons. However, the amount of hydrogen produced by other means other than water splitting in steps (a) and / or (b) should be as small as possible.

[0103] Preferably, in step (a) of the method of the present invention, ≤50%, preferably ≤30%, most preferably ≤20%, and even more preferably ≤10% of the hydrogen is produced by a method other than hydrolysis. In one embodiment, the hydrogen in step (a) is produced exclusively by hydrolysis, preferably by electrolysis.

[0104] Preferably, in step (b) of the method of the present invention, ≤50%, preferably ≤30%, most preferably ≤20%, and even more preferably ≤10% of the hydrogen is produced by a method other than hydrolysis. In one embodiment, the hydrogen in step (b) is produced exclusively by hydrolysis, preferably by electrolysis.

[0105] More preferably, in steps (a) and (b) of the method of the present invention, ≤50%, preferably ≤30%, most preferably ≤20%, and even more preferably ≤10% of the hydrogen is produced by methods other than hydrolysis. In one embodiment, the hydrogen in step (a) is produced exclusively by hydrolysis, preferably by electrolysis.

[0106] Preferably, the hydrogen of step (a) and / or step (b) has a total product carbon footprint from cradle to gate of <5 kg CO2e / 1 kg of hydrogen, preferably <4.6 kg CO2e / 1 kg of hydrogen, more preferably <3.5 kg CO2e / 1 kg of hydrogen, most preferably <2.5 kg CO2e / 1 kg of hydrogen, and even more preferably <2 kg CO2e / 1 kg of hydrogen.

[0107] The term "at least partly from non-fossil resources" is explained above.

[0108] Alkoxylated compounds such as polyalkylene glycols and compounds containing alkylene glycol groups are used in a variety of industrial fields, for example, in home care products, cosmetics, pharmaceutical products, food products, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, lubricating greases, thermal conductive fluids, metalworking oils and transmission fluids, defoamers, softeners, rheological modifiers, emulsifiers, dispersants, thickeners, stabilizers, pesticides such as metalworking oils and insecticides, textile and leather auxiliaries, bioprocessing, fuel performance packaging, and poly(urethane) adhesives, where they exhibit high performance when used.

[0109] A review of polyalkylene glycols is provided in Chem. Rev. 2016, 116, 2170-2243. It states that polyalkylene glycols are aliphatic polyethers generated by ring-opening polymerization (ROP) of epoxide monomers, particularly ethylene oxide (EO), propylene oxide (PO), and to a lesser extent, butylene oxide (BO). The characteristic properties of polyether-derived materials stem from their unique skeleton, specifically their high mobility leading to a low glass transition below -60°C, and their hydrophilicity in bonding to COC bonds.

[0110] Poly(ethylene glycol) (or polyethylene glycol) is a biocompatible polymer that has become the gold standard for pharmaceutical, cosmetic, and medical applications, and is used in an extremely wide range of products, from skincare products to tablet formulations and food additives. Polymers of EO with high molecular weights are generally called poly(ethylene) oxide (PEO) or sometimes poly(oxyethylene) (POE), while polymers with a molecular weight of less than 30,000 g / mol are called poly(ethylene glycol) (PEG). The abbreviation mPEG refers to PEG with a monomethyl ether terminus, and its single terminal hydroxyl group can be further functionalized for block copolymer synthesis or bioconjugation with PEG, commonly known as "pegylation."

[0111] Poly(propylene oxide) (PPO), often referred to as poly(propylene glycol) (or polypropylene glycol) (PPG) when its molecular weight is low, is generally produced by ROP of PO. In contrast to PEG or PEO, PPO is insoluble in water at room temperature. However, PPG, which can be considered rather low molecular weight, is soluble in aqueous solutions at low temperatures. Industrial polymerization of PO with basic initiators mostly relies on potassium hydroxide and alcohols as initiators. Since the majority of PO is used in the preparation of star-shaped polymers, so-called polyether polyols, polyfunctional initiators such as glycerol, pentaerythritol, or sorbitol are often used. PPO-based star-shaped polyether polyols play a key role in the synthesis of flexible polyurethane foams due to their chain mobility, i.e., low glass transition and amorphous nature. In general, PPG is often used in combination with PEG (for example, as a block copolymer) as a lubricant, defoamer, softener, rheological modifier, poly(urethane) adhesive, and nonionic surfactant.

[0112] In contrast to EO and PO, 1,2-butylene oxide monomer (BO) must be produced through a two-step industrial process and cannot be obtained by the direct oxidation of the respective alkenes. Synthesis relies on the oxidation of butadiene to vinyl oxirane and subsequent hydrogenation. The properties of poly(butylene oxide) (or polybutylene glycol) (PBO) are similar to those of PPO, however, as expected, it is highly hydrophobic. The high hydrophobicity of PBO is advantageous in several applications, such as polyurethanes that must be stable to water or hot steam. Adding small amounts of PBO to lubricants can help improve their properties. In some examples, BO is used as a comonomer to modify the properties of other polyethers, i.e., to increase their nonpolar and amorphous structure. The increased hydrophobicity of PBO is advantageous for surfactants to combine PEO and PBO blocks.

[0113] In this application, the terms "polyalkylene glycol," "polyethylene glycol," "polypropylene glycol," and "polybutylene glycol" are used for each polymer or polymer block of any molecular weight.

[0114] For example, consumers of home care products, skincare products, tablet formulations, and food additives are pressuring producers to stop distributing non-degradable ingredients that inevitably accumulate in the environment. The most prominent examples are microplastics and water-soluble performance polymers. However, another goal is to improve the carbon footprint and greenhouse gas balance of these products as a whole. The dilemma is that any substance claimed to be biodegradable will decompose, with at least 60% of its carbon content converted to CO2 after 28 days (OECD 301B). Therefore, any improvement in biodegradability would require industry to convert potential carbon and CO2 sinks into designated CO2 emissions into the atmosphere. In this sense and timeframe, producers are compelled to worsen their total product carbon footprint (PCF), as such Scope 3 (downstream) emissions are also part of the equation. For some products, such as many surfactants, the use of bio-based raw materials is a viable option. However, when we speak of mass-produced goods, especially alkoxylated compounds, land use and water footprints also represent a significant burden on the environment and society; moreover, it goes without saying that approximately 25% of the Earth's GHGs are a consequence of agricultural and food production.

[0115] A further object of the present invention is to provide a solution to the aforementioned dilemma, namely, to provide an alkoxylated compound that has a product carbon footprint (PCF) from low cradle to grave (i.e., including Scope 3 downstream*) and is generally biodegradable at the same time.

[0116] *In this application, "material carbon" in polymer products refers only to the additional CO2 emissions generated for "graveyard" emissions at the end of their lifespan; all other emissions, such as those related to transportation and use at the product end-user and consumer stages, are outside the scope.

[0117] The purpose of this is, i) 20 wt% to <100 wt%, preferably 30 wt% to <99.3 wt%, ethylene oxide units and / or propylene oxide units, ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of ethylene oxide and propylene oxide units, and at least one alkylene oxide unit different from the ethylene oxide and propylene oxide units. iii) At least one initiator unit having a Zerevitinoff active hydrogen atom, in an amount of >0 wt% to 80 wt%, preferably 0.2 wt% to 70 wt%, (Here, the sum of the units listed in i), ii), and iii) is 100 wt%.) A method for preparing an alkoxylated compound, comprising: The following steps: (b) A step of forming methanol by reacting hydrogen with carbon dioxide, (c) A step of converting methanol in step (b) to ethene and / or propene, (d) A step of reacting the ethene and / or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and (e0) A step of forming an alkoxylated compound by reacting ethylene oxide and / or propylene oxide obtained in step (d) and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide with at least one initiator unit having a Zerevichnov active hydrogen atom in one or more steps. Includes, The carbon dioxide in step (b) is obtained, at least in part, from industrial exhaust gases, air, or ocean water or other natural water, or from a biological process, such as a fermentation process from waste or biomass, and preferably, the hydrogen in step (b) is obtained, at least in part, by water splitting, preferably by electrolysis, and the water splitting, preferably by electrolysis, is achieved by using energy, preferably at least in part, produced from non-fossil resources.

[0118] The objective is to obtain alkoxylated compounds by the method according to the present invention, generally <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, even more preferably <6.90×C-0.560×E+0.464×P-0.495, even more preferably <6.48×C-0.489×E+0.239×P-0.436, and even more preferably <6.06×C-0.418×E-0.014× This is further achieved by alkoxylated compounds having a total product carbon footprint from cradle to grave of P-0.377, more preferably <5.64×C-0.347×E-0.211×P-0.318, and even more preferably <5.21×C-0.276×E-0.436×P-0.259 (wherein C is the mass ratio of carbon content in the alkoxylated compound, E is the mass ratio of EO content in the alkoxylated compound, and P is the mass ratio of "the sum of PO and other alkoxides other than PO and EO" content in the alkoxylated compound, where each mass ratio is in the range of 0 to 1, and the sum of the mass ratios of C+E+P is 1).

[0119] Preferably, the alkoxylated compound of the present invention satisfies the biodegradability requirements specified in OECD 301B.

[0120] This objective is further achieved by the use of the alkoxylated compounds of the present invention in home care products, cosmetics, pharmaceutical products, food products, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, lubricating greases, thermal conductive fluids, metalworking oils and transmission fluids, defoamers, softeners, rheological modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking oils, pesticides such as insecticides, textile and leather auxiliaries, bioprocessing, fuel performance packaging and poly(urethane) adhesives.

[0121] The present invention further relates to a method for preparing ethylene oxide or propylene oxide, comprising the following steps: (b) A step of forming methanol by reacting hydrogen with carbon dioxide, (c) A step of converting methanol in step (b) to ethene and / or propene, (d) A step of reacting the ethene and / or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide. Includes, The carbon dioxide in process (b) is recovered, at least in part, from industrial exhaust gases, air, ocean water, or other natural water sources, or obtained from biological processes, such as fermentation processes from waste or biomass. and / or The present invention relates to a method wherein the hydrogen in step (b) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably electrolysis, uses energy which is preferably at least in part derived from non-fossil resources.

[0122] The present invention further specifies a ratio of <1.7 kg CO2e / ethylene oxide 1 kg, preferably <1.6 kg CO2e / ethylene oxide 1 kg, more preferably <1.5 kg CO2e / ethylene oxide 1 kg, even more preferably <1.4 kg CO2e / ethylene oxide 1 kg, most preferably <1.3 kg CO2e / ethylene oxide 1 kg, even more preferably <1.2 kg CO2e / ethylene oxide 1 kg, even more preferably <1.1 kg CO2e / ethylene oxide 1 kg, still more preferably <1.0 kg CO2e / ethylene oxide 1 kg, still more preferably <0.9 kg CO2e / ethylene oxide 1 kg, still more preferably <0.8 kg CO2e / ethylene oxide 1 kg, still more preferably <0.7 kg CO2e / ethylene oxide 1 kg, still more preferably <0.6 kg CO2e / ethylene oxide 1 kg, still more preferably <0.5 kg Ethylene oxide obtained in step (d) having a total product carbon footprint from cradle to gate of 1 kg of CO2e / ethylene oxide, more preferably <0.4 kg, 1 kg of CO2e / ethylene oxide, more preferably <0.3 kg, and 1 kg of CO2e / propylene oxide, more preferably <3.4 kg, 1 kg of CO2e / propylene oxide, more preferably <3.3 kg, more preferably <3.2 kg, 1 kg of CO2e / propylene oxide, more preferably <3.1 kg, 1 kg of CO2e / propylene oxide, most preferably <3.0 kg, 1 kg of CO2e / propylene oxide, more preferably <2.9 kg, 1 kg of CO2e / propylene oxide, more preferably <2.8 kg, 1 kg of CO2e / propylene oxide, more preferably <2.7 kg, 1 kg of CO2e / propylene oxide, more preferably <2.6 kg CO2e / propylene oxide 1 kg, more preferably <2.5 kg; CO2e / propylene oxide 1 kg, more preferably <2.4 kg; CO2e / propylene oxide 1 kg, more preferably <2.This relates to propylene oxide obtained in process (c) having a total product carbon footprint from cradle to gate of 3 kg CO2e / 1 kg propylene oxide.

[0123] The methods and products in steps (b), (c), and (d) of the present invention are not based on starting materials derived from biomass raw materials or biomass balance raw materials.

[0124] The terms ethene and propene are the IUPAC names for compounds of the formulas CH2=CH2 and CH3CH=CH2, respectively, and are also known as ethylene and propylene.

[0125] The IUPAC name for the term ethylene oxide as used in this application is oxirane (C2H4O).

[0126] In the context of this application, propylene oxide refers to 1,2-propylene oxide. The IUPAC name for the term propylene oxide as used in this application is 2-methyloxirane (C3H6O). Another name for it is 1,2-epoxypropane.

[0127] Ethylene oxide units are the form of ethylene oxide after reaction in alkoxylated compounds, propylene oxide units are the form of propylene oxide after reaction in alkoxylated compounds, and alkylene oxide units are the form of alkylene oxide after reaction in alkoxylated compounds.

[0128] As used in this application, the term "alkoxylated compound" encompasses alkoxylated compounds comprising at least one ethylene oxide unit and / or propylene oxide unit and at least one initiator unit having a Zerewitinoff active hydrogen atom.

[0129] According to REACH (Article 3(5)) (REACH Regulation (EC) 1907 / 2006 of the European Parliament and the Council of 18 December 2006), a polymer is defined as a substance that meets the following criteria: (a) More than 50 percent by weight of the substance consists of polymer molecules (see definition below); and, (b) The amount of polymer molecules exhibiting the same molecular weight must be less than 50 weight percent of the substance.

[0130] In relation to this definition, A "polymer molecule" is a molecule that contains an array of at least three monomer units covalently bonded to at least one other monomer unit or other reactant. • A "monomer unit" refers to the post-reaction form of a monomer substance in a polymer (for example, the polymer formation mechanism is considered when identifying one or more monomer units in the chemical structure of a polymer). A "sequence" is a continuous chain of monomer units within a molecule, uninterrupted by units other than monomer units that are covalently bonded to each other. This continuous chain of monomer units may, in some cases, follow any arbitrary network within the polymer structure. "Other reactants" refers to molecules that can be linked to one or more monomer units but cannot be considered monomers under the relevant reaction conditions used in the polymer formation process.

[0131] The term "polymer," as used herein, includes both homopolymers and copolymers. A "polymer" can be linear or branched.

[0132] To address this objective, the relevant PCFs in the preparation of alkoxylated compounds and upstream compounds were calculated based on the following guidelines: “The Product Carbon Footprint Guideline for the Chemical Industry” launched by TfS (Together for Sustainability), Version 2.0, November 2022 (https: / / www.tfs-initiative.com / ) (hereinafter referred to as the “TfS Guideline”). This guideline is “audit-ready,” ISO compliant, GHG protocol approved, and “open source,” making it useful for industries worldwide that use chemical materials.

[0133] The applicant's proprietary Verbund system creates an efficient value chain extending from basic chemicals to consumer products. This enables the collection of reliable data on greenhouse gas (GHG) emissions generated by products within and beyond the Verbund, particularly alkoxylated compounds and upstream compounds and their preparation methods, across different stages of their lifecycle, from cradle to gate (upstream Scope 1, 2, and 3) and from cradle to grave* (upstream and downstream Scope 1, 2, and 3).

[0134] *In this application, "material carbon" in polymer products refers only to CO2 emissions generated as additional emissions in the "graveyard" emissions at the end of their lifespan; all other emissions, such as those related to transportation and use at the product end-user and consumer use stages, are outside the scope of this application.

[0135] The preparation of alkoxylated compounds, particularly their precursors ethylene oxide and propylene oxide, requires a large amount of energy, and many of the steps (b) to (e0) of the preparation of alkoxylated compounds can be carried out by several alternative methods. The inventors have found a method for preparing alkoxylated compounds in which each step is optimized to obtain, or at least prepared for, the acquisition of alkoxylated compounds with a low carbon footprint.

[0136] If there is any improvement in terms of biodegradability, one idea of ​​the present invention for resolving the dilemma that industry faces in converting potential carbon and CO2 sinks into the approved amount of CO2 released into the atmosphere, as described above, is the reuse of CO2 released into the atmosphere in the preparation of alkoxylated compounds.

[0137] This objective is achieved in the method of the present invention by selecting the reaction of hydrogen with carbon dioxide as the methanol preparation step (b), where carbon dioxide is recovered at least in part, preferably entirely, from industrial exhaust gases or air or from ocean water or other natural water, or obtained from a fermentation process from waste or biomass.

[0138] Those skilled in the art know that because the backpack discharge rate for propylene oxide is much higher than that for ethylene oxide, alkoxylated compounds with high content of propylene oxide and higher epoxides (i.e., ethylene oxide and epoxides other than propylene oxide) always have a higher cradle-to-grave PCF compared to alkoxylated compounds with high ethylene oxide content. However, surprisingly, it has been found that the flow changes when using the method of the present invention (CO2 recovery in one or more of steps (b) to (e0), preferably electrolytic H2, preferably green energy). After rigorous analysis of different method steps for obtaining alkoxylated compounds according to the present invention, it was found that the cradle-to-grave PCF of the product decreases with increasing content of propylene oxide and higher epoxides. This means that for products with high content of propylene oxide and higher epoxides, the flow changes when switching to raw materials and processes with lower discharge rates (see Figure 8).

[0139] In a preferred embodiment of the present invention, the propylene oxide of step (d) is therefore obtained by oxidation of propene with hydrogen peroxide as the oxidizing agent.

[0140] Regarding large-scale production methods for propylene oxide, there are various different methods, namely the chlorohydrin process (CHPO; a multi-step process in which a chlorohydrin intermediate is formed by adding hypochlorous acid to propylene, followed by dehydrochlorination to produce an epoxide), and oxidation of propylene by organic peroxides including tert-butyl hydroperoxide and ethylbenzene hydroperoxide (MTBE). It should be considered that the following methods are known in the art: the PO method: by-products include t-butyl alcohol (TBA) for the production of methyl tert-butylethyl (MTBE); the SMPO method: by-products include ethylbenzene for the production of styrene); the cumene hydroperoxide method (CHP; epoxidation of propylene using cumene hydroperoxide (CHP); CHP is obtained by oxidation of cumene with air; when oxygen is cut off to propylene, CHP is converted to cumyl alcohol, which can be dehydrated to α-methylstyrene, and then hydrogenated to return it to cumene); and the hydrogen peroxide method (HPPO; production of propylene oxide from propylene and hydrogen peroxide).

[0141] Furthermore, the inventors have found that when the hydrogen used in the preparation of methanol in step (b) is obtained at least in part by hydrolysis, preferably by electrolysis, based at least in part on electricity generated from non-fossil resources, a particularly low PCF of alkoxylated compounds can be obtained.

[0142] Through rigorous analysis of various different methods and processes for obtaining alkoxylated compounds, it has been found that steps (b), (c), and (d) are critically important for obtaining alkoxylated compounds with a low product carbon footprint from cradle to grave. Therefore, the present invention further relates to a method for preparing ethylene oxide or propylene oxide as described above.

[0143] Steps (b), (c), and (d) in the method for preparing ethylene oxide or propylene oxide according to the present invention are the same as steps (b), (c), and (d) in the method for preparing alkoxylated compounds according to the present invention, and the definitions of steps (b), (c), and (d) above and below apply to both methods.

[0144] More preferably, in the method for preparing an alkoxylated compound, energy in the form of heating energy and / or electricity is used in step (b), and in one or two of steps (c), (d), and (e0), and at least part of the energy used is derived from non-fossil resources. Most preferably, energy in the form of heating energy and / or electricity is used in all of steps (b) to (e0), and at least part of the energy used in steps (b) to (e0) is derived from non-fossil resources.

[0145] More preferably, in a method for preparing ethylene oxide or propylene oxide, energy in the form of heating energy and / or electricity is used in step (b) and in one or both of steps (c) and (d), and at least part of this energy is derived from non-fossil resources. Most preferably, energy in the form of heating energy and / or electricity is used in all of steps (b) to (d), and at least part of this energy is derived from non-fossil resources.

[0146] According to the requirements of TfS, the PCF of the final product must take into account all processing steps leading up to the production of the final finished product. Therefore, a person skilled in the art would not expect that highly processed products, such as alkoxylated compounds with a low total product carbon footprint from cradle to grave, as described below, are achievable and can resolve the aforementioned dilemma. Clearly, these products require energy-intensive starting materials and numerous subsequent energy-intensive processing steps.

[0147] However, means of using carbon dioxide, at least partially recovered from industrial exhaust gases, air, seawater, or other natural water sources, or obtained from fermentation processes from waste or biomass, should be considered insufficient for obtaining particularly low cradle-to-grave PCF of alkoxylated compounds. In addition, minimizing the yield at each step of the process, and consequently the generation of waste, has been found to be a powerful leverage. Another important factor is the specific method selected, in particular, for the preparation of ethene and propene (steps (b) and (c)), and, in a preferred embodiment, the specific method selected for obtaining propylene oxide (step (d)).

[0148] In the term "at least part from non-fossil resources" in the method for preparing ethylene oxide, propylene oxide, and alkoxylated compounds, it means that some of the energy may still be generated from fossil fuels, preferably natural gas, because the carbon dioxide emissions per megajoule of energy produced by the combustion of natural gas are far less than those from the combustion of coal. However, the amount of energy generated from fossil fuels must be as small as possible, preferably in step (b), preferably in step (b), and in one or two of steps (c), (d), and (e0), more preferably in all of steps (b) to (e0), ≤50%, more preferably ≤30%, most preferably ≤20%, and even more preferably ≤10% of the energy is generated from fossil resources.

[0149] More preferably, in step (b), preferably in step (b), and in one or two of steps (c), (d), and (e0), more preferably in all of steps (b) to (e0), at least 50%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90%, and most preferably 100% of the total energy input required is generated from non-fossil resources.

[0150] Most preferably, in the method for preparing the alkoxylated compound, in step (b), preferably in step (b), and in one or two of steps (c), (d), and (e0), more preferably in all of steps (b) to (e0), the energy is derived exclusively from non-fossil resources.

[0151] Most preferably, in a method for preparing ethylene oxide or propylene oxide, in step (b), preferably in step (b), and further in one or both of steps (c) and (d), and more preferably in all of steps (b) to (e0), the energy is derived exclusively from non-fossil resources.

[0152] In a more preferred embodiment, at least 50%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90%, and most preferably 100% of the total energy input required for use in the method of the present invention is generated from non-fossil resources.

[0153] Generally, the energy used in these processes (b), (c), (d) and (e0) is used in the form of heating energy and / or electricity.

[0154] More preferably, at least a portion of the energy used in the method of the present invention is utilized from exothermic chemical methods other than the method steps of the present invention (typical examples: production of acrylic acid, formaldehyde, or ethylene oxide), for example, from excess energy generated in a chemical "Verbund" production setup that distributes excess energy, such as steam, to endothermic treatment consumers. The excess steam can replace steam generated by fossil fuels and can be allocated CO2e credits as an exothermic treatment source, thus enabling the CO2 balance to be tightened as described in the "TfS PCF Guidelines". Such a Verbund plant is preferably supplied with additional energy generated from non-fossil resources.

[0155] Various methods for certifying and transporting "energy source mixtures" are set up in accordance with local legislation. Certificates such as "non-fossil fuel certificate agreements" are common practice for tracking the proportion of non-fossil energy used in industrial processes and related activities (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / ).

[0156] Preferably, the energy is generated, at least in part, from non-fossil resources selected from solar energy (heat, photovoltaic and concentrated solar thermal power), wind power, hydropower (tidal, wave, hydroelectric dams, river fluid dynamics), geothermal energy, heat recovered by heat pumps, bioenergy (biofuels, biomass), a renewable portion of waste energy sources, nuclear energy, and mixtures thereof.

[0157] In further embodiments, the energy is generated, at least in part, from non-fossil resources selected from renewable resources, preferably from solar energy (heat, photovoltaic and concentrated solar thermal power), wind power, hydroelectric power (tidal, wave, hydroelectric dams, river fluid dynamics), geothermal energy, heat recovered by heat pumps, bioenergy (biofuels, biomass), renewable portions of waste, and mixtures thereof.

[0158] The types of energy resources described above are generally known to those skilled in the art. Preferred energy resources will be discussed later.

[0159] The alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines, alkoxylated polyethyleneimines and surfactants of the present invention are known in themselves, widely used today, or have only recently been disclosed, as will be further detailed below, and are therefore known to those skilled in the art.

[0160] Since the development of the Haber-Bosch process for ammonia preparation, the vast majority of ammonia has been produced by direct synthesis from hydrogen and nitrogen in the presence of a catalyst, particularly an iron-containing catalyst. Special care must be taken in providing the starting materials, hydrogen and nitrogen. They must be of high purity and substantially free of catalyst poisoning agents such as carbon monoxide and sulfur compounds like H2S and SO2. In modern methods, large quantities of hydrogen are supplied by steam reforming, and therefore from natural gas.

[0161] However, petrochemical steam reforming processes have negative impacts on their carbon footprint, including the consumption of large amounts of fossil-derived natural resources and energy.

[0162] Recently, it has become crucial to be able to reliably trace the origin of hydrogen and downstream compounds obtained from clean energy sources. This is particularly important to ensure the following: • Hydrogen and downstream compounds are produced in accordance with sustainability standards. • Renewable energy attributes are not subject to double counting.

[0163] Consequently, companies are increasingly prioritizing the procurement of green energy. Therefore, it is necessary to develop systems that track the origin of the energy used in the preparation of hydrogen and downstream compounds.

[0164] U.S. Patent Application Publication No. 2011 / 136097 relates to a method for determining the origin of food, more specifically, the geographical and / or biological origin of food containing alcohols or sugars, by using specific isotopic ratios influenced by climatic conditions and place of origin as a specific factory isotopic "fingerprint" of sugars from different factories.

[0165] However, the deuterium content used in this invention is not a natural "fingerprint," but rather the finding that the deuterium content of hydrogen obtained by electrolysis of water is lower than that of naturally occurring hydrogen. Furthermore, the method of hydrogen preparation is determined rather than the geographical region of origin being determined.

[0166] U.S. Patent No. 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 used in the method of U.S. Patent No. 6,495,609 is present in syngas, such as natural gas or refinery off-gas.

[0167] The specification of UK Patent Application Publication No. 2 464 691 A relates to the production of methanol from agricultural by-product cellulosic / lignin materials. In the first section of the synthesis plant, cellulosic / lignin material by-products remaining after the harvest of agricultural products are converted to carbon dioxide by exothermic oxidation. In another section of the synthesis plant, hydrogen gas is produced by electrolysis, and methanol is produced by reacting it with carbon dioxide.

[0168] International Publication No. 2016 / 149507 A1 relates to the oxidative coupling of methane for obtaining a variety of different products. For example, claim 217 discloses a method for producing oxalate compounds.

[0169] U.S. Patent No. 7,119,231 B2 relates to a method for preparing alkanolamines by reacting ammonia with alkylene oxide in a reaction space in the presence of a catalyst to obtain monoalkanolamines, dialkanolamines, or trialkanolamines, or mixtures of two or three of these compounds. There are no particular hints regarding the deuterium content of the hydrogen-containing compounds used in U.S. Patent No. 7,119,231 B2, or regarding the use of non-fossil energy.

[0170] French Patent Application Publication No. 2 851 564 A1 relates to a method for preparing ethylene oxides and ethanolamines. French Patent Application Publication No. 2 851 564 A1 contains no hints whatsoever about the presence of deuterium in these hydrogen-containing compounds or the use of non-fossil energy.

[0171] U.S. Patent Application Publication No. 2008 / 0283411 A1 relates to a method for converting carbon and hydrogen sources into hydrocarbons. It states that the method and apparatus are useful for producing alternative energy sources to fossil fuels, storing renewable energy, sequestrating carbon dioxide from the atmosphere, preventing global warming, and storing carbon dioxide in liquid fuels.

[0172] International Publication No. 2015 / 102985 A1 relates to a method for preparing ethanolamines by reacting an aqueous ammonia solution with ethylene oxide. However, International Publication No. 2015 / 102985 A1 does not provide any particular hints regarding the preparation of hydrogen by electrolysis, the use of renewable energy, or the presence of deuterium in the hydrogen-containing compounds disclosed in International Publication No. 2015 / 102985 A1.

[0173] German Patent Application Publication No. 195 34 493 A1 relates to a method for preparing aziridines in the presence of a particulate shell catalyst. These aziridines are prepared by dehydrating alkanolamines in the presence of the catalyst. However, German Patent Application Publication No. 195 34 493 A1 makes no mention of the electrolysis of water for the preparation of hydrogen, nor of the deuterium content of hydrogen-containing compounds, nor of the use of renewable energy.

[0174] Therefore, a further object of the present invention is to provide environmentally friendly alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines ("inventive compounds"), and environmentally friendly methods for producing them, which use as little fossil-derived energy as possible, ideally no fossil-derived energy at all, and therefore add as little as possible to CO2 emissions, ideally no addition at all.

[0175] This objective is also achieved by using the molar occupancy of deuterium in hydrogen bonded to hydrogen-derived compounds of the present invention to trace the origin, particularly the energy origin, of the hydrogen bonded in those hydrogen-derived inventive compounds; a method for tracing the origin, particularly the energy origin, of hydrogen bonded to downstream compounds of hydrogen, by determining the molar occupancy of deuterium in hydrogen bonded in the said inventive compounds, is also part of the present invention. Methods for determining the molar occupancy of deuterium in hydrogen and downstream compounds derived from hydrogen are known to those skilled in the art, and include mass spectrometry and NMR techniques.

[0176] Specifically, this objective is achieved by alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines, which are produced by known means using non-fossil-derived ethylene oxide and / or propylene oxide, preferably by a method leading to ethylene oxide, and then using it to produce the compounds of the present invention, where the molar content of deuterium is lower than that of products made using ethylene oxide (EO) and / or propylene oxide (PO), preferably EO from fossil-derived sources only. The deuterium content is preferably at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, for example, 60, 70, 80 or even more than 90 percent lower in products using non-fossil-derived EO and / or PO, preferably EO, compared to products using fossil-derived EO and / or PO only, preferably EO only (such percentages are based on the total hydrogen content of units resulting from the reaction of EO and / or PO, preferably EO, with the compounds of the present invention).

[0177] In a further embodiment of the present invention, the objective is a method for producing alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines, comprising the following steps: (a0) A step of providing hydrogen having a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated in part from non-fossil energy. (a) A step of forming ammonia by reacting the hydrogen from step (a0) with nitrogen, (b) A step of forming methanol by reacting the hydrogen from step (a0) with carbon oxides, preferably carbon dioxide, (c) a step of converting methanol in step (c) to ethylene and / or propylene, preferably ethylene, and (d) a step of further converting it to ethylene oxide and / or propylene oxide, preferably ethylene oxide, preferably together with oxygen or an oxidizing agent. (e1) A step of converting the ethylene oxide and / or propylene oxide, preferably ethylene oxide, of step (d) to alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines in one or more steps using known methods. This is achieved by a method that includes [a specific method].

[0178] In a further embodiment of the present invention, the object is a method for producing alkoxylated polyethyleneimine, comprising the following steps: (a0) A step of providing hydrogen having a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated in part from non-fossil energy. (a) A step of forming ammonia by reacting the hydrogen from step (a0) with nitrogen, (b) A step of forming methanol by reacting the hydrogen from step (a0) with carbon oxides, preferably carbon dioxide, (c) A step of converting the methanol in step (c) to ethylene and / or propylene, preferably ethylene, and (d) a step of further converting it, preferably together with oxygen, to ethylene oxide and / or propylene oxide, preferably ethylene oxide. (e) A step of converting the ammonia from step (b) together with the ethylene oxide from step (d) into ethanolamines in one or more steps, and (f) A step to separate monoethanolamine from the ethanolamines obtained in step (e), (g) A process of converting monoethanolamine to ethyleneimine, (h) A step of polymerizing ethyleneimine in step (g) to polyethyleneimine; and (i) A step of alkoxyling the polyethyleneimine of step (g) with ethylene oxide and / or propylene oxide, preferably ethylene oxide, and optionally other alkylene oxides and / or lactones, thereby obtaining alkoxylated polyethyleneimines. This is achieved by a method that includes [a specific method].

[0179] Furthermore, it is crucial to be able to reliably trace the origins of hydrogen and downstream compounds obtained from clean energy sources.

[0180] This is especially true • Hydrogen and downstream compounds are produced in accordance with sustainability standards. • Renewable energy attributes are not subject to double counting. This is to ensure that it is true.

[0181] Companies are increasingly prioritizing the procurement of green energy. Therefore, there is a need to develop systems that track the origin of the energy used in the preparation of hydrogen and downstream compounds.

[0182] The objective can also be achieved by using the molar occupancy of hydrogen and hydrogen-derived downstream compounds, particularly the energy origin, for tracing the origin of hydrogen and hydrogen-derived downstream compounds, wherein the compounds are preferably alkoxylated diamines, oligoamines, and polyamines and alkoxylated polyethyleneimines, and by determining the molar occupancy of hydrogen and hydrogen-derived downstream compounds, particularly the energy origin, wherein the compounds are preferably alkoxylated diamines, oligoamines, and polyamines and alkoxylated polyethyleneimines.

[0183] Methods for determining the molar occupancy of deuterium in hydrogen and hydrogen-derived downstream compounds are known to those skilled in the art. Preferred methods are described in the examples of this application.

[0184] As science and technology advance further, and as increasingly sophisticated measurement techniques are developed, the resolution of measurement methods for determining deuterium content relative to total hydrogen content will become increasingly precise. Therefore, it is expected that in the future, even more precise determinations will be possible, and even the ability to distinguish minute differences will become possible. However, the inventions disclosed herein will not change through these scientific advancements; rather, the likelihood of recognizing the inventions will increase.

[0185] A further environmental advantage of the environmentally friendly alkoxylated diamines, oligoamines, and polyamines and alkoxylated polyethyleneimines according to the present invention is their use in carbon capture processes, because the alkoxylated diamines, oligoamines, and polyamines and alkoxylated polyethyleneimines according to the present invention are produced using as little as possible, and ideally no, fossil-derived energy, in terms of the content derived from at least EO and / or PO, preferably EO, and therefore the addition to CO2 emissions is as small as possible, and ideally, nothing at all.

[0186] Naturally, the present invention would be even more environmentally friendly if environmentally friendly methods were used for other components, such as amines. Therefore, the present invention also encompasses such even more environmentally friendly products, where the amines used herein, as well as other components such as the aforementioned alkylene oxides and lactones, are sourced from or produced from renewable, or even better, non-fossil sources. Such sources are already known.

[0187] Therefore, a further embodiment of the present invention is the use of alkoxylated diamines, oligoamines, and polyamines, as well as alkoxylated polyethyleneimines, according to the present invention, as liquid or solid CO2 absorbents in a CO2 recovery method.

[0188] Detailed method for preparing alkoxylated diamines, oligoamines, and polyamines, as well as alkoxylated polyethyleneimines, including various method steps as described above.

[0189] A further object of the present invention is to provide an environmentally friendly surfactant with a low molar occupancy of deuterium, wherein the surfactant comprises at least one structural unit derived from ethylene oxide, methanol, ammonia, or ethanolamine, or is produced with hydrogen.

[0190] The objective is to further encompass an environmentally friendly method of producing it, a method that uses as little, ideally no, fossil-derived energy as possible, and thus such a method that adds as little, ideally nothing, to CO2 emissions; a further objective is the use of the molar occupancy of deuterium in hydrogen, and by extension, the use to trace the origin of hydrogen, in particular the energy origin, in such surfactants derived from hydrogen, which contain at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or hydrogen produced with hydrogen; and by extension, the use to trace such surfactants derived from hydrogen, which contain at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or hydrogen produced with hydrogen.

[0191] Methods for determining the molar occupancy of deuterium in hydrogen and in downstream compounds derived from hydrogen are known to those skilled in the art, and include mass spectrometry and NMR techniques.

[0192] Specifically, this objective is achieved by a surfactant of the present invention, which comprises at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or ethene or ethylene oxide, when a method is used that comprises the steps of generating hydrogen from a non-fossil source, optionally in a further step of generating methanol, ammonia, ethanolamine, or ethene or ethylene oxide, and then using it—or a combination thereof in various orders—to produce the surfactant of the present invention by known means, wherein the molar occupancy of deuterium is lower than that of a product made using hydrogen, methanol, ammonia, ethanolamine, or ethene or ethylene oxide from fossil sources alone (each of these individually as a “starting material”, and at least two of these as “starting materials”). The deuterium content is preferably at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, for example 60, 70, 80, or even more than 90 percent lower in products using one or more non-fossil starting materials compared to products using only fossil materials (such percentages are based on the total hydrogen content of units resulting from the reaction of one or more starting materials with the compound of the present invention).

[0193] In a further embodiment of the present invention, the object is a method for preparing a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, or ethanolamine, or produced with hydrogen, wherein the method comprises the following steps: (a0) A step of providing hydrogen having a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated in part from non-fossil energy. (a) A step of forming ammonia by reacting the hydrogen from step (a0) with nitrogen, (b) A step of forming methanol by reacting the hydrogen from step (a0) with carbon oxides, preferably carbon dioxide, (c) a step of converting methanol in step (b) to ethylene and (d) a step of further preferably converting it to ethylene oxide together with oxygen, (e) A step of converting the ammonia from step (a) together with the ethylene oxide from step (d) into ethanolamines in one or more steps, and (f) A step of separating monoethanolamine, diethanolamine, and triethanolamine from the ethanolamines obtained in step (e), (g0) A step of converting any of the products of steps a), b), c), d), and e) into a surfactant containing at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or hydrogen, by at least one known method step. This is achieved by including a method to obtain a surfactant that contains less deuterium on a basis of total hydrogen content compared to chemically identical surfactants obtained solely from fossil sources.

[0194] The present invention further relates to a method for tracing surfactants back to their origin, particularly to their energy origin, and also to non-fossil resources in the surfactants of the present invention derived from such hydrogen, by using the molar occupancy of deuterium in hydrogen, which is also part of the present invention.

[0195] Methods for determining the molar occupancy of deuterium in hydrogen and hydrogen-derived downstream compounds are known to those skilled in the art and are described above and below. Preferred methods are described in the examples of this application.

[0196] A further environmental advantage of the environmentally friendly surfactant according to the present invention is its use in carbon capture processes, for the surfactant according to the present invention is produced with as little, ideally no, use of fossil-derived energy as possible, in terms of its content of at least hydrogen and carbon (from carbon dioxide or carbon monoxide from non-fossil-based sources) and - optionally - methanol, ammonia, ethanolamine or ethene or ethylene oxide prepared using such hydrogen from non-fossil-based sources, and therefore the addition to CO2 emissions is as small as possible, ideally no addition at all.

[0197] Naturally, if environmentally friendly methods are used for other components necessary for the preparation of surfactants, such as alcohols and fatty acids, and—more preferably—if such components also originate from non-fossil sources, the present invention will be even more environmentally friendly. Accordingly, the present invention also includes such even more environmentally friendly products, wherein the other components used in the preparation of the final surfactant are sourced from and / or made from renewable, or even better, non-fossil sources. Such sources are already known to date for at least some of these other components, such as methanol and higher alcohols, fatty acids, fatty alcohols, etc.

[0198] A further embodiment of the present invention is the use of a surfactant according to the present invention as a liquid or solid CO2 absorbent in a CO2 recovery method.

[0199] Further embodiments of the present invention involve the use of the surfactant according to the present invention as a component in a composition, product, or formulation, such composition, product, or formulation is as is currently known with respect to the use of conventionally produced surfactants that are chemically identical except for differences in deuterium content.

[0200] A detailed method for preparing the surfactant of the present invention, including various method steps as described above.

[0201] In the present application, the molar fraction of deuterium in hydrogen and downstream compounds derived from hydrogen is given in ppm units based on the total hydrogen content, which is the molar ppm content of deuterium based on the total hydrogen content (in hydrogen or in the compound under consideration, respectively).

[0202] In the present application, the deuterium content of hydrogen and downstream compounds derived from hydrogen is given in atomic ppm based on the total molar hydrogen content (total atoms of protium H and deuterium 2 H). The terms "deuterium content" and "molar fraction of deuterium" are used synonymously throughout the present application.

[0203] In physical organic chemistry, the kinetic isotope effect is the change in the reaction rate of a chemical reaction when one of the atoms in the reactant is replaced by one of its isotopes. Formally, this is the ratio of the rate constants k L and k H for reactions involving reactants (isotopologs) substituted with light and heavy isotopes, respectively, which is k L / k H . Such a change in the reaction rate is mainly a quantum mechanical effect caused by the fact that the heavier the isotopolog, the lower its vibrational frequency compared to the corresponding lighter one. In most cases, this implies that the heavier isotopolog requires a larger energy input to reach the transition state, resulting in a slower reaction rate.

[0204] The change in the rate of an isotope is most pronounced when the relative mass change is greatest, because this effect is related to the vibrational frequency of the bond being affected. For example, the change from a hydrogen atom (H) to its isotope deuterium (D) corresponds to a 100% increase in mass, while 12 replacing 13 C with 12 C results in only an 8 percent increase in mass. The rate of reactions involving a C-H bond is typically 6 to 10 times that of the corresponding C-D bond, while 13 C reactions are only about 4 percent of the corresponding 12 C reactions.

[0205] First-order kinetic isotope effects can be observed when bonds to isotopic atoms are formed or broken. Second-order kinetic isotope effects are observed when bonds to isotopic atoms in the reactants are not broken or not formed. Second-order kinetic isotope effects tend to be much smaller than first-order kinetic isotope effects; however, secondary deuterium isotope effects can be as large as 1.4 per deuterium atom.

[0206] The present invention provides a method for producing alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines, alkoxylated polyethyleneimines and surfactants, which includes providing hydrogen with a deuterium molar occupancy rate of less than 90 ppm relative to the total hydrogen content by electrolysis based on electricity generated at least partially from non-fossil energy (sometimes referred to as step (a0) in the specification of the present invention).

[0207] Electricity is generated, at least partially, from non-fossil fuels.

[0208] The term "at least a portion" means that a portion of the electricity may still be generated from fossil fuels, preferably natural gas, because the carbon dioxide emissions per megajoule of electrical energy generated by the combustion of natural gas are far less than those from the combustion of coal. However, the amount of energy generated from electrofossil fuels should be as small as possible, preferably 50% or less, preferably 30% or less, most preferably 20% or less, and most preferably 10% or less. In one embodiment, the electricity is generated exclusively from non-fossil resources.

[0209] Various methods for certifying and transporting "energy source mixtures" are being set up in accordance with local legislation. Certificates such as "non-fossil fuel certificate agreements" are a common practice for the proportion of non-fossil energy used in industrial production and the transport of related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / ).

[0210] Preferably, the electricity is generated in part from wind power, solar energy (heat, photovoltaic power generation and concentrated solar thermal power generation), hydropower (tidal power, wave power, hydroelectric dams, river fluid dynamics), geothermal energy, ambient heat or industrial heat recovered by heat pumps, bioenergy (biofuels, biomass), a renewable portion of waste energy sources, or nuclear energy (nuclear fission).

[0211] In further embodiments, the electricity is generated, at least in part, from renewable resources, preferably wind power, solar energy (heat, photovoltaic and concentrated solar thermal power), hydropower (tidal, wave, hydroelectric dams, river fluid dynamics), geothermal energy, ambient heat recovered by heat pumps, bioenergy (biofuels, biomass), or a renewable portion of waste.

[0212] The types of power resources described above are generally known to those skilled in the art. Preferred energy resources will be discussed later.

[0213] This specification describes the steps (a0) in the method for preparing alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants: (a0) A process of providing hydrogen by electrolysis based on electricity generated at least partially from non-fossil energy, wherein the molar occupancy of deuterium is in the range of ≤100 ppm, preferably 10 to ≤95 ppm, more preferably 10 to ≤90 ppm, and most preferably 10 to ≤80 ppm, based on the total hydrogen content. This is mentioned.

[0214] The same features are described at the end of method claims 12 (Method for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines), 13 (Method for preparing alkoxylated polyethyleneimines), and 14 (Method for preparing surfactants): "The hydrogen from steps (a) and (b) is electrolyzed based on electricity generated at least partially from non-fossil energy, resulting in a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, relative to the total hydrogen content."

[0215] The definition of the molar occupancy of deuterium generally applies to all embodiments of methods for producing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, alkoxylated polyethyleneimines and surfactants. Specific embodiments of specific methods are described above and below.

[0216] The definition of electrolysis based on energy, particularly electricity generated at least partially from non-fossil energy, generally also applies to all embodiments of methods for producing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, alkoxylated polyethyleneimines and surfactants. However, the definition also applies to other methods of the present invention for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimines and alkoxylated compounds. Specific embodiments of specific methods are described above and below.

[0217] Steps (b), (c) and (d) in the method for preparing ethylene oxide or propylene oxide in the present invention are generally the same as steps (b), (c) and (d) in the method for preparing ethanolamines, polyethyleneimine, alkoxylated compounds, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimine, and surfactants of the present invention. The definitions of steps (b), (c) and (d) above and below apply to all methods.

[0218] Specific embodiments of steps (b), (c) and (d) in the method for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimine, alkoxylated compounds, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimine, and surfactants of the present invention, as well as specific embodiments of further preparation steps for ethanolamines, polyethyleneimine, alkoxylated compounds, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimine, and surfactants will be described later.

[0219] Steps (a), (b), (c), (d) and (e) in the method for preparing ethanolamines of the present invention are generally the same as steps (a), (b), (c), (d) and (e) in the method for preparing polyethyleneimine, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimine, and surfactants of the present invention. The definitions of steps (a), (b), (c), (d) and (e) above and below apply to all methods mentioned in this paragraph.

[0220] Specific embodiments of steps (a), (b), (c), (d) and (e) in the method for preparing polyethyleneimine, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimine, and surfactants of the present invention, as well as specific embodiments of further steps for preparing polyethyleneimine, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimine, and surfactants will be described later.

[0221] Steps (a), (b), (c), (d), (e), (f), and (g) in the method for preparing polyethyleneimine of the present invention are generally the same as steps (a), (b), (c), (d), (e), (f), and (g) in the method for preparing alkoxylated polyethyleneimine and surfactant of the present invention, and the above and below definitions of method steps (a), (b), (c), (d), (e), (f), and (g) apply to all methods referred to in this paragraph.

[0222] Specific embodiments of steps (a), (b), (c), (d), (e), (f), and (g) in the method for preparing polyethyleneimine, alkoxylated polyethyleneimine, and surfactant of the present invention, as well as specific embodiments of further steps for preparing polyethyleneimine, alkoxylated polyethyleneimine, and surfactant, will be described later.

[0223] Steps (a), (b), (c), (d), (e), (f), (g), and (h) in the method for preparing polyethyleneimine of the present invention are generally the same as steps (a), (b), (c), (d), (e), (f), (g), and (h) in the method for preparing alkoxylated polyethyleneimine of the present invention, and the above and below definitions of method steps (a), (b), (c), (d), (e), (f), (g), and (h) apply to all methods referred to in this paragraph.

[0224] Specific embodiments of steps (a), (b), (c), (d), (e), (f), (g), and (h) in the method for preparing polyethyleneimine and alkoxylated polyethyleneimine of the present invention, as well as specific embodiments of further steps for preparing alkoxylated polyethyleneimine, will be described later.

[0225] Preferred energy resources In a preferred embodiment of the method of the present invention, the energy (electricity) from non-fossil resources used in the method according to the present invention, for example, in electrolysis, may be generated at least in part by nuclear energy. Nuclear energy can be obtained by nuclear fission.

[0226] Nuclear fission occurs when a neutron enters a larger atomic nucleus, forcing it to become excited and split into two smaller atoms—also known as fission products. Further neutrons are also released, which can trigger a chain reaction. A tremendous amount of energy is released when each atom splits. In nuclear reactors, uranium and plutonium isotopes are most commonly used for nuclear fission reactions because they are easy to induce and control. The energy released by fission in these reactors heats water, turning it into steam. This steam is then used to rotate turbines, generating carbonless electricity.

[0227] The electricity generated from non-fossil resources used in water electrolysis according to the present invention is preferably generated from wind, solar, biomass, hydroelectric, and geothermal energy.

[0228] In a preferred embodiment of the method of the present invention, the energy (electricity) used in the method according to the present invention, for example, electrolysis, is generated at least in part from wind power. Wind power can be used to drive a wind turbine. Modern, practical-scale wind turbines have a rated output in the range of approximately 600 kW to 9 MW. The power available from wind power is a function of the cube of the wind speed, so as the wind speed increases, the power output increases up to the maximum output of that particular turbine. Areas with strong and consistent winds, such as offshore and high-altitude areas, are preferred locations for wind power plants.

[0229] In a more preferred embodiment of the method of the present invention, the energy (electricity) used in the method according to the present invention is generated at least in part from solar power, particularly from a photovoltaic power system. A photovoltaic power system converts light into direct current (DC) by utilizing the photoelectric effect. Concentrated solar thermal (CSP) systems use lenses or mirrors and tracking systems to focus sunlight over a wide area into a narrow beam. Currently, CSP Stirling is the most efficient and stands out among all solar energy technologies.

[0230] In a preferred embodiment of the method of the present invention, the energy (electricity) used in the method according to the present invention, for example in electrolysis, is generated at least in part from hydropower. Hydropower takes many forms. Traditionally, hydropower is generated by constructing large hydroelectric dams and reservoirs. Small-scale hydro systems are hydroelectric power plants that typically generate up to 50 MW of output. These are often used on small rivers or as developments with little impact on larger rivers. Run-of-river hydroelectric power plants draw energy from rivers without the need for large reservoirs. Water is typically transported along the riverbanks of a valley (using channels, pipes and / or tunnels) and, once it reaches high above the plains at the bottom of the valley, can be dropped through penstocks to drive a turbine.

[0231] Wave power, which recovers the energy of ocean surface waves, and tidal power, which converts the energy of tides, are two forms of hydropower with future potential.

[0232] In a more preferred embodiment of the method of the present invention, the energy (electricity) used in the method according to the present invention, for example in electrolysis, is generated at least in part from geothermal energy. Geothermal energy is heat generated from below the Earth's surface. This is contained in the rocks and liquids just below the Earth's crust and can be found as magma, which is the Earth's hot lava far below.

[0233] To generate electricity from geothermal energy, wells are drilled deep into underground reservoirs, and the steam and hot water available there can then be used to drive turbines connected to generators. There are three types of geothermal power plants: dry steam, flash, and binary.

[0234] Dry steam is the oldest geothermal technology, extracting steam from underground and using it to directly drive turbines. Flash power plants use high-pressure hot water that has been cooled to low pressure, while binary power plants pass hot water through a secondary liquid with a lower boiling point, which then turns into steam that drives the turbine.

[0235] In a more preferred embodiment of the method of the present invention, the energy (electricity) used in the method according to the present invention, for example in electrolysis, is generated in part from biomass. Biomass is biological material derived from living or recently living organisms. This most often refers to plants or plant-derived materials, particularly lignocellulosic biomass. Biomass as an energy source may be used directly by combustion to generate heat (e.g., heat from fermentation processes) or electricity, or it may be used indirectly after being converted into various forms of biofuels and gases. The conversion from biomass to biofuels can be achieved by a variety of different methods, which can be broadly classified into thermal, chemical, and biochemical methods. As of 2012, wood was the largest biomass energy source; examples include forest residues—dead trees, branches, and stumps, etc.—grass from lawns, wood chips, and even municipal waste. Industrial biomass can be cultivated from a wide variety of plants, including Japanese pampas grass, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and various tree species ranging from eucalyptus to oil palm (palm oil).

[0236] Plant energy is produced by crops specifically cultivated for use as fuel, providing high biomass output per hectare with low energy input. Grains can be used as liquid transport fuel, while straw can be burned to generate heat or electricity. Biomass can be converted into other usable forms of energy, such as transport fuels like methane gas or ethanol and biodiesel. Decaying food waste, as well as agricultural waste and human waste, all release methane gas—also known as landfill gas or biogas. Fermenting crops such as corn and sugarcane can produce transport fuel, ethanol. Biodiesel, another transport fuel, can be produced from leftovers such as vegetable oil and animal fat.

[0237] Biopower technology converts renewable biomass fuels into heat and electricity using methods similar to those used for fossil fuels. There are three methods for recovering energy stored in biomass to generate biopower: combustion, bacterial decomposition, and conversion into gaseous or liquid fuels. Biopower can offset the need for carbon fuels burned at power plants, thereby reducing the carbon intensity of power generation. Unlike some forms of intermittent renewable energy, biopower can increase the flexibility of power generation and improve the reliability of the power grid.

[0238] Preparation (generation) of hydrogen: Hydrogen can generally be obtained by any method known in the art. Hydrogen can be produced using several different methods. Thermochemical processes use heat and chemical reactions to release hydrogen from organic materials such as fossil fuels and biomass, or from materials such as 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 through biological processes. The said 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).

[0239] 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 heavy hydrocarbons, and coal gasification.

[0240] Preferably, the hydrogen in step (a) and / or (b) is obtained using energy (especially electricity) at least partly generated from non-fossil resources.

[0241] More preferably, the hydrogen in step (a) and / or (b) in the method for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimine and alkoxylated compounds of the present invention is obtained at least partly by water splitting, preferably by electrolysis. Most preferably, water splitting using energy at least partly generated from non-fossil resources, preferably electrolysis.

[0242] The term "at least part by water splitting" means that some of the hydrogen may still be produced by other means, generally by steam reforming of natural gas and / or other light hydrocarbons, partial oxidation of heavy hydrocarbons, and coal gasification, preferably by steam reforming of natural gas and / or other light hydrocarbons. However, the amount of hydrogen produced by other means other than water splitting in steps (a) and / or (b) should be as small as possible.

[0243] Preferably, in steps (a) and / or (b) of the method for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimine and alkoxylated compounds of the present invention, ≤50%, preferably ≤30%, most preferably ≤20%, and even more preferably ≤10% of the hydrogen is produced by a method other than hydrolysis. In one embodiment, the hydrogen in step (a) is produced exclusively by hydrolysis, preferably by electrolysis.

[0244] Preferably, the hydrogen in step (a) and / or (b) of the method for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimines and alkoxylated compounds of the present invention has a total product carbon footprint from cradle to gate of <5 kg CO2e / 1 kg of hydrogen, preferably <4.6 kg CO2e / 1 kg of hydrogen, more preferably <3.5 kg CO2e / 1 kg of hydrogen, most preferably <2.5 kg CO2e / 1 kg of hydrogen, and even more preferably <2 kg CO2e / 1 kg of hydrogen.

[0245] More preferably, the hydrogen in steps (a) and / or (b) of the method for preparing alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants of the present invention is obtained by electrolysis based on electricity generated in part from non-fossil energy.

[0246] The term "at least partly from non-fossil resources" is explained above.

[0247] Classification of hydrogen: Hydrogen can be defined according to the energy source used for its production, and is often classified using color coding. For example, hydrogen produced using renewable energy can be called renewable hydrogen or green hydrogen. Hydrogen produced from coal can be called brown hydrogen, and hydrogen produced from natural gas or oil can be called gray hydrogen. The production of brown or gray hydrogen combined with carbon capture and storage / sequesteration can be called blue hydrogen. Hydrogen produced from nuclear energy can be called pink hydrogen or clean hydrogen.

[0248] The hydrogen used in steps (a) and / or (b) of the method of the present invention is not preferably obtained by electrolysis, but rather by any known method in the art using any suitable energy, i.e., the hydrogen may be any of the colors described above. In one embodiment, the hydrogen is not preferably obtained by electrolysis, but rather by steam methane reforming (SMR) with carbon dioxide capture and storage (CCS), i.e., a method used to produce hydrogen gas from natural gas while capturing and storing the resulting carbon dioxide emissions.

[0249] The hydrogen used in steps (a) and / or (b) of the method of the present invention is obtained using energy generated from fossil resources, rather than by hydrosplitting, preferably by electrolysis, although this may generally be obtained by any energy generated from fossil resources known in the art. Natural gas is a preferred fossil resource because the amount of carbon dioxide emissions per megajoule of energy produced by the combustion of natural gas is far less than, for example, the combustion of coal. However, the amount of energy produced from fossil fuels should be as small as possible in the method of the present invention. Most preferably, when the hydrogen in steps (a) and / or (b) is obtained by hydrosplitting, preferably by electrolysis, the energy is entirely derived from non-fossil resources.

[0250] Water splitting, preferably electrolysis of water, is an environmentally friendly method for producing hydrogen because it uses renewable H2O and produces only pure oxygen as a byproduct. Water splitting can generally be carried out by known methods such as electrolysis; photocatalytic water splitting, also known as photoelectrochemical (PEC) water splitting; electrolysis with chemical additives, e.g., electrolysis of water with carbon / hydrocarbon additives (CAWE); radiolysis; ultrasonic; thermal decomposition, especially with solar energy, e.g., heating water by directly collecting solar energy using solar concentrators; thermal decomposition with biomass; thermal decomposition with nuclear aid, e.g., in high-temperature gas-cooled reactors (HTGRs); thermochemical cycles that combine a single heat source (thermo) with a chemical reaction to split water into its hydrogen and oxygen components, e.g., the sulfur-iodine cycle (SI cycle); ferrosilicon methods; photobiological water splitting and mixtures thereof.

[0251] Generally, any water source can be used for water splitting.

[0252] Preferably, the water splitting in the method for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimine, and alkoxylated compounds of the present invention is carried out by electrolysis and / or photocatalytic water splitting, more preferably by electrolysis.

[0253] In photocatalysis (photoelectrochemistry (PEC)), hydrogen is produced from water using sunlight, and one or more photocatalysts, which are specialized semiconductors generally called photoelectrochemical materials, use light energy to directly dissociate water molecules into hydrogen and oxygen.

[0254] The photocatalysts (semiconductor materials) used in the photocatalytic emission control (PEC) method are similar to those used in solar power generation. However, in the application of photocatalysis (PEC), the photocatalysts (semiconductors) are generally immersed in an aqueous electrolyte, where sunlight provides energy for the water splitting process.

[0255] PEC reactors can be assembled, for example, as an electrode system in panel form (similar to solar power generation panels) or as a slurry-based particle system.

[0256] The most preferred method of water electrolysis generally utilizes direct current (DC) from non-fossil energy resources as its power source, at least partially.

[0257] Herein, a key observation of the present invention, particularly concerning alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants, is that, by electrolysis of water, the deuterium atom content of hydrogen is observed to be lower than that of petrochemically generated hydrogen, such as that contained in fossil-derived synthesis gas, i.e., ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content. The deuterium atom content of hydrogen produced by electrolysis can be as low as 10 ppm. Other deuterium exists mainly in the form of DH rather than D2.

[0258] One suitable method of water electrolysis is alkaline water electrolysis. Hydrogen production by alkaline water electrolysis is a well-established technology, reaching the megawatt range at a commercial level. In alkaline water electrolysis, two water molecules in an alkaline solution (KOH / NaOH) are initially reduced at the cathode to produce one hydrogen molecule (H2) and two hydroxyl ions (OH). - ) becomes. When the generated H2 is released from the cathode surface in gaseous form, a hydroxyl ion (OH) is formed. - Under the influence of an electric field, ions move from the anode to the cathode through a porous membrane, where they are released as half an oxygen molecule (O2) and one water molecule (H2O). Alkaline electrolysis operates at lower temperatures, such as 30-100°C, preferably 30-80°C, using an alkaline aqueous solution (KOH / NaOH) as the electrolyte, with an electrolyte concentration of approximately 20-30%. The diaphragm in the center (intermediate) of the electrolytic cell separates the cathode and anode, as well as the gases generated from each electrode, preventing mixing of the generated gases. However, alkaline electrolysis has limitations in terms of current density (400 mA / cm²). 2 There are negative aspects, such as low operating pressure and low energy efficiency (below a certain threshold).

[0259] An overview of hydrogen production by alkaline water electrolysis powered by renewable energy is provided in J. Brauns and T. Turek in Processes, 8(2)(2020), pp.248.

[0260] In a further embodiment of the method of the present invention, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variants of polymer electrolyte membrane water electrolysis include proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).

[0261] PEM water electrolysis technology is similar to PEM fuel cell technology, where solid polysulfone oxide films (Nafion®, fumapem®) are used as the electrolyte (proton conductor). These proton exchange films have low gas permeability and high proton conductivity (0.1 ± 0.02 Scm). -1 It has many advantages, such as its thin thickness (20-300 μm) and the ability to operate at high pressure. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most preferred methods for converting renewable energy into high-purity hydrogen. PEM water electrolysis has many advantages, including its compact design, high current density (above 2 A cm-2), high efficiency, fast reaction, low temperature operation (20-90°C), and the production of ultra-high-purity hydrogen. The current state of the field for electrode catalysts in PEM water electrolysis is a highly active precious metal such as Pt / Pd for hydrogen evolution activity (HER) at the cathode and IrO2 / RuO2 for oxygen evolution reaction (OER) at the anode.

[0262] One of the greatest advantages of PEM water electrolysis is its ability to operate at high current densities. This can reduce operating costs, especially in systems combined with energy sources that have extremely high dynamic properties, such as wind and solar power, where energy would otherwise be lost due to sharp spikes in energy output. With polymer electrolytes, high operating pressures are still possible, and the PEM water electrolysis cell can be operated with an extremely thin membrane (approximately 100-200 μm), resulting in low resistive losses, mainly caused by proton conduction across the membrane (0.1 S / cm) and the output of compressed hydrogen.

[0263] A PEM water electrolytic cell uses a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while the electrodes are electrically insulated. Under standard conditions, the enthalpy required for water formation is 285.9 kJ / mol. Part of the energy required for a sustained electrolytic reaction is supplied by thermal energy, and the remainder by electrical energy.

[0264] The half-reaction that occurs on the anode side of a PEM water electrolysis cell is generally called the oxygen evolution reaction (OER). Here, liquid water reactants are supplied to the catalyst, where they are oxidized to oxygen, protons, and electrons.

[0265] The half-reaction that occurs on the cathode side of a PEM water electrolysis cell is generally called hydrogen evolution activity (HER). Here, protons that have moved across the membrane are reduced to gaseous hydrogen.

[0266] PEMs can be made of pure polymer films or composite films, where other materials are embedded in the polymer matrix. One of the most common commercially available PEM materials is the fluoropolymer PFSA (e.g., Nafion®, manufactured by DuPont). Nafion® is an ionomer with a perfluorinated skeleton, like Teflon®, but there are many other structural motifs used to create ionomers for proton exchange membranes. Many use polycyclic aromatic polymers, while others use partially fluorinated polymers.

[0267] An overview of hydrogen production by PEM water electrolysis is provided in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442-4454.

[0268] An overview of hydrogen production by anion exchange membrane water electrolysis is provided in HAMiller et al., Sustainable Energy Fuels, 2020, 4, pp.2114-2133.

[0269] K. Harada et al., International Journal of Hydrogen Energy 45 (2020), pp. 31389-31395, reported a 2-3 fold deuterium depletion in polymer electrolyte membrane water electrolysis. Separation coefficient β β = ([H] / [D]) ガス / ([H] / [D]) 液体 In the formula, "gas" is the generated gas, and "liquid" is the amount of 1.0-2.0 A·cm² corresponding to the stoichiometric number λ of 4-9 at the mass flow rate of water at the anode during electrolysis. -2 This is water before its current density is found to be 2-3. The stoichiometric number λ is defined as follows: λ = V × ρ / (J / 2F × 60 × M) H2O ) In the formula, V(mL min -1 ρ is the mass flow rate of water at the anode, F is the Faraday constant, J is the electrolytic current (A), and ρ is the density of water (g·mL). -1 ) and M H2O (g·mol -1 λ is the molar weight of water. A stoichiometric number λ of 10 means that 10 times the amount of fresh water that can be theoretically consumed by electrolysis at a given electrolytic current is supplied to the anode.

[0270] H. Sato et al., International Journal of Hydrogen Energy 46 (2021), pp. 33 689-33 695, reported that in anion exchange membrane water electrolysis, when λ=4, the deuterium concentration of the generated hydrogen gas is diluted to about one-fifth of that of the supplied water.

[0271] Therefore, in polymer electrolyte membrane water electrolysis, the deuterium in the generated hydrogen gas can be easily depleted to 1 / 2 to 1 / 5 of the supply water. Depending on the electrolysis conditions (water flow rate, current density), an even larger depletion ratio is possible. Since the average deuterium content of water is approximately 150 ppm relative to the total hydrogen content, the hydrogen provided in step (a) of the method of the present invention may have a deuterium content of 30 to 75 ppm relative to the total hydrogen content, or even lower.

[0272] AEM water electrolysis technology employs low-cost catalyst materials, similar to those used in alkaline electrolysis, and solid polymer electrolytes, similar to those used in PEM electrolysis technology. Because AEM electrolysis technology operates in an alkaline environment (pH approximately 10), it allows for the use of small amounts of non-precious metal electrode catalysts (i.e., catalysts free of platinum group metals = PGM-free catalysts) while also being compatible with zero-gap configurations. The membranes used in this type of electrolysis are polymer membranes containing quaternary ammonium salts. These are relatively inexpensive and have low interaction with atmospheric CO2.

[0273] catalyst: As an example of a hydrogen-evolving active (HER) catalyst, a catalyst based on Ni-Mo alloy material is preferred.

[0274] As examples of oxygen evolution reaction (OER) catalysts, highly active oxides mixed with transition metals are preferred. Specific examples include CuxCo3_xO4, NiCo2O4:Fe, and Ni-Fe alloys on a Ni foam support, such as PGM-free catalysts (Ni-Fe, Ni-Mo, Ni / (CeO2-La2O3) / C, and CuxCo3_xO4).

[0275] Membranes and ionomers: The chemical stability of AEM under alkaline conditions has been significantly improved, due to the development of stabilized functional groups on the polymer backbone. This makes it possible to use such films at high temperatures for extended periods during AEM electrolysis. Suitable films and ionomers are known to those skilled in the art and are described, for example, in the review below. One example is the commercially available film Tokuyama A201.

[0276] Preparation of membrane electrode assemblies and cell performance: Based on the physical and electrochemical characterization of the film electrode assemblies prepared by either the catalyst-catalyst coated substrate (CCS) or catalyst coated film (CCM) method, it is suggested that CCM is preferred because the improvement in ionic conductivity is far more important than any improvement in electronic conductivity.

[0277] Liquid electrolyte: When pure water is supplied, the current density generally becomes poor, but 1% K2CO3 or dilute KOH solutions yield good results. Good electrolytic performance is achieved with a 1% K2CO3 electrolyte. Therefore, it is preferable that the aqueous electrolyte contains 0.1-2 wt% K2CO3 or KOH.

[0278] An overview of hydrogen production by anion exchange membrane water electrolysis is provided in HAMiller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0279] Beyond alkaline water electrolysis, AEM, and PEM, another commercially available electrolysis technology is solid oxide electrolysis (SOE).

[0280] In a SOEC (Solid Oxide Electrolytic Cell), water is supplied to the cathode, where it undergoes a water reduction reaction (WRR), converting it into hydrogen gas and oxide ions. This hydrogen gas is then transported to a purification module, where it is decomposed from the remaining water. Next, oxide ions move from the cathode to the anode, releasing electrons into the external circuitry, and are converted into oxygen gas via an oxygen evolution reaction (OER). Typically, SOFCs operate at temperatures of 800-1000°C, because high temperatures are necessary to thermally activate the movement of oxide ions and accelerate the electrochemical reactions at both electrodes. As a result, overall efficiency is improved. SOECs are described, for example, in K. Kamlungsua et al., FUEL CELLS 20, 2020, No. 6, 644-649.

[0281] Preferably, the electrolysis for obtaining hydrogen (sometimes defined as step (a0) in this specification) is water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0282] In a more preferred embodiment, the electrolysis for obtaining hydrogen is solid oxide water electrolysis (SOE).

[0283] In the art, it is known that the deuterium in the hydrogen gas generated can be depleted with respect to the feedwater in water electrolysis, such as in polymer electrolyte membrane water electrolysis. The depletion coefficient depends on the electrolysis conditions (water flow rate, current density). Since the average deuterium content (molar occupancy of deuterium) of water is about 150 ppm relative to the total hydrogen content, the hydrogen provided in step (a) of the method of the present invention has a molar occupancy (deuterium content) of deuterium of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm relative to the total hydrogen content, or even lower.

[0284] In general, any water source can be used in the preferred water electrolysis in step (a). However, since the hydrogen prepared in step (a) has a deuterium molar occupancy (deuterium content) of less than 100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, it is preferable to use water in which the deuterium molar occupancy (deuterium content) is less than 160 ppm based on the total hydrogen content.

[0285] Vienna Standard Mean Seawater (VSMOW) is an isotopic standard for water defined by the International Atomic Energy Agency in 1968. Despite the somewhat misleading term "seawater," VSMOW refers to pure water (H2O) and does not contain any salts or other substances typically found in seawater. VSMOW serves as a reference standard when comparing the isotopic ratios of hydrogen and oxygen, which are mostly found in water samples. Extremely high-purity distilled VSMOW water is also used to improve the accuracy of measurements of the physical properties of water and to define laboratory standards, because it represents "average seawater" and is considered to effectively represent the Earth's water content.

[0286] The isotopic composition of VSMOW water is specified as the ratio of the molar abundance of the rare isotope in question to the molar abundance of its most abundant isotope, and is expressed as parts per million (ppm). For example 16 O (the most abundant isotope of oxygen, containing 8 protons and 8 neutrons) is found in seawater. 17 It is found in approximately 2,632 times more abundance than O (which has additional neutrons).

[0287] The isotopic ratio of VSMOW water is defined as follows: 2 H / 1 H = 155.76 ± 0.1 ppm (ratio of 1 part per approximately 6420 copies) 3 H / 1 H = 1.85 ± 0.36 and multiples; 10-11 ppm (ratio and multiples of 1 part per 5.41 parts; ignoring work related to physical properties, 10 16 Department) 18 O / 16 O = 2005.20 ± 0.43 ppm (approximately 1 part per 498.7 parts) 17 O / 16 O = 379.9 ± 1.6 ppm (ratio of 1 part per approximately 2632 parts) (See https: / / en-academic.com / dic.nsf / enwiki / 753132)

[0288] More preferably, the water in step (a) has an average deuterium content of 1 ppm (up to 156 ppm based on the total hydrogen content for ultralight water, most preferably 2 ppm to 150 ppm based on the total hydrogen content).

[0289] Methods for depleting deuterium in water are known to those skilled in the art. However, such methods are generally energy-consuming electrolytic methods, as described, for example, in Chinese Patent Application Publication No. CN103848399A.

[0290] Therefore, when using deuterium-depleted water, it is preferable to use deuterium-depleted water obtained from the following resources: - By-product of "heavy water" (D2O) formation (heavy water has applications in organic chemistry, drug development, and nuclear reactors); (deuterium content approximately 10-120 ppm) - Water from high-altitude areas; (deuterium content approximately 120-150 ppm) - Surface rivers and lake waters; (deuterium content approximately 130-150 ppm) - Any water source where the deuterium content is lower with the seasons, for example, water collected at low temperatures (winter cold water has a lower deuterium content than summer warm water); for example, water obtained during winter time, such as from snow or ice; (deuterium content approximately 120-150 ppm) - Polar water and Antarctic glacier water (deuterium content approximately 90-150 ppm) - Low-salinity seawater, such as that from near river mouths, desalination, brackish water, and wastewater treatment effluent; (deuterium content approximately 130-155 ppm)

[0291] Process (a) Step (a) relates to the step of forming ammonia by reacting hydrogen with nitrogen. In the method for preparing ethylene oxide or propylene oxide, ethanolamines, polyethyleneimine and alkoxylated compounds of the present invention, hydrogen is preferably obtained by electrolysis, preferably by water splitting using energy that is at least partially produced from non-fossil resources. Preferred methods for producing the hydrogen in step (a) are described above.

[0292] In the method for preparing alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants of the present invention, hydrogen is obtained by electrolysis based on electricity generated, at least partially, from non-fossil energy.

[0293] The reaction in step (a) preferably follows the Haber-Bosch process.

[0294] Catalysts commonly used in the Haber-Bosch process generally fall into one of two categories: molten iron catalysts and supported metal catalysts. Molten iron catalysts are derived from iron oxide, which has three potential forms: Fe2O3, Fe3O4, and Fe1-xO, known as hematite, magnetite, and wustite, respectively. Industrially, these iron catalysts are multiple-enhanced with accelerators such as K2O, BaO, KOH, CaO, MgO, and Al2O3, which are present in small amounts, on the order of several weight percent.

[0295] A supported metal catalyst is a catalyst composed of a metal catalyst material, and typically ruthenium or cobalt present on the surface of the support material for the ammonia synthesis reaction, and usually activated carbon or a metal oxide. Generally, the weight percentage of the metal catalyst is approximately 2-10%.

[0296] Other catalysts that can be used include nickel and nitride catalyst systems or electride, hydride, nitride, oxynitride / hydride-enhanced Ru, Fe, Co, and Ni catalysts.

[0297] The catalyst described above can be used in both conventional centralized, large-scale Haber-Bosch ammonia synthesis plants and decentralized, small-scale ammonia production using the same method.

[0298] In one embodiment of the present invention, step (a) is carried out at a pressure in the range of 50 to 350 bar (absolute value), preferably 150 to 300 bar (absolute value).

[0299] In one embodiment of the present invention, step (a) is carried out at a temperature in the range of 300 to 600°C, preferably 400 to 500°C.

[0300] The overall kinetic isotope effect is cumulative because it will similarly be present in any subsequent production process downstream in the value chain. By carrying out process (a), ammonia is formed. The deuterium content may even be lower than that corresponding to the distribution obtained by the classical petrochemical route.

[0301] Process (b) Step (b) relates to the step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide. In the method for preparing ethanolamines of the present invention, in the method for preparing polyethyleneimine of the present invention, in the method for preparing ethylene oxide or propylene oxide of the present invention, and in the method for preparing alkoxylated compounds of the present invention, hydrogen is obtained, at least in part, by hydrolysis using energy produced at least in part from non-fossil resources, preferably by electrolysis. Preferred methods for producing hydrogen in step (b) are described above.

[0302] In the method for preparing ethylene oxide or propylene oxide according to the present invention, and in the method for preparing alkoxylated compounds according to the present invention, step (b) generally includes a step of forming methanol by reacting hydrogen with carbon dioxide.

[0303] In the present invention, a method for producing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines, in the method for producing alkoxylated polyethyleneimines and a method for producing surfactants, step (b) preferably involves reacting hydrogen having a molar occupancy of deuterium in the range of ≤100 ppm, preferably 10 to ≤95 ppm, more preferably 10 to ≤90 ppm, and most preferably 10 to ≤80 ppm, based on the total hydrogen content, with carbon oxides, preferably carbon dioxide, by electrolysis based on electricity generated at least partially from non-fossil energy (for example, from step (a0) of the method described herein), thereby forming methanol.

[0304] Suitable carbon oxides are carbon monoxide, carbon dioxide, or a mixture of both, where carbon dioxide is preferred.

[0305] In one embodiment of the method for preparing ethylene oxide or propylene oxide according to the present invention, and in one embodiment of the method for preparing alkoxylated compounds according to the present invention, it is essential that the carbon dioxide in step (b) is obtained, in whole or in part, from industrial exhaust gases or from the air or from ocean water or other natural water sources, or from biological processes, such as fermentation processes from waste or biomass. According to the method of the present invention, the alkoxylated compounds, and ethylene oxide or propylene oxide, respectively, are provided with a low cradle-to-grave (i.e., including Scope 3 downstream (see above for details)) product carbon footprint (PCF), and these alkoxylated compounds generally also exhibit good biodegradability.

[0306] The term “at least a portion is recovered from industrial exhaust gases or from air or from seawater or other natural waters, or obtained from biological processes, for example, from fermentation processes from waste or biomass” means that a portion of the carbon dioxide may still be obtained from other sources. For example, carbon dioxide can be technically obtained by burning coke in excess air or as a by-product of lime calcination and subsequent refining, and natural gas sources (mineral water) may also be used for extraction. However, the amount of carbon dioxide obtained from sources other than recovery from industrial exhaust gases or from air or from seawater or other natural waters, or from biological processes, for example, from fermentation processes from waste or biomass, should be as small as possible in the method of the present invention, preferably 50% or less, preferably 30% or less, most preferably 20% or less, and even more preferably 10% or less. In one most preferred embodiment, carbon dioxide is obtained exclusively from industrial exhaust gases, from air, or from ocean water or other natural water sources, or from biological processes, such as fermentation processes from waste or biomass.

[0307] Any available recovery technology can be used.

[0308] More preferably, at least 50%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90%, and most preferably 100% of all carbon dioxide required to be used in step (a) of the method of the present invention is recovered from industrial exhaust gases or from air or from ocean water or other natural water, or obtained from a biological process, for example, from a fermentation process from waste or biomass.

[0309] By carrying out step (b) according to the embodiment of the method for preparing ethylene oxide or propylene oxide and the method for preparing alkoxylated compounds according to the present invention (where it is essential that all or at least part of the carbon dioxide in step (b) is recovered from industrial exhaust gas, air, seawater or other natural water, or obtained from a biological process, for example, from a fermentation process from waste or biomass), CH3OH, methanol is formed by reacting the carbon dioxide, which is at least part recovered from industrial exhaust gas, air, seawater or other natural water, or obtained from a fermentation process from waste or biomass, with hydrogen.

[0310] The process conditions for the hydrogenation of carbon monoxide or a mixture of carbon monoxide and carbon dioxide are known in themselves, and include, for example, low-pressure synthesis, medium-pressure synthesis, and high-pressure synthesis.

[0311] i) Low-pressure synthesis Low-pressure synthesis is generally carried out at a pressure of 50–100 bar. The temperature is generally 220–300°C. Generally, catalysts based on Cu, Zn, and Al₂O₃ (e.g., CuO / ZnO / Al₂O₃) are used. Low-pressure synthesis is the most preferred method for preparing methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0312] ii) Medium-pressure synthesis Intermediate-pressure synthesis is generally carried out at a pressure of 100–250 bar. The temperature is generally up to 300°C. Catalysts generally used are based on Zn / Cr2O3 or Zn-Cu catalysts.

[0313] iii) High-pressure synthesis. High-pressure synthesis is generally carried out at a pressure of 250–350 bar. The temperature is generally 320–380°C. As a catalyst, zinc-chromium oxide-based catalysts are generally used. This method is not very preferable for the production of methanol from carbon monoxide or from a mixture of carbon monoxide and carbon dioxide.

[0314] The current global energy system for the chemical industry is still primarily based on the use of fossil fuels, and although the use of renewable energy sources is increasing, this will likely continue in the medium and short term. The large-scale use of fossil fuels in industry and transportation results in large amounts of CO2 emissions. The object of the present invention is to provide environmentally friendly ethanolamines, polyethyleneimines and ammonia, as well as environmentally friendly ethylene oxide, propylene oxide, alkoxylated compounds, alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines and surfactants, and environmentally friendly methods for producing them. Therefore, methanol is hydrogen, - In the case of ethanolamines, polyethyleneimines, ammonia, ethylene oxide, propylene oxide, and alkoxylated compounds, hydrogen is obtained, preferably by electrolysis, by water splitting using energy that is at least partially derived from non-fossil resources. and - In the case of alkoxylated diamines, oligoamines and polyamines, alkoxylated polyethyleneimines, and surfactants, hydrogen having a deuterium molar occupancy of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated at least partially from non-fossil energy (for example, from step (a0) of the method described herein). of, It is prepared by reacting with carbon dioxide in step (b) of the method of the present invention.

[0315] In a preferred embodiment, all or at least part of the carbon dioxide provided in step (b) is recovered from industrial exhaust gases or air, preferably ambient air, or—in the case of ethanolamines, polyethyleneimines, ammonia, ethylene oxide, propylene oxide, alkoxylated compounds—from seawater or other natural water. Any available recovery technology may be used.

[0316] An overview of commercially available CO2 capture technologies is provided in Koytsoumoa et al., The Journal of Supercritical Fluids, Volume 132, February 2018, Pages 3-16 and NexantECA, Carbon Capture and Sequestration (CCS) Technologies, TECH 2022S7, Christopher Ho, Caleb Chong, Alexander Zoelle, October 2022. Information on CO2 capture from ocean water and other natural water sources can be found, for example, at https: / / arpa-e.energy.gov / technologies / exploratory-topics / direct-ocean-capture.

[0317] CO2 capture is most cost-effective at point sources, such as large-scale carbon-based energy facilities, industries with significant CO2 emissions (e.g., cement production, ammonia synthesis, steelmaking), natural gas processing, synthetic fuel plants, and fossil fuel-derived hydrogen production plants. While CO2 can be extracted from the air, this method is expensive because the lower concentration of CO2 in the air compared to combustion sources complicates engineering.

[0318] In some preferred embodiments, the carbon dioxide provided in step (b) is recovered in whole or in part from industrial exhaust gases.

[0319] Major industrial sources of CO2 include power plants based on the combustion of fossil fuels, oil refineries, biogas sweetening (e.g., fermentation), and the production of chemicals. Relevant chemical production processes include, for example, naphtha cracking of C1-C4 olefins and C6 aromatics, as well as downstream chemicals, particularly ammonia (based on steam reforming of natural gas) and other CO2-intensive products. Furthermore, industrial paper, food, cement, mineral, and steel production can be cited as examples.

[0320] In post-combustion recovery, CO2 is extracted after the combustion of fossil fuels—this is a scheme that can be applied to fossil fuel power plants. CO2 is recovered from exhaust gas at the power plant or other point source. Absorption, or amine scrubbing of carbon, is the dominant recovery technology. Currently, this is the only carbon recovery technology used industrially. Preferred post-carbon recovery methods include, for example, absorption (chemical, physical), adsorption (chemical, physical), membrane treatment, biological treatment, and cryogenic treatment.

[0321] Pre-conversion recovery refers to the recovery of CO2 generated as an undesirable byproduct of intermediate reactions in conversion processes. Several examples include ammonia production and coal gasification in power plants. In ammonia production, before ammonia synthesis can proceed, the CO2 produced along with hydrogen during steam reforming must be removed – absorption with monoethanolamine (MEA) and / or diethanolamine (DEA) is commonly used for this purpose. Similarly, in integrated gasification combined cycle (IGCC) power plants, CO2 must be separated from hydrogen. This is typically achieved using physical solvents such as the Selexol and Rectisol methods. Note that in power plant applications, pre-conversion recovery is also referred to as pre-combustion recovery.

[0322] Oxyfuel combustion technology involves the combustion of carbonaceous fuels in the presence of pure oxygen instead of air. Because this oxidizer (O2) does not contain other components of the air (such as nitrogen), the CO2 concentration in the exhaust gas becomes extremely high, while water vapor content can be easily removed.

[0323] CO2 is adsorbed onto the MOF (metal-organic frame) by physical or chemical adsorption based on the MOF's porosity and selectivity, leaving behind a gas flow with little CO2. Next, the CO2 is stripped from the MOF using thermal swing adsorption (TSA) or pressure swing adsorption (PSA), allowing the MOF to be reused.

[0324] In some other preferred embodiments, the carbon dioxide provided in step (b) is recovered in whole or in part from air, preferably ambient air.

[0325] Direct air capture (DAC) is a method for directly capturing carbon dioxide (CO2) from ambient air to produce a concentrated CO2 stream for sequestration, utilization, or the production of carbon-neutral fuels. CO2 extraction is achieved by contacting ambient air with a chemical medium, typically an aqueous alkaline solvent or adsorbent. From such a chemical medium, CO2 is stripped by the subsequent application of energy (i.e., heat), resulting in a CO2 stream that can be dehydrated and compressed, while simultaneously regenerating the chemical medium for reuse.

[0326] In Chen, Lackner et al., Angew. Chem. Int. Ed. 2020, 59, 6984-7006, “Sorbents for the Direct Capture of CO2 from Ambient Air,” the main types of adsorbents designed to recover CO2 from ambient air are described, classified by their adsorption mechanism, namely physical adsorption, chemical adsorption, and moisture swing adsorption.

[0327] Kommalapati et al., Energy Technol. 2017, 5, 822-833, describes the application of polyethyleneimine in carbon dioxide recovery and separation.

[0328] Diluted CO2 can be efficiently separated using an anion exchange polymer resin called Marathon MSA, which absorbs CO2 from the air when dry and releases it when exposed to moisture. Most of the energy for this process is supplied by the latent heat of the phase transition of water. Other materials that can be used are metal-organic structures (or MOFs). Membrane separation of CO2 relies on semipermeable membranes.

[0329] In some other preferred embodiments—for ethanolamines, polyethyleneimines, ammonia, ethylene oxide, propylene oxide, and alkoxylated compounds—all or at least part of the carbon dioxide provided in step (b) is recovered from seawater and other natural waters (direct ocean recovery (DOC)).

[0330] DOC (Derived Oxide Concentration) is one of the main pathways from the perspective of carbon dioxide removal (CDR). Non-biological DOC technologies include, for example, electrochemical ocean recovery (EOC), mineralization, and ocean alkalinity enhancement (OAE). There is clearly visible attention being paid to EOC. There are various different methods, including the use of bipolar membrane electrodialysis (BPMED), three-chamber electrolytic cation exchange modules (E-CEM), and electrochemical hydrogen loop (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 (November 21, 2022). Proceedings of the 16th Greenhouse Gas Control Technologies Conference (GHGT-16) 23-24 Oct 2022 (SSRN: available at https: / / ssrn.com / abstract=4282969 or http: / / dx.doi.org / 10.2139 / ssrn.4282969)).

[0331] In one embodiment of the present invention, the ethanolamines, which are a mixture of monoethanolamine, diethanolamine, and triethanolamine according to the present invention, or each thereof, preferably a mixture of monoethanolamine (MEA) and diethanolamine (DEA), and / or polyethyleneimine, are used in a CO2 recovery method. The ethanolamines of the present invention, which are a mixture of monoethanolamine, diethanolamine, triethanolamine, and polyethyleneimine, or each thereof, add as little as possible to the CO2 emissions, and in a preferred embodiment, add nothing at all, and therefore contribute as little as possible, preferably none at all, to the CO2 emissions themselves, i.e., the cradle-to-gate PCF values ​​of the polyethyleneimine and ethanolamines (monoethanolamine, diethanolamine, and triethanolamine) of the present invention are as low as possible, where specific cradle-to-gate PCF values ​​are described above.

[0332] In further embodiments, the present invention relates to the use of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, preferably ethanolamines selected from a mixture of monoethanolamine (MEA) and diethanolamine (DEA), or polyethyleneimine (liquid and / or solid) as a CO2 absorbent in a CO2 recovery method.

[0333] Suitable carbon capture processes have been described above and are known in the relevant technical field.

[0334] In step (b), methanol is formed by reacting carbon oxides, preferably carbon dioxide, and hydrogen.

[0335] The process conditions for the hydrogenation of carbon oxides, preferably carbon dioxide, are known in themselves. Various different treatment methods are under development for the synthesis of methanol by the hydrogenation of CO2: (1) heterogeneous catalytic action, (2) homogeneous catalytic action, (3) electrochemical action, and (4) photocatalytic action (see R. Guil-Lopez, Materials 2019, 12, 3902; doi:10.3390 / ma12233902). Preferably, the synthesis of methanol by the hydrogenation of carbon dioxide is carried out in the presence of a heterogeneous catalyst.

[0336] Generally, methanol production is carried out in a synthetic converter, such as a fixed-bed catalytic reactor.

[0337] The average temperature inside the reactor is generally in the range of 150 to 300°C. The average pressure inside the reactor is generally in the range of 50 to 150 bar (absolute value).

[0338] An overview of suitable heterogeneous catalyst systems is provided in Kristian Stangeland, Hailong Li & Zhixin Yu, Energy, Ecology and Environment volume 5, pages 272-285 (2020). This process requires a multi-component catalyst system. Interactions between components are essential for the high activity and selectivity of CO2-to-methanol catalysts. This has been demonstrated by numerous catalyst systems composed of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., Al2O3, ZnO, ZrO2, In2O3). Such composite systems may include mixtures of metallic phases, alloy phases, and metal oxide phases. Currently, the most promising catalyst systems for large-scale industrial processes are Cu-based and In-based catalysts due to their superior catalytic performance. A suitable catalyst is, for example, copper-zinc-alumina.

[0339] By carrying out step (b), CH3OH and methanol are formed by reacting carbon oxides, preferably carbon dioxide, with hydrogen, preferably obtained by electrolysis, which is at least partly obtained by water splitting using energy that is at least partly produced from non-fossil resources.

[0340] Furthermore, by carrying out step (b), CH3OH, methanol is formed by reacting carbon oxides, preferably carbon dioxide, with hydrogen having a molar deuterium content in the range of ≤100 ppm, preferably 10 to ≤95 ppm, more preferably 10 to ≤90 ppm, and most preferably 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated at least partially from non-fossil energy (e.g., from step (a0) of the method described herein). The deuterium content may even be lower than that corresponding to the distribution obtained by classical petrochemical routes.

[0341] Processes (c) and (d) Process (c) In step (c), the methanol from step (b) is - In the method for preparing ethanolamines of the present invention, and in the method for preparing polyethyleneimines of the present invention, converted to -ethene - In the method for preparing ethylene oxide or propylene oxide according to the present invention, in the method for preparing alkoxylated compounds according to the present invention, and in the method for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines according to the present invention, it is converted to -ethene and / or propene, preferably in the method for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimines according to the present invention, it is converted to -ethene.

[0342] Preferably, the ethene and / or propene in step (c) are obtained by a methanol-to-olefin (MTO) process.

[0343] The methanol-to-olefin (MTO) process is a method for producing olefins (particularly ethenes and propenes) from methanol.

[0344] The MTO process is generally known to those skilled in the art. Examples of the MTO process are generally described below: This method can be divided into three main steps.

[0345] Firstly, methanol is supplied to a reactor, preferably a fluidized bed reactor. In the reactor, a catalyst is used to produce gases that are particularly ethylene-rich and propylene-rich. The percentage yields of ethylene and propylene are determined, in particular, by the selection of the catalyst and the control of the reactor temperature and pressure, as is known to those skilled in the art. For example, to achieve the highest possible yield of ethylene, the reactor is operated at a preferred temperature of 300 to 600°C and a preferred pressure of 0.1 to 0.3 MPa. More general temperature and pressure ranges are shown below. The gas stream leaving the reactor generally contains light olefins (generally ethene, propene, butadiene, and butene) as well as carbon monoxide (CO) and carbon dioxide (CO2).

[0346] Secondly, the gas stream leaving the reactor is preferably cooled to about 95–115°C. This is preferably done by quenching. This also generally removes water and dust from the gas stream. Any dimethyl ether and methanol that may have formed remaining in the gas stream are returned to the reactor.

[0347] Thirdly, the individual gas fractions are fractionated. This is generally similar to fractionation during production through a vapor cracking apparatus as is known in the art.

[0348] The MTO process is generally an acid-catalyzed reaction. Preferred catalysts are zeolites such as silica and alumina-containing zeolites (e.g., ZSM-5) and silicon-alumina-phosphate zeolite catalysts (SAPO) (e.g., SAPO-34).

[0349] This reaction generally takes place at temperatures between 300 and 600°C. The pressure is generally between 0.1 and 0.3 MPa.

[0350] This method is preferably carried out in a fluidized bed reactor.

[0351] The molar ratio of propylene to ethylene can be adjusted by selecting appropriate process conditions, ranging from 0.77 in ethylene production mode to 1.33 in propylene production mode.

[0352] Examples of commercial MTO technology licensors include UOP (e.g., UOP Advanced MTO process), Energy Technology Co. Ltd. (DMTO process), and Sinopec (SMTO process).

[0353] For further details, see, for example, “Ethylene” by Adam Chan, Nexant, TECH 2018-1, July 2018, pp. 100-109.

[0354] Steps (c) and (d) are generally known as CO2-to-olefin (CO2MTO) via the methanol-to-olefin pathway. The specific conditions for each step are described above.

[0355] In the method for preparing ethanolamines of the present invention, and in the method for preparing polyethyleneimine of the present invention, and also preferably in the method for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimine of the present invention, preferred step (c) will be described later:

[0356] Process (c) In step (c), the methanol from step (b) is converted to ethylene.

[0357] Preferably, the ethylene in step (c) is obtained by a methanol-to-olefin (MTO) process.

[0358] The MTO process is an acid-catalyzed reaction. Preferred catalysts are zeolites such as silica and alumina-containing zeolites (e.g., ZSM-5) and silicon-alumina-phosphate zeolite catalysts (SAPO) (e.g., SAPO-34).

[0359] This reaction generally takes place at temperatures between 300 and 600°C. The pressure is generally between 0.1 and 0.3 MPa.

[0360] This method is preferably carried out in a fluid catalyst reactor.

[0361] The ratio of propylene to ethylene can be adjusted by selecting appropriate process conditions, ranging from 0.77 in ethylene production mode to 1.33 in propylene production mode.

[0362] Examples of commercial MTO technology licensors include UOP (e.g., UOP Advanced MTO process), Energy Technology Co. Ltd. (DMTO process), and Sinopec (SMTO process).

[0363] For further details, see, for example, “Ethylene” by Adam Chan, Nexant, TECH 2018-1, July 2018, pp. 100-109.

[0364] The preferred steps (b) and (c) are generally known as CO2-to-olefin (CO2MTO) via the methanol-to-olefin pathway. The specific conditions for each step are described above.

[0365] Process (d) In step (d), ethylene oxide and / or propylene oxide are formed by reacting the ethene and / or propene from step (c) with oxygen or an oxidizing agent.

[0366] Ethylene oxide: In general, ethylene oxide can be prepared by any method known in the art. Preferably, the ethylene oxide of step (d) is obtained by oxidation of ethene (direct oxidation method).

[0367] The direct oxidation method is preferably carried out in the gas phase, for example with oxygen or air, in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0368] The direct oxidation of ethene is generally carried out at a temperature of 230–270°C. The pressure is preferably in the range of 10–30 bar.

[0369] In a preferred embodiment, the direct oxidation of ethene in step (d) is carried out by gas-phase selective ethene oxidation, which is typically performed in a fixed-bed tubular reactor at 230-270°C and 10-30 bar using an Ag / Al2O3-supported catalyst.

[0370] A preferred catalyst for the direct oxidation process of ethene in step (d) is: - Preferably a Re / Cs / Ag / Al2O3 supported catalyst operating with an excess amount of C2H4 / O2; or - Preferably a silver-based catalyst, such as an alkali metal (Na, Cs)-promoted Ag / Al2O3-supported catalyst that operates with an excess amount of O2 / C2H4.

[0371] Oxides of Mo and S are also known to promote the Re / Cs / Ag / Al2O3 supported system for ethylene oxide (EO) formation. Therefore, the Re / Cs / Ag / Al2O3 supported system may also contain oxides of Mo and / or S as accelerators.

[0372] In addition, C2H4Cl2 may also be added to the Cl deposited on the catalyst, which acts as an accelerator.

[0373] For an example of the explanation, see, for instance, “Ethylene Oxide” by Mia Monconduit and Karen Jobes, IHS Markit, Chemical Economics Handbook, 22 December 2020, pp. 14-16.

[0374] In the method for preparing ethanolamines of the present invention, and in the method for preparing polyethyleneimine of the present invention, and also preferably in the method for preparing alkoxylated diamines, oligoamines and polyamines or alkoxylated polyethyleneimine of the present invention, preferred step (d) will be described later:

[0375] Process (d) In step (d), ethylene oxide is formed by reacting the ethylene from step (c) with oxygen.

[0376] Preferably, the ethylene oxide in step (d) is obtained by oxidation of ethylene (direct oxidation method).

[0377] The direct oxidation method is preferably carried out in the gas phase, for example with oxygen or air, in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0378] Step (d) is generally carried out at a temperature of 230–270°C. The pressure is preferably in the range of 10–30 bar.

[0379] In a preferred embodiment, step (d) is carried out in a fixed-bed tubular reactor by gas-phase selective ethylene oxidation, typically performed at 230-270°C and 10-30 bar with an Ag / Al2O3-supported catalyst.

[0380] A preferred catalyst for method (d) is: - Preferably a Re / Cs / Ag / Al2O3 supported catalyst operating with an excess amount of C2H4 / O2; or - Preferably a silver-based catalyst, such as an alkali metal (Na, Cs)-promoted Ag / Al2O3-supported catalyst that operates with an excess amount of O2 / C2H4.

[0381] Oxides of Mo and S are also known to promote the formation of the Re / Cs / Ag / Al2O3 supported system for EO formation. Therefore, the Re / Cs / Ag / Al2O3 supported system may also contain oxides of Mo and / or S as accelerators.

[0382] In addition, C2H4Cl2 may also be added to the Cl deposited on the catalyst, which acts as an accelerator.

[0383] For an example of the explanation, see, for instance, “Ethylene Oxide” by Mia Monconduit and Karen Jobes, IHS Markit, Chemical Economics Handbook, 22 December 2020, pp. 14-16.

[0384] Surprisingly, the method according to the present invention, particularly in the case of ethylene oxide, shows a measurable increase in epoxide selectivity compared to conventional methods using fossil-derived raw materials (resulting in fewer by-products such as acetaldehyde and CO2 formed, and a longer usage period for the catalyst run).

[0385] In particular, for propylene oxide (see below) (HPPO process), it was found that the reliability of the catalyst run lifecycle was significantly improved. Higher run reliability has the advantage of improving the planning efficiency in industrial production practices, especially in processes with relatively high catalyst regeneration cycle frequencies, such as HPPO.

[0386] Propylene oxide: Generally, propylene oxide can be prepared by any method known in the art. Preferred methods for preparing propylene oxide are described above. Preferably, the propylene oxide of step (d) is generally obtained by oxidation of propene with hydrogen peroxide as the oxidizing agent in the presence of a catalyst, preferably a zeolite catalyst, and more preferably Titansilikalit-1 (TS-1) (HPPO method).

[0387] The HPPO process is generally carried out at temperatures below 90°C and pressures below 35 bar. This method may be performed in a single or multi-reactor system, for example, in a tubular reactor, for example, in a fixed-bed or trickle-bed reactor.

[0388] The HPPO method and other industrially relevant methods are described, for example, in M. Di Serio et al., Ind. Eng. Chem. Res. 2013, 52, 1168-1178.

[0389] Preferably, the hydrogen peroxide used as an oxidizing agent in the HPPO method performed for the preparation of propylene oxide according to the present invention may be obtained by any known method. Generally, hydrogen peroxide is obtained by the anthraquinone method (NexantECA study publication by Jia Lin and Adam Chan, Propylene Oxide, TECH 2022-3, December 2022).

[0390] The anthraquinone process is based on the catalytic hydrogenation of anthraquinone to anthrahydroquinone by hydrogen on a catalyst, such as a palladium catalyst. Subsequently, the anthraquinone is modified by reoxidation with oxygen, such as pure oxygen or atmospheric oxygen, under the desorption of hydrogen peroxide.

[0391] Generally, the runs of the anthraquinone process are carried out under mild reaction conditions (generally a pressure below 1 MPa, i.e., 10 bar, and generally a temperature below 100°C), and preferably continuously.

[0392] Since aggregation of anthraquinone to anthrahydroquinone should not occur during this process, the solubility can be adapted by the alkyl substituent and solvent composition. For this purpose, alkylated derivatives such as 2-ethyl-, 2-tert-butyl-, or 2-amylanthraquinone are used. To keep the anthraquinone in solution, a nonpolar substance, such as a C9 / C10 alkylbenzene mixture, is often part of the working solution. A polar substance such as tris-(2-ethylhexyl)-phosphate, diisobutylcarbinol, tetrabutylurea or urea or methylcyclohexyl acetate may take over this task in place of the hydroquinone.

[0393] For information on the preparation of hydrogen peroxide, see, for example, 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 NexantECA study publication by Sandrine Romand, Hydrogen Peroxide, TECH 2019-8, September 2019.

[0394] In a preferred embodiment of the present invention, propylene oxide in step (d) is obtained by oxidation of propene with hydrogen peroxide as the oxidizing agent, preferably by the HPPO method.

[0395] Preferably, the present invention relates to a method for preparing propylene oxide, comprising the following steps: (b) A step of forming methanol by reacting hydrogen with carbon dioxide, (c) A step of converting methanol in step (a) to propene, (d) A step in which the propene from step (b) is reacted with an oxidizing agent to form propylene oxide. Includes, The carbon dioxide in process (b) is at least partially recovered from industrial exhaust gases, air, ocean water, or other natural water sources, or obtained from biological processes, such as fermentation processes from waste or biomass. and / or The hydrogen in step (b) of the method of the present invention is preferably obtained by hydrolysis, preferably by electrolysis, and the by-product of hydrolysis, preferably electrolysis, is pure oxygen, which is usually released into the environment without further use; and Therefore, the propylene oxide in step (d) is preferably obtained by the HPPO method, by oxidation of propene with hydrogen peroxide as the oxidizing agent. This relates to a method for obtaining hydrogen peroxide, preferably by the anthraquinone method.

[0396] More preferably, the present invention relates to a method for preparing propylene oxide, comprising the following steps: (e) A step of forming methanol by reacting hydrogen with carbon dioxide, (f) A step of converting methanol in step (a) to propene, (g) A step in which the propene from step (b) is reacted with an oxidizing agent to form propylene oxide. Includes, The carbon dioxide in process (b) is at least partially recovered from industrial exhaust gases or from air or from ocean water or other natural water sources, or obtained from biological processes, such as fermentation processes from waste or biomass, and Therefore, the propylene oxide in step (d) is preferably obtained by the HPPO method, by oxidation of propene with hydrogen peroxide as the oxidizing agent. This relates to a method for obtaining hydrogen peroxide, preferably by the anthraquinone method.

[0397] As mentioned above, the hydrogen in step (b) of the method of the present invention is preferably obtained by hydrolysis, preferably by electrolysis, at least in part. The by-product of hydrolysis, preferably electrolysis, is pure oxygen, which is usually released into the environment without further use.

[0398] In one embodiment of the present invention, the oxygen in step (d) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably electrolysis, uses energy that is preferably generated at least in part from non-fossil resources.

[0399] The oxygen in step (d) described above is preferably oxygen that can be used by direct oxidation in the preparation of ethylene oxide, and oxygen used in the preparation of the oxidizing agent used in the preparation of propylene oxide. The oxidizing agent is preferably hydrogen peroxide, more preferably hydrogen peroxide prepared by the anthraquinone method.

[0400] The following are obtained in step (d) of the method of the present invention: preferably <1.7 kg CO2e / ethylene oxide 1 kg, preferably <1.6 kg CO2e / ethylene oxide 1 kg, more preferably <1.5 kg CO2e / ethylene oxide 1 kg, even more preferably <1.4 kg CO2e / ethylene oxide 1 kg, most preferably <1.3 kg CO2e / ethylene oxide 1 kg, even more preferably <1.2 kg CO2e / ethylene oxide 1 kg, even more preferably <1.1 kg CO2e / ethylene oxide 1 kg, still more preferably <1.0 kg CO2e / ethylene oxide 1 kg, still more preferably <0.9 kg CO2e / ethylene oxide 1 kg, still more preferably <0.8 kg CO2e / ethylene oxide 1 kg, still more preferably <0.7 kg CO2e / ethylene oxide 1 kg, still more preferably <0.6 kg CO2e / ethylene oxide 1 kg, still more preferably <0.5 kg Ethylene oxide having a total product carbon footprint from cradle to gate of 1 kg of CO2e / ethylene oxide, more preferably <0.4 kg of CO2e / ethylene oxide, more preferably <0.3 kg of CO2e / ethylene oxide.

[0401] Accordingly, the present invention further relates to ethylene oxide obtained by the method according to the present invention, and also to <1.7 kg CO2e / ethylene oxide 1 kg, preferably <1.6 kg CO2e / ethylene oxide 1 kg, more preferably <1.5 kg CO2e / ethylene oxide 1 kg, even more preferably <1.4 kg CO2e / ethylene oxide 1 kg, most preferably <1.3 kg CO2e / ethylene oxide 1 kg, even more preferably <1.2 kg CO2e / ethylene oxide 1 kg, even more preferably <1.1 kg CO2e / ethylene oxide 1 kg, still more preferably <1.0 kg CO2e / ethylene oxide 1 kg, still more preferably <0.9 kg CO2e / ethylene oxide 1 kg, still more preferably <0.8 kg CO2e / ethylene oxide 1 kg, still more preferably <0.7 kg CO2e / ethylene oxide 1 kg, still more preferably <0.6 kg CO2e / ethylene oxide 1 kg, still more preferably <0.5 kg This relates to ethylene oxide having a total product carbon footprint from cradle to gate of 1 kg of CO2e / ethylene oxide, more preferably <0.4 kg of CO2e / ethylene oxide, and more preferably <0.3 kg of CO2e / ethylene oxide.

[0402] The propylene oxide obtained in step (d) of the method of the present invention is preferably <3.4 kg CO2e / propylene oxide 1 kg, preferably <3.3 kg CO2e / propylene oxide 1 kg, more preferably <3.2 kg CO2e / propylene oxide 1 kg, even more preferably <3.1 kg CO2e / propylene oxide 1 kg, most preferably <3.0 kg CO2e / propylene oxide 1 kg, even more preferably <2.9 kg CO2e / propylene oxide 1 kg, still more preferably <2.8 kg CO2e / propylene oxide 1 kg, still more preferably <2.7 kg CO2e / propylene oxide 1 kg, still more preferably <2.6 kg CO2e / propylene oxide 1 kg, still more preferably <2.5 kg CO2e / propylene oxide 1 kg, still more preferably <2.4 kg The total product carbon footprint from cradle to gate is 1 kg of CO2e / propylene oxide, more preferably <2.3 kg.

[0403] Accordingly, the present invention further relates to propylene oxide obtained by the method according to the present invention, and to propylene oxide in quantities of <3.4 kg CO2e / propylene oxide 1 kg, preferably <3.3 kg CO2e / propylene oxide 1 kg, more preferably <3.2 kg CO2e / propylene oxide 1 kg, even more preferably <3.1 kg CO2e / propylene oxide 1 kg, most preferably <3.0 kg CO2e / propylene oxide 1 kg, even more preferably <2.9 kg CO2e / propylene oxide 1 kg, still more preferably <2.8 kg CO2e / propylene oxide 1 kg, still more preferably <2.7 kg CO2e / propylene oxide 1 kg, still more preferably <2.6 kg CO2e / propylene oxide 1 kg, still more preferably <2.5 kg CO2e / propylene oxide 1 kg, still more preferably <2.4 kg This invention relates to propylene oxide having a total product carbon footprint from cradle to gate of 1 kg of CO2e / propylene oxide, more preferably <2.3 kg CO2e / propylene oxide.

[0404] One carbon source in step (b) (methanol production) during the production of ethylene oxide and propylene oxide is recovered carbon dioxide. Therefore, the byproduct spectrum of methanol used in the method for preparing ethylene oxide and propylene oxide according to the present invention differs from the byproduct spectrum of methanol obtained by conventional methods (i.e., using synthesis gas "syngas," which is a combination of various amounts of H2, CO, and CO2 often derived from gasified coal or natural gas). For example, methanol obtained by conventional methods generally contains more methylformiate, acetone, and higher alcohols (≧C3) than methanol obtained by the method according to the present invention. The by-product spectra of ethene and propene produced by cracking fossil hydrocarbon raw materials such as naphtha or natural gas, which are used to obtain ethylene oxide and propylene oxide by conventional methods, are even more different from those of ethylene oxide and propylene oxide obtained by CO2-to-olefin (CO2MTO) via the methanol-to-olefin pathway according to the present invention, for example, due to the presence of highly undesirable sulfur components, particularly in naphtha.

[0405] The different by-product spectra of methanol, ethene and propene, respectively, are also reflected in downstream products, such as ethylene oxide and propylene oxide, and the alkoxylated compounds obtained by this invention.

[0406] Process (e) In step (e), the ammonia from step (a) is converted by ethylene oxide in step (d) to ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof in one or more steps.

[0407] The reaction products obtained in step (e) generally include monoethanolamine, diethanolamine, and triethanolamine.

[0408] The preparation in step (e) is preferably carried out in the presence of water, generally in a closed-cycle process with a very small supply of fresh water. However, ethanolamines can also be prepared by the reaction of ammonia and ethylene oxide in an anhydrous manner. In the anhydrous manner, a fixed-bed catalyst, such as an organic ion exchange resin or a thermally more stable acidic clay, inorganic clay, or zeolite is preferably used.

[0409] In the preferred method, the reaction occurs in the aqueous phase, and the reactor pressure is usually high enough to prevent the evaporation of ammonia and ethylene oxide at the reaction temperature.

[0410] The ammonia concentration in the water is preferably 50-100%.

[0411] The reaction pressure in the aqueous phase reaction is generally a maximum of 160 bar, preferably 90 to 130 bar (absolute value).

[0412] The reaction temperature in the aqueous phase reaction is generally a maximum of 150°C, preferably 40-130°C.

[0413] Generally, aqueous phase reactions use an excess of up to 40 moles of ammonia per mole of ethylene oxide.

[0414] Unconsumed ammonia and water are generally separated from the product in a distillation line located downstream of the reactor and then recycled.

[0415] The product distribution of these three ethanolamines can be controlled by the appropriate selection of the ammonia:ethylene oxide ratio.

[0416] The above reaction can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, but obtaining monoethanolamine usually requires a workup by distillation to remove diethanolamine and triethanolamine.

[0417] The preparation of polyethyleneimine described in steps (f), (g), and (h) below requires monoethanolamine, which is generally separated by distillation from ethanolamines obtained as a mixture of monoethanolamine, diethanolamine, and triethanolamine in steps (a) to (e) of the method according to the present invention (see step (f) below).

[0418] In the method for producing surfactants of the present invention, monoethanolamine, diethanolamine, and triethanolamine can each be separated by distillation from ethanolamines obtained as a mixture of monoethanolamine, diethanolamine, and triethanolamine in steps (a) to (e) of the method according to the present invention (see step (f)).

[0419] The method for producing alkoxylated polyethyleneimines of the present invention, as described in steps (h) and (i) below, requires monoethanolamine, which is generally separated by distillation from ethanolamines obtained as a mixture of monoethanolamine, diethanolamine, and triethanolamine in steps (a) to (e) of the method according to the present invention (see step (f)).

[0420] However, when the ethanolamines according to the present invention are used in applications different from the preparation of polyethyleneimines, separation of monoethanolamine may not be necessary. In carbon recovery, for example, a mixture of monoethanolamine and diethanolamine may be used, and only triethanolamine generally needs to be separated by distillation.

[0421] Ethanolamines are a family of chemicals that function as components in personal care products, cleaning products, and industrial applications.

[0422] Further applications of ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof according to the present invention include, for example, the following:

[0423] Personal care products Ethanolamines, particularly MEA and TEA, are used as ingredients in personal care products and cosmetics. In these types of products, ethanolamines help remove dirt and oil from the skin by dissolving fats and mixing them with other important ingredients. Because ethanolamines do not impart a strong odor, they are often used in products like hair dyes. Ethanolamines like MEA help adjust the pH to prevent decomposition when stored in containers, thus extending the shelf life of the product.

[0424] Home care and industrial cleaning products Ethanolamines such as MEA are commonly used ingredients in cleaning products such as floor and tile cleaners, as well as laundry detergents.

[0425] 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.

[0426] industrial use MEA acts as a plasticizer, helping to make plastics flexible and pliable. In chemical manufacturing plants, MEA is used to remove carbon dioxide from ammonia gas in the production of synthetic ammonia.

[0427] DEA is used in pesticides as a chemical intermediate, where it helps increase the water-soluble capacity of the insecticide. In the production of waxes, polishes, and coatings, DEA acts as an emulsifier, aiding in the mixing of ingredients and preventing corrosion of other materials.

[0428] MEA and DEA can also be used in industrial applications such as chemical manufacturing and gas processing. In refinery and natural gas flow processing processes, MEA and DEA help remove contaminants from gasoline.

[0429] TEA is used in pesticides to help disperse insecticides within crops, which in turn helps insects repel them. As a petroleum-based demulsifier, TEA helps separate oil from water and other substances. In cement additives, TEA helps promote the setting and / or hardening of cement. TEA is also used as a corrosion inhibitor for steel and zinc materials used in buildings and construction.

[0430] For an example of the explanation, see, for instance, “Ethanolamines” by Mia Monconduit and Tison Keel, IHS Markit, Chemical Economics Handbook, 14 February 2020, pp. 19-20.

[0431] Step (e0) Preparation of the alkoxylated compound of the present invention In the preparation of the alkoxylated compound of the present invention, step (e0) is generally carried out following step (d) described above.

[0432] In step (e0), ethylene oxide and / or propylene oxide obtained in step (d), and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide, are reacted in one or more steps with at least one initiator unit having a Zerevichnioff active hydrogen atom to form an alkoxylated compound.

[0433] The alkoxylated compounds prepared in the method of the present invention are i) 20 wt% to <100 wt%, preferably 30 wt% to <99.3 wt%, ethylene oxide units and / or propylene oxide units, ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of ethylene oxide and propylene oxide units, and at least one alkylene oxide unit different from the ethylene oxide and propylene oxide units. iii) At least one initiator unit having >0 wt% to 80 wt%, preferably 0.2 wt% to 70 wt%, of Tserevichnov active hydrogen atoms, (Here, the sum of the units listed in i), ii), and iii) is 100 wt%.) Includes.

[0434] i) Ethylene oxide units and / or propylene oxide units: The alkoxylated compound according to the present invention contains ethylene oxide units (EO), propylene oxide units (PO), or both.

[0435] EO and PO can exist in various weight ratios. Typically, alkoxylated compounds have EO:PO weight ratios of 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 values ​​of these ratios.

[0436] ii) At least one alkylene oxide unit different from ethylene oxide and propylene oxide units: The alkoxylated compound according to the present invention may contain at least one alkylene oxide unit different from ethylene oxide and propylene oxide units.

[0437] Examples of alkylene oxide units different from ethylene oxide and propylene oxide units include those based on 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, 1,3-propylene oxide, or tetrahydrofuran, preferably 1,2-butylene oxide or 2,3-butylene oxide, and more preferably 1,2-butylene oxide (BuO).

[0438] Preferably, no alkylene oxide units other than ethylene oxide and propylene oxide units are present; that is, the alkoxylated compound prepared in the method of the present invention contains 0 wt% alkylene oxide units other than ethylene oxide and propylene oxide units.

[0439] Alkylene oxide units may exist in the alkoxylated compound in the form of exclusively one type of alkylene oxide unit, i.e., exclusively ethylene oxide units or exclusively propylene oxide units, for example in the form of a homopolymer in the case of polymer alkylene oxide units, or in the form of two or more different alkylene oxide units, for example ethylene oxide units and propylene oxide units in the above-mentioned ratio, or ethylene oxide units and / or propylene oxide units and 1,2-butylene oxide units, for example in the form of a random copolymer or block copolymer in the case of polymer alkylene oxide units.

[0440] In certain embodiments, the polymer is EO-capped. In other embodiments, the polymer is PO-capped. Such capping may be referred to as small blocks, for example, small blocks of EO that act as caps. When a polymer is capped, it may be referred to as a block copolymer in the art. In certain embodiments, the polymer is a block PAG. Such a block PAG may include blocks that are all EO or PO, blocks of random EO / PO monomers where at least two blocks have different EO / PO ratios, or a combination of blocks that are all EO or PO and blocks that are random EO / PO.

[0441] The preferred ethylene oxide unit and / or propylene oxide unit according to the present invention is characterized by the following formula: [ka] During the ceremony, n, m, n', and m' are each independently 1 to 500, preferably 1 to 100, more preferably 2 to 50; and the base in formula (Ic) [ka] These are arranged in the form of two or more blocks, preferably two or three blocks, and / or randomly.

[0442] The total average molecular weight of ethylene oxide units is in the range of 88 to 22000 Da, preferably 88 to 4400 Da, and more preferably 88 to 2200 Da, and the total average molecular weight of propylene oxide units is in the range of 116 to 29000 Da, preferably 116 to 5800 Da, and more preferably 116 to 2900 Da. The average molecular weight of ethylene oxide units and / or propylene oxide units can be calculated based on their monomer structure.

[0443] iii) At least one initiator unit having an active hydrogen atom (Zerewitinoff) The active hydrogen of a chemical substance is reactive when determined by the Zerewitinoff method as described in the Analyst 1963, 88, 782-790. The quantitative determination of the active hydrogen of a chemical substance by adding methylmagnesium iodide in pentyl ether to a solution of the substrate and quantitatively measuring the volume of gaseous methane produced is generally known as the Zerewitinoff determination.

[0444] Preferably, the initiator unit having a Zerewitinoff active hydrogen atom is selected from the group consisting of at least one of water, monofunctional, difunctional, or polyfunctional alcohols, monofunctional, difunctional, or polyfunctional amines, and monofunctional, difunctional, or polyfunctional thio compounds. More preferred initiator units are water, monofunctional, difunctional, or polyfunctional alcohols and / or monofunctional, difunctional, or polyfunctional amines.

[0445] The initiator unit preferably contains 1 to 100, more preferably 2 to 50, most preferably 2 or 8, and even more preferably 2 or 3 Zerewitinoff active hydrogen atoms.

[0446] In the case of polyethyleneimines as the initiator unit, a preferred polyethyleneimine initiator unit having an amine value of 3 to 30 mmol / g, preferably 5 to 25 mmol / g, and more preferably 10 to 22 mmol / g.

[0447] The amine value refers to the ratio of amines present in a given element. The amine value is determined according to DIN 53176 (2000-12 edition).

[0448] Suitable examples of monofunctional, difunctional, or polyfunctional alcohols include higher alcohols such as monools, diols, triols, tetrols, or polyols, which may also be referred to in the art. In certain embodiments, the alcohol is a monool. Suitable examples of monools include C1-C 20 Alcohols, for example, n-butanol, iso-butanol, 2-ethylhexanol, 2-propylheptanol, butyl glycol, butyldiethylene glycol, butyltriethylene glycol, butylpropylene glycol, butyldipropylene glycol, butyltripropylene glycol, methyl diglycol, methyltriglycol, methyldipropylene glycol, methyldipropylene glycol, methanol, ethanol, hexanol, iso-nonanol, decanol, 2-butyloctanol, oleyl alcohol, octadecanol (C 18 Alcohol (e.g., stearyl alcohol), isononadecanol, C 12 Alcohol, C 13 Alcohol, C 14 Alcohol, C 15 Alcohol, C 16 Alcohol, C 17Alcohol, 2-ethylhexanol, 2-propylheptanol, 2-butyloctanol, 2-pentylnonanol, 2-hexyldecanol, and C 13 ~C 15 Alcohol, C 12 ~C 18 Alcohol, C 16 ~C 18 Alcohol, or C 12 ~C 14 Examples include mixtures of the aforementioned alcohols, such as alcohols. In other embodiments, the alcohol is a diol. Suitable examples of diols include ethylene glycol, 1,2-propylene glycol, 1,2-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. In yet another embodiment, the alcohol is a polyol. Suitable examples of polyols include glycerol, trimethylolpropane, and pentaerythritol.

[0449] Various amines can be used to form alkoxylated compounds. Suitable amines include monoamines, diamines, triamines, or higher-grade amines that may also be called polyamines in the art. Specific examples of suitable amines include alkanolamines, ethylenediamines, diethylenetriamines, and polyethyleneimines.

[0450] In relation to this invention, the term "polyethyleneimine" refers not only to polyethyleneimine homopolymers, but also to polymers containing NH-CH2-CH2-NH structural elements together with other alkylenediamine structural elements, such as NH-CH2-CH2-CH2-NH structural elements, NH-CH2-CH(CH3)-NH structural elements, NH-(CH2)4-NH structural elements, NH-(CH2)6-NH structural elements, or NH-(CH2)8-NH structural elements (however, in terms of molar occupancy, NH-CH2-CH2-NH structural elements) Polyalkyleneimines (which make up the majority) also refer to polyethyleneimines. Preferred polyethyleneimines contain NH-CH2-CH2-NH structural elements, which make up the majority in terms of molar occupancy, for example, reaching 60 mol% or more, more preferably at least 70 mol%, relative to the total alkyleneimine structural elements. In a special embodiment, polyethyleneimine refers to polyalkyleneimines that support one or zero alkyleneimine structural elements different from NH-CH2-CH2-NH per molecule.

[0451] In relation to this invention, "polyethyleneimine" is either linear or branched. The degree of branching can be determined by those skilled in the art according to actual application by 13C NMR.

[0452] Polyalkyleneimines, including polyethyleneimines, can be characterized by their degree of branching (DB). To define the degree of branching, refer to H. Frey et al., Acata Polym. 1997, 48, 30. In that document, the degree of branching DB is defined as follows: DB(%)=(T+Z) / (T+Z+L)×100 [in the formula, T is the average number of monomer units (primary amino groups) attached to the terminals. Z is the average number of branched monomer units (tertiary amino groups). L is defined as the average number of linearly linked monomer units (secondary amino groups). T, Z, and L can be determined by 13C-NMR in D2O.

[0453] The branching degree DB of the polyalkyleneimines, particularly polyethyleneimines, according to the present invention is preferably in the range of 55 to 95%, preferably in the range of 57 to 90%, and more preferably in the range of 60 to 80%.

[0454] The polyalkylene imine, preferably polyethyleneimine, used in the reaction mixture may have a weight-average molecular weight (MW) of preferably 300 to 20,000, for example 300 to 15,000, preferably 300 to 10,000, more preferably 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) using hexafluoroisopropanol and 0.05 w% ammonium acetate as eluents and a narrowly distributed polyethylene glycol standard as the stationary phase.

[0455] Preparation: There are no special requirements regarding the method for obtaining 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.

[0456] Alkoxylation can generally be carried out by three methods: (i) anionic polymerization (using a basic initiator), (ii) polymerization using an acidic initiator, and (iii) coordination polymerization.

[0457] The anionic polymerization of epoxides corresponds to the “classical” technique for synthesizing the respective polymers / compounds containing ethylene oxide and / or propylene oxide units. Anionic polymerization is typically carried out by adding a catalyst, ethylene oxide and / or propylene oxide, and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide, to at least one initiator unit having a Zerevichnioff active hydrogen atom.

[0458] As catalysts, highly nucleophilic metal compounds, preferably alkali metal (particularly sodium, potassium, or cesium) compounds, can be used. Examples include alkali metal hydroxides, alkali metal salts, alkali metal hydrides, or alkali metal amides. Potassium hydroxide is of most practical importance (see, for example, U.S. Patent No. 6,156,720 A).

[0459] A further preferred class of catalysts is polymetallic cyanide compounds, preferably dimetallic cyanide compounds, particularly zinc hexacyanometalate. These catalysts are also frequently referred to as DMC catalysts. Polyether alcohols prepared using polymetallic cyanide components are characterized by extremely low content of unsaturated components. A further advantage of using polymetallic cyanide compounds as catalysts is the clear increase in space-time yield when alkylene oxides are added. For example, DD 203 735, DD 203 734, International Publication No. 97 / 29146, International Publication No. 98 / 03571, International Publication No. 00 / 14143, International Publication No. 99 / 44739 and U.S. Patent Application Publication No. 2008 / 0161509 A1 are described.

[0460] The solvents used for the anionic polymerization of epoxides are generally polar and aprotic; therefore, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO), and hexamethylphosphoramide (HMPA) are frequently used. Furthermore, polymerization with bulk monomers is possible and is a preferred method.

[0461] Alkoxides with sodium, potassium, or cesium counterions in THF or other polar aprotic solvents correspond to the commonly used initiator systems.

[0462] By adding complexing agents suitable for each cation, such as sodium crown ethers, the anionic polymerization of epoxides can be strongly accelerated.

[0463] The temperature during alkoxylation is typically 80-200°C, preferably 90-180°C.

[0464] The alkoxylated compounds of the present invention can be prepared by batch, semi-batch, or continuous methods.

[0465] In semi-batch alkoxylation, for example, a catalyst and at least one initiator are supplied initially, while the epoxide (ethylene or propylene oxide) is added during the reaction. This detailed synthetic strategy is due to the high reactivity of alkoxides and the high heat involved in alkoxylation reactions.

[0466] The polymerization rate of EO is considerably faster than that of PO, and it plays an important role in the frequently used anionic copolymerization of EO and PO. Generally, the reactivity of alkylene oxides decreases with increasing length and bulkiness of the alkyl substituent in the epoxide moiety.

[0467] The alkoxylated polyethyleneimines of the present invention can be obtained by alkoxylation of polyethyleneimines by methods generally known in the art. For example, alkoxylation of polyethyleneimines using ethylene oxide, propylene oxide, and butylene oxide is described in Houben-Weyl, Methoden der organischen Chemie, 4.Ed., Vol.14 / 2, p.440 ff. (1963) and Vol.E 20, p.1367 f. (1987). The alkoxylated polyethyleneimines of the present invention can be obtained, for example, as described in U.S. Patent No. 5,445,765 and German Patent Application Publication No. 2,227,546.

[0468] If at least one initiator unit is a monofunctional, difunctional, or polyfunctional alcohol, the resulting alcohol alkoxide component (alkoxlated alcohols) can be converted to alkyl ether sulfates by sulfurizing it using sulfuric acid or a sulfuric acid derivative in a manner known to itself (see, for example, U.S. Patent Application Publication 2008 / 0207939 A1). The sulfation reaction of alcohols has already been described, for example, in U.S. Patents 3,462,525, 3,420,875 and 3,524,864. Further details on carrying out this reaction are also provided in “Ullmann's Encyclopedia of Industrial Chemistry”, 5th edition, Vol. A25 (1994), pages 779-783 and the references provided therein.

[0469] When sulfuric acid itself is used for esterification, it is convenient to use an acid with a strength of generally 75-100% by weight, preferably 85-98% by weight (referred to as "concentrated sulfuric acid" or "monohydrate"). Esterification can be formed in a solvent or diluent if desired for controlling the reaction, for example, the generation of heat.

[0470] Generally, the alcohol reactant is introduced first, and the sulfation reagent is gradually added while mixing continues. If complete esterification of the alcohol alkoxide component is desired, the sulfation reagent and the alcohol alkoxide component are generally used in a molar ratio of 1:1 to 1:1.5, preferably 1:1 to 1:1.2. When a mixture of alcohol alkoxylates is used, a smaller amount of sulfation reagent may be advantageous. Esterification is usually carried out at a temperature in the range of 25 to 85°C, preferably 45 to 75°C. If appropriate, esterification may be carried out at the boiling point of a low-boiling-point water-immiscible solvent and diluent, so that the water formed by esterification is removed azeotropically.

[0471] Instead of sulfuric acid at the concentrations described above, for example, sulfur trioxide, sulfur trioxide complexes, sulfur trioxide solution in sulfuric acid ("fuming sulfuric acid"), chlorosulfonic acid, sulfuryl chloride, or in other cases sulfamic acid can also be used for the sulfurization of the alcohol alkoxide component of the present invention. The reaction conditions must then be appropriately modified as is known to those skilled in the art.

[0472] When sulfur trioxide is used as the sulfation reagent, the reaction can also be carried out in a countercurrent or parallel flow, preferably in a fall-film reactor, and, if appropriate, continuously. After esterification, the batch is neutralized by adding alkali and, if appropriate, work-up after removing any excess alkali metal sulfate and any present solvent.

[0473] When chlorosulfonic acid is used as the sulfation reagent, the corresponding alcohol alkoxide component is introduced into a stirring apparatus under inert conditions. The corresponding amount of chlorosulfonic acid is added dropwise while vigorously stirring. The molar ratio of the alcohol component to chlorosulfonic acid is generally 0.5:1 to 1:0.5, preferably 0.75:1 to 1:0.75. Most preferably, the molar ratio of the alcohol alkoxide component to chlorosulfonic acid is 1:1. After gas removal, the reaction batch is adjusted to a weakly alkaline pH using a sodium hydroxide solution.

[0474] The alkoxylated compounds obtained in process (e0) are characterized by a lower cradle-to-grave product carbon footprint (see description above) compared to the same alkoxylated compounds obtained by conventional methods (i.e., without CO2-to-olefin (CO2MTO) via the methanol-to-olefin pathway, without carbon recovery, etc.). Accordingly, the present invention solves the above dilemma and provides alkoxylated compounds with a low cradle-to-grave (i.e., including Scope 3 downstream (see description above)) product carbon footprint and generally good biodegradability at the same time.

[0475] While there is considerable variation in PCF values ​​(cradle-to-grave total carbon footprint) for various industrial alkoxylated compounds due to diverse initiator chemistry, initiator, ethylene oxide, propylene oxide, butylene oxide, and higher epoxide content, and diverse alkoxylation process conditions, the inventors of this invention have surprisingly found a single formula, scenarios i), ii), and iii) described in this part of the embodiment, that can describe all of the diverse alkoxylate compounds included in this invention.

[0476] This novel formula allows those skilled in the art to predict the cradle-to-grave *PCF of a particular alkoxylated compound prepared according to specific scenarios i), ii), or iii). This formula enables the comparison of the total product carbon footprint (PCF) from cradle to grave for alkoxylated compounds.

[0477] *In this application, "material carbon" in polymer products refers only to the additional CO2 emissions generated for "graveyard" emissions at the end of their lifespan; all other emissions, such as those related to transportation and use at the product end-user and consumer stages, are outside the scope.

[0478] The three scenarios i), ii), or iii) are as follows: i) Conventional fossil method: Ethylene oxide and / or propylene oxide are not prepared by steps b) and c), but instead, fossil-derived ethene and / or propene, obtained, for example by naphtha cracking, are used directly in step d). In addition, steps d) and e) are carried out using fossil energy (comparative example); ii) Scenario according to the present invention: The carbon dioxide used in step (b) is obtained by electrolysis based on electricity generated from non-fossil resources; in addition, the hydrogen in step (b) is obtained by electrolysis based on electricity generated from non-fossil resources. Steps (c) and (d) are based on CO2MTO (CO2-to-olefin via the methanol-to-olefin pathway); only hydrogen from SMR via CCS (carbon capture and storage) is used to prepare the oxidizing agent (hydrogen peroxide) required for the preparation of propylene oxide by HPPO in step (d). iii) Best scenario according to the present invention: all of steps b) to d) and the production of hydrogen and oxygen are carried out primarily on non-fossil energy.

[0479] The formulas for scenarios i), ii), or iii) are as follows: Scenario i): 8.88 × C - 0.253 × E + 1.33 × P - 0.940 Scenario ii): 6.90 × C - 0.560 × E + 0.464 × P - 0.495 Scenario iii): 5.21 × C - 0.276 × E - 0.436 × P - 0.259 During the ceremony, C = Carbon content [mass ratio] in alkoxylated compounds E = EO content in alkoxylated compounds [mass ratio] P = Total content of "PO and higher epoxides" in alkoxylated compounds [by mass ratio] Here, each mass ratio is in the range of 0 to 1 (equivalent to 0 to 100 wt%). Furthermore, the total mass balance must be closed, which means C + E + P = 1 (100%).

[0480] Therefore, the present invention generally applies to a ratio of <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, even more preferably <6.90×C-0.560×E+0.464×P-0.495, and even more preferably <6.48×C-0.489× The present invention relates to alkoxylated compounds having a total product carbon footprint from cradle to grave (see description above) of E+0.239×P-0.436, more preferably <6.06×C-0.418×E-0.014×P-0.377, even more preferably <5.64×C-0.347×E-0.211×P-0.318, and still more preferably <5.21×C-0.276×E-0.436×P-0.259 (where C, E, and P are defined above).

[0481] In a preferred embodiment of the present invention, the weight fraction of alkylene oxide units other than ethylene oxide and propylene oxide units is 0 wt%. In this case, it is the P=PO content [mass ratio] in the alkoxylated compound.

[0482] The present invention further relates to alkoxylated compounds obtainable by the method of the present invention. Preferably, generally <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, even more preferably <6.90×C-0.560×E+0.464×P-0.495, and even more preferably <6.48×C-0.489× The alkoxylated compound (where C, E, and P are defined above) has a cradle-to-grave (see description above) product carbon footprint of E+0.239×P-0.436, more preferably <6.06×C-0.418×E-0.014×P-0.377, even more preferably <5.64×C-0.347×E-0.211×P-0.318, and still more preferably <5.21×C-0.276×E-0.436×P-0.259.

[0483] As discussed above, the different by-product spectra of methanol, ethene, and propene, and of ethylene oxide and propylene oxide, are also reflected in the downstream products, namely the alkoxylated compounds obtained by the present invention.

[0484] Surprisingly, the present inventors have found that the amount of polymer by-products generated during the alkoxylation process is less when using the ethylene oxide and / or propylene oxide according to the present invention compared to generally prepared ethylene oxide and / or propylene oxide.

[0485] In the preparation of polyurethanes (from polyether polyols), the reduction of these high molecular weight by-products is desirable because the ultra-high molecular weight by-product fractions are known to be strong surfactants, which can cause collapse of polyurethane foams or adversely affect other applications, such as causing turbidity or precipitation of the blend.

[0486] Preferably, the alkoxylated compound according to the present invention satisfies the biodegradability requirements specified in OECD 301B (as described above).

[0487] Both the alkoxylated compounds and methods of the present invention achieve a low cradle-to-grave (see description above) product carbon footprint and generally good biodegradability.

[0488] i) 20 wt% to <100 wt%, preferably 30 wt% to 99.3 wt%, ethylene oxide units and / or propylene oxide units. ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of ethylene oxide and propylene oxide units, and at least one alkylene oxide unit different from the ethylene oxide and propylene oxide units. iii) At least one initiator unit having >0 wt% to 80 wt% and 0.2 wt% to 70 wt% of Tserevichnov active hydrogen atoms, (Here, the sum of the units listed in i), ii), and iii) is 100 wt%.) (Ethylene oxide units and / or propylene oxide units, alkylene oxide units different from ethylene oxide and propylene oxide units, and initiator units having a Tserevichnov active hydrogen atom are defined above.) The present invention comprises an alkoxylated compound.

[0489] In one embodiment, the alkoxylated compound of the present invention comprises an EO:PO weight ratio of 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 values ​​of these values.

[0490] Ethylene oxide units and / or propylene oxide units, alkylene oxide units different from ethylene oxide and propylene oxide units, and initiator units having a Zerewitinoff active hydrogen atom are defined above.

[0491] The alkoxylated compound of the present invention has a number-average molecular weight of generally 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 a PEG standard.

[0492] The alkoxylated compounds of the present invention have a wide range of applications across various industries. Some of these applications are as follows: - Lubricants: Alkoxylated compounds can be used as lubricants in various industries such as automotive, aerospace, and industrial machinery. They provide excellent lubrication properties, high thermal stability, and oxidation resistance. - Personal care products: Alkoxylated compounds can be used in formulations of personal care products such as lotions, creams, and shampoos. This imparts, for example, moisturizing and conditioning properties to the skin and hair. - Home care products: Alkoxylated products can be used as surfactants in laundry detergents, hard surface cleaners, and rinse aids. This imparts excellent wetting, cleaning, and emulsifying properties. - Pharmaceutical Industry: Alkoxylated compounds can be used in the pharmaceutical industry as excipients to improve drug solubility, stability, and bioavailability. They are also used in formulations of ointments, creams, and gels. - Textile Industry: Alkoxylated compounds can be used in the textile industry as softeners and antistatic agents. They can improve the texture and feel of fabrics and reduce static electricity. - Food Industry: Alkoxylated compounds can be used in the food industry as emulsifiers, thickeners, and stabilizers. They can be used in the production of ice cream, dairy products, and baked goods. - Petroleum and Gas Industry: Alkoxylated compounds can be used in the petroleum and gas industry as hydraulic oils, oil breakers, and heat transfer fluids. This provides, for example, excellent lubrication properties and high thermal stability. - Agriculture / Agricultural Chemicals: Alkoxylated compounds can be used in agriculture, for example, as adjuvants to improve the effectiveness of herbicides and insecticides. - Chemical Industry: Alkoxylated compounds can be used in the chemical industry as reaction media, surfactants, and dispersants. They can be used in the production of polymers, resins, and coatings. - Building materials: Alkoxylated compounds can be used in the construction industry as additives to improve, for example, the workability, strength, and durability of cement, concrete, and plaster. - Polyurethane production: Alkoxylated compounds can be used as starting materials for the production of polyurethane foams, adhesives, and coatings, for example. They can act as chain extenders and crosslinking agents in the polymerization process. - Metalworking fluids: Alkoxylated compounds can be used as coolants and lubricants in metalworking processes such as cutting, grinding, and drilling. This provides, for example, excellent thermal stability, low volatility, and high lubricity. - Electronics: Alkoxylated compounds can be used as thermal conductive fluids in electronic cooling systems. This provides, for example, high thermal conductivity, low viscosity, and compatibility with various materials. - Fuels and Energy: Alkoxylated compounds can be used as additives in fuels and lubricants, such as in fuel performance packages, to improve their performance and reduce emissions. They can also be used as heat conduction fluids in solar and geothermal energy systems. - Water treatment: Alkoxylated compounds can be used as flocculants and coagulants in water treatment processes. This can help remove suspended particles and impurities from water. - Adhesives and sealants: Alkoxylated compounds can be used as binders and thickeners in adhesive and sealant formulations. This can improve adhesion, flexibility, and moisture resistance.

[0493] Accordingly, the present invention further relates to the use of the alkoxylated compound of the present invention in any one of the above-described applications.

[0494] Preferably, the present invention further comprises at least one of the alkoxylated compounds according to the present invention or alkoxylated compounds obtained by the method according to the present invention, for use in home care products, cosmetics, pharmaceutical products, food products, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, lubricating greases, thermal conductive fluids, metalworking oils and transmission fluids, defoamers, softeners, rheological modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking oils, pesticides such as insecticides, textile and leather additives, bioprocessing, fuel performance packaging and poly(urethane) The present invention relates to the use of alkoxylated compounds according to the present invention or alkoxylated compounds obtained by the method according to the present invention in adhesives, home care products, cosmetics, pharmaceutical products, food products, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, lubricating greases, thermal conductive fluids, metalworking oils and transmission fluids, defoamers, softeners, rheological modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking oils, pesticides such as insecticides, textile and leather auxiliaries, bioprocessing, fuel performance packaging and poly(urethane) adhesives.

[0495] Process (f): Step (f) includes separating monoethanolamine from the ethanolamines obtained in step (e).

[0496] Reaction step (e) can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, but separation to remove diethanolamine and triethanolamine is usually required to obtain monoethanolamine. The workup is generally known in the art and is usually carried out by distillation, preferably under reduced pressure, such as vacuum distillation.

[0497] For an example of a method for producing monoethanolamine, see, for instance, “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.

[0498] Process (g): In step (g), the monoethanolamine from step (f) is preferably converted to ethylene by catalytic gas-phase synthesis to form an imine (aziridine).

[0499] One objective of the present invention is to provide an environmentally friendly polyethyleneimine. Surprisingly, the inventors have found that the greenhouse gas (GHG) emissions generated by the conversion of monoethanolamine to ethyleneimine by catalytic gas-phase synthesis are significantly lower than the GHG emissions generated by the conversion of monoethanolamine to ethyleneimine by other methods.

[0500] The PCF of ethyleneimine and consequently polyethyleneimine obtained by catalytic gas-phase synthesis is therefore significantly lower than that of ethyleneimine and polyethyleneimine obtained by other methods (where only step (g) differs in the method for preparing ethyleneimine and polyethyleneimine).

[0501] Furthermore, surprisingly, the inventors of the present invention have found that the service life of the catalyst is improved by using monoethanolamine from step (f) in step (g) of the method of the present invention, that is, monoethanolamine derived from hydrogen obtained at least partly by hydrolysis, preferably by electrolysis, where hydrolysis, preferably electrolysis, uses energy produced at least partly from non-fossil resources.

[0502] Suitable methods for preparing ethyleneimine from monoethanolamine are generally known in the art.

[0503] Suitable catalytic gas phase methods for the preparation of ethyleneimine from monoethanolamine are generally known in the art; for example, see U.S. Patent No. 4,841,061 for suitable examples of catalyst compositions and U.S. Patent No. 4,966,980 for the respective ethyleneimine gas phase method conditions.

[0504] In this method, ethyleneimine is prepared by dehydrating monoethanolamine at a temperature of generally 350–450°C and under a reduced pressure of generally 30–500 mbar (absolute value).

[0505] This method is generally carried out in the presence of a catalyst having weakly basic and acidic moieties, such as a Si-Cs-P or Si-Rb-P base. For an overview of this production technique and optimal catalyst compositions with high yield (e.g., up to 80 mol%), selectivity, and activity, refer to 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 564-8512, Japan. Despite the short contact time, this method is prone to catalyst deactivation and loss of active components due to coking and sintering caused by high processing temperatures. To improve the lifespan of the catalyst, for example, a catalyst regeneration cycle by trimethyl phosphate treatment can be utilized, 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 564-8512, Japan. Another example of a suitable catalyst preparation method is a regeneration method, which is described in International Publication No. 2015090084 and Chinese Patent Application Publication No. 104475144.

[0506] Catalytic gas-phase dehydration is typically carried out in the gas phase in a flow-tube reactor, preferably a fixed-bed flow-tube reactor. Alternatively, for the dehydration of monoethanolamine, a fluidized-bed reactor can be used, as catalyst contact and heat transfer are more efficient.

[0507] The resulting mixture of products is typically separated by quenching and subsequent multi-stage distillation to obtain high-purity ethyleneimine, while unreacted monoethanolamine is returned to the reactor.

[0508] Another preferred commercially available method is the Wenkel method, which is liquid-phase dehydration as originally described in H. Wenker, J. Am. Chem. Soc. 57 (1935) 2328. This technique is generally a two-step process in which monoethanolamine is reacted generally with sulfuric acid to produce 2-aminoethyl bisulfate as an intermediate product. Dehydration is then generally achieved under pressure and high temperature by adding sodium hydroxide, as described in H. Kindler, W. Sanne, R. Sinn, A. Wittwer, Chem. Ing. Tech. 37 (1965) 400 and DE 1302658, 1971 (R. Sinn, W. Sanne, H. Kindler; BASF Aktiengesellschaft).

[0509] The liquid-phase ethyleneimine method can generally be carried out in batch or continuous mode, yielding high-purity ethyleneimine in an extremely high yield of 85-90 mol% after distillation. This ethyleneimine possesses the excellent properties required for, for example, high molecular weight polyethyleneimines and other derivatives.

[0510] Process (h) In step (h), the ethyleneimine from step (g) is polymerized with polyethyleneimine.

[0511] A suitable method for preparing polyethyleneimine by polymerization of ethyleneimine (aziridine) is known to those skilled in the art.

[0512] Polyethyleneimines are preferably prepared by cationic ring-opening polymerization of ethyleneimines in the presence of a Brønsted acid, a Lewis acid, a haloalkane, or carbon dioxide. Examples are given in U.S. Patent Nos. 2,182,306 and 3,203,910 and U.S. Patent Application Publication No. 2001 / 0039318.

[0513] For further references, including more examples of polyethyleneimine synthesis, see “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.

[0514] Polymerization may be carried out, for example, by a batch method, in which water and 1,2-dichloroethane as a catalyst are placed in a reaction vessel, the mixture is heated to a temperature of 70-100°C, and ethyleneimine is continuously added while stirring the reaction mixture.

[0515] The polyethyleneimines available are generally branched or hyperbranched polyethyleneimines.

[0516] The polyethyleneimine obtained has a weight-average molecular weight M, preferably in the range of 500 to 2,000,000 g / mol, and more preferably in the range of 500 to 100,000 g / mol. w It holds.

[0517] The degree of branching of polyethyleneimines is D 2 In O 13 The degree of branching is determined by 13C NMR spectroscopy and 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. The degree of branching is calculated as (D+T) / (D+T+L). In this formula, D refers to a dendritic (or tertiary) amino (amin) group, L (linear) refers to a secondary amino group, and L (linear) refers to a primary amino group.

[0518] Surprisingly, the inventors found that the polyethyleneimine obtained by the method of the present invention, compared to polyethyleneimine prepared by conventional methods, has an increased proportion of secondary amino groups at the expense of the proportion of primary amino groups. The aforementioned ratio of primary, secondary, and tertiary amino groups in the polyethyleneimine of the present invention is beneficial for the stability of polyethyleneimine during carbon recovery.

[0519] The present invention provides environmentally friendly ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine, ethyleneimine, ethylene oxide and ammonia, and environmentally friendly methods for producing them, which use as little fossil energy as possible.

[0520] In a further embodiment of the present invention, the polyethyleneimine of the present invention is characterized by a low molar occupancy of deuterium, with 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.

[0521] The present invention further relates to polyethyleneimine in which the molar occupancy of deuterium is ≤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, based on the total hydrogen content.

[0522] The polyethyleneimines are preferably prepared by a method comprising at least step (a) according to the present invention. More preferably, the polyethyleneimines are prepared by a method of the present invention comprising steps (a) to (h).

[0523] The polyethyleneimines according to the present invention are characterized by a low deuterium molar content. This differs from the deuterium content of petrochemically produced polymers and ethanolamines produced by petrochemical methods, i.e., fossil energy-derived polymers.

[0524] A further key feature of the ethanolamines and polyethyleneimines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the present invention is a low deuterium molar occupancy. This low deuterium molar occupancy is mainly introduced by the hydrogen used in the method according to the present invention. Accordingly, the ammonia prepared by the reaction of the hydrogen with nitrogen is also characterized by a low deuterium molar occupancy.

[0525] Step (e1) and (i)-alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines Process (i) and process (e1) In this step, polyethyleneimine is further reacted with at least ethylene oxide and / or propylene oxide, preferably ethylene oxide obtained from at least step (d) by a known alkoxylation reaction, to obtain ethoxylated and / or propoxylated, preferably ethoxylated polyethyleneimine. Such compounds are well known and are available by the present invention as compounds from non-fossil sources.

[0526] 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.

[0527] When other alkylene oxides are used in alkoxylation reactions, other typical alkoxylated polyethyleneimines are obtained; typical alkylene oxides known for such use are butylene oxide (especially n-butylene oxide, nBuO) and higher alkylene oxides. nBuO is used in most cases. Known products include, for example, BASF's Sokalan® PG617, a polyethyleneimine typically alkoxylated to a PEI-10EO-7PO block structure at about 7EO and 5PO, and BASF's Sokalan® HP20, a polyethyleneimine typically ethoxylated at about 20EO units per NH, with a molecular weight reported to be about 600 or 800 g / mol depending on the source.

[0528] Accordingly, according to the present invention, these Sokalan® products—Sokalan® PG617 and Sokalan® HP20 and polyethyleneimine—and all similar products using EO for alkoxylation—and optionally further components, such as the aforementioned lactones and other alkylene oxides other than EO, can be obtained by known methods, however such products have a much lower content of fossil-derived components based on the molar weight of those products.

[0529] For further disclosures of such alkoxylated PEI products (particularly in the field of detergents), see, for example, European Patent Application Publication No. 2 014 753 A1 and European Patent No. 2 925 848 B1; further, for alkoxylated PEI and alkoxylated diamines / oligoamines / polyamines—sometimes including further alkylene oxides and / or lactones (typically included in the alkoxylation reaction or as a separate "polylactone block" or as an insertion of a single lactone or two or fewer or possibly three lactones into an alkylene oxide chain, such alkylene oxide chains being derived solely from EO or from EO and other alkylene oxides, and such two or more alkylene oxides being in any configuration depending on the method step, such as random or block arrangement)—see, for example, International Publication 2021 / 165468. You can refer to Brochure A, International Publication No. 2021 / 165493, International Publication No. 2022 / 136408 A, International Publication No. 2022 / 136409 A, International Publication No. 2023 / 021104 A, International Publication No. 2023 / 021105 A, International Publication No. 2023 / 021103 A, International Publication No. 2023 / 021101 A, International Publication No. 2022 / 136389 A, and International Publication No. 2023 / 117494 A, European Patent No. 3665209 and International Publication No. 2023017794. All (dissisclosed) compounds disclosed in the above documents can also be prepared by applying them to these disclosures using the present invention. Further disclosures of compounds that have been alkoxylated using PEI or diamine / oligoamine / polyamine, and then at least EO, are available in the present invention. Accordingly, all compounds and methods disclosed in the disclosures explicitly mentioned in this paragraph are incorporated into the present invention by using EO and / or PEI prepared in accordance with the methods and disclosures of the prior art documents, and otherwise prepared according to the methods and disclosures of those prior art documents.

[0530] The present invention provides environmentally friendly alkoxylated diamines, oligoamines, and polyamines, as well as alkoxylated polyethyleneimines, and environmentally friendly methods for producing them, which use as little fossil energy as possible.

[0531] The aforementioned environmentally friendly prepared compounds, namely alkoxylated diamines, oligoamines, and polyamines, as well as alkoxylated polyethyleneimines, have been found to be particularly characterized by a low deuterium molar content.

[0532] As mentioned above, it is important to be able to reliably trace the origin of hydrogen and downstream compounds obtained from clean energy sources.

[0533] Today, most hydrogen is produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavy hydrocarbons, and coal gasification.

[0534] However, until now, there has been no way to distinguish between hydrogen obtained through steam reforming, partial oxidation, and coal gasification—that is, hydrogen obtained from fossil resources—and hydrogen obtained through electrolysis. As discussed above, hydrogen obtained through electrolysis is preferably obtained using non-fossil energy sources. It is expected that the electrification (power generation) of fossil sources will be completely replaced by power generation using non-fossil resources in the near future.

[0535] Accordingly, the inventors have found a method for tracing the origin of hydrogen and its downstream products, preferably alkoxylated diamines, oligoamines, and polyamines, and alkoxylated polyethyleneimines, by the deuterium molar content of the said compounds. These downstream products derived from hydrogen, such as hydrogen obtained by electrolysis, and hydrogen itself, can be distinguished from chemically identical compounds prepared by fossil energy-based methods, i.e., by petrochemical methods, by their deuterium molar content.

[0536] Furthermore, in the subsequent synthesis routes of alkoxylated diamines, oligoamines, and polyamines, as well as alkoxylated polyethyleneimines, the use of carbon monoxide and preferably carbon dioxide along with hydrogen in the same carbon oxide compounds as petrochemical synthesis gas has been found to result in a uniquely low molar content of deuterium in these compounds, as demonstrated by excellent traceability.

[0537] Accordingly, the present invention relates to the use of the molar occupancy of deuterium in hydrogen and hydrogen-derived downstream compounds for tracing the origin, particularly the energy origin, of hydrogen and hydrogen-derived downstream compounds, wherein the compound is preferably an alkoxylated diamine, oligoamine and polyamine, and an alkoxylated polyethyleneimine.

[0538] The present invention further relates to a method for tracing the origin, particularly the energy origin, of hydrogen and downstream compounds derived from hydrogen by determining the molar occupancy of hydrogen and deuterium in the downstream compounds derived from hydrogen, wherein the compounds are preferably alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines.

[0539] Hydrogen-derived downstream products are generally products prepared using hydrogen, preferably alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines. The preparation of these downstream products, as well as other hydrogen-derived downstream products, is known in the art.

[0540] In the context of this invention, "tracing" is synonymous with "tracking."

[0541] In the sense of this invention, the origin refers to the method of preparing the hydrogen used, particularly electrolysis, and / or the energy source, i.e., a non-fossil energy source. As mentioned above, it is expected that the electrification (power generation) of fossil fuel sources will be completely replaced by power generation using non-fossil resources in the near future. In this case, the hydrogen produced by electrolysis is hydrogen of non-fossil origin. Examples of non-fossil power sources are described above.

[0542] The present invention's method for tracing the origin, particularly the energy origin, of hydrogen and the downstream compounds described above may be used as a single tracing method or in combination with further tracing methods.

[0543] The preferred molar content of hydrogen derived compounds, particularly alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, as well as hydrogen obtained from hydrogen produced by electrolysis, especially hydrogen obtained by the method of the present invention, is referred to in this application.

[0544] The inventive compounds made available by the present invention encompass all such alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines; such compounds are well known, namely, alkoxylated diamines, oligoamines and polyamines and alkoxylated polyethyleneimines as made available by the present invention, and in particular as detailed above herein, more specifically as disclosed in the following prior art disclosures, for example, very preferably as disclosed by their structure and / or method of production, European Patent Application Publication No. 2014 753 A1, European Patent No. 2925 848 B1, International Publication No. 2021 / 165468 A, International Publication No. 2021 / 165493, International Publication No. 2022 / 136408 A, International Publication No. 2022 / 136409 A, International Publication No. 2023 / 021104 A, International Publication No. 2023 / 021105 This includes, in particular, those disclosed in Brochure A, International Publication No. 2023 / 021103 A, International Publication No. 2023 / 021101 A, International Publication No. 2022 / 136389 A, and International Publication No. 2023 / 117494 A, European Patent No. 3665209 and International Publication No. 2023017794, and especially those produced by replacing at least one element of BASF products known commercially under the trade names Sokalan® PG617, Sokalan® HP20 and Sokalan HP 96 (which are ethoxylated hexamethylenediamines) with the elements of the present invention using the present invention, for example, by replacing standard fossil-derived PEI, EO and / or PO, amines, etc. with PEI and / or EO and / or PO and / or amines that can be produced, or preferably produced by the method of the present invention.

[0545] Generally, such products are sometimes referred to as "polyfunctional polyethyleneimines" (e.g., BASF's Sokalan® HP20 and Sokalan PG617, both of which are preferred structures of the inventive compound) and "polyfunctional diamines" (e.g., BASF's Sokalan® HP96, which is a preferred structure of the inventive compound). Such polyfunctional polyethyleneimines—which are the inventive compounds according to the present invention—are typically ethoxylated polyethyleneimines with 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 polyfunctional polyethyleneimines have ethylene oxide side chains in an amount of 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.%, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. Suitable polyethyleneimine core molecules are polyethyleneimines with a weight-average molecular weight Mw in the range of 500 to 5000 g / mol. Preferably, molecular weights of 500 to 1000 g / mol are used, and Mw of 600 to 800 g / mol is even more preferred. 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 per NH functional group. The present invention encompasses similarly polyfunctional diamines, typically ethoxylated C2-C12 alkylenediamines, preferably hexamethylenediamines, which may be further quaternized and / or optionally sulfated. Typical polyfunctional diamines have a weight-average molecular weight Mw in the range of 2000-10000, more preferably 3000-8000, and most preferably 4000-6000 g / mol.In preferred embodiments of the present invention, ethoxylated hexamethylenediamine, and moreover quaternized and sulfated hexamethylenediamine, are preferred compounds, which contain an average of 10 to 50, preferably 15 to 40, and more preferably 20 to 30 ethylene oxide (EO) groups per NH functional group, and which preferably support two cationic ammonium groups and two anionic sulfate groups.

[0546] All of the aforementioned compounds are included in the present invention when they are produced by using the present invention to replace at least one element of the prior art methods / starting materials with an element of the present invention, for example, by replacing standard fossil-derived 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 as produced by it.

[0547] The uses of such inventive compounds and products / formulations / compositions containing them, as disclosed and defined in the preceding paragraphs, are the same as those known in the art; such uses of such inventive compounds and products / formulations / compositions are, in particular, disclosed in any of the following disclosures: European Patent Application Publication No. 2014753 A1, European Patent No. 2925848 B1, International Publication No. 2021 / 165468 A, International Publication No. 2021 / 165493, International Publication No. 2022 / 136408 A, International Publication No. 2022 / 136409 A, International Publication No. 2023 / 021104 A, International Publication No. 2023 / 021105 A, International Publication No. 2023 / 021103 A, International Publication No. 2023 / 021101 A, International Publication No. 2022 / 136389 A, and International Publication No. 2023 / 117494 This includes Brochure A, European Patent No. 3665209, and International Publication Brochure 2023017794, as well as known uses of products / formulations / compositions containing Sokalan® PG617, Sokalan® HP20, and Sokalan® HP 96 - in the state of the art. In any of these disclosures, compounds in the state of the art can be partially or completely replaced by at least one element of the present invention with inventive compounds having the same or very similar chemical structure, which are produced by replacing, for example, standard fossil-derived PEI, EO and / or PO and / or 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 as produced therein.

[0548] Process (g0) - Surfactant In step (g0), any of the products from steps a), b), c), d), and / or e) are converted in at least one known method step to at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or to a hydrogen-containing surfactant, thereby obtaining a surfactant with a lower deuterium content on a basis of total hydrogen content compared to chemically identical surfactants obtained solely from fossil sources.

[0549] As mentioned above, it is important to be able to reliably trace the origin of hydrogen obtained from clean energy sources, and consequently, downstream compounds such as the surfactants of the present invention.

[0550] Today, most hydrogen is produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavy hydrocarbons, and coal gasification.

[0551] However, until now, there has been no way to distinguish between hydrogen obtained through steam reforming, partial oxidation, and coal gasification—that is, hydrogen obtained from fossil resources—and hydrogen obtained through electrolysis. As discussed above, hydrogen obtained through electrolysis is preferably obtained using non-fossil energy sources. It is expected that the electrification (power generation) of fossil sources will be completely replaced by power generation using non-fossil resources in the near future.

[0552] Accordingly, the inventors have found a method for tracking the origin of hydrogen and its downstream products, preferably the surfactants of the present invention, by the deuterium molar content of the compound. These downstream products derived from hydrogen, such as hydrogen obtained by electrolysis, i.e., surfactants as detailed herein, and hydrogen itself, can be distinguished from chemically identical compounds prepared by fossil energy-based methods, i.e., petrochemical methods, by their deuterium molar content.

[0553] Furthermore, in the subsequent synthesis pathway of surfactants, the use of carbon monoxide and preferably carbon dioxide along with hydrogen in the same carbon dioxide compounds as petrochemical synthesis gas was found, through excellent traceability, to result in a uniquely low molar content of deuterium in these compounds.

[0554] Accordingly, the present invention relates to the use of the molar occupancy of deuterium in hydrogen and hydrogen-derived downstream compounds for tracing the origin, particularly the energy origin, of hydrogen and hydrogen-derived downstream compounds, wherein the compound is preferably a surfactant as detailed herein.

[0555] The present invention further relates to a method for tracing the origin, in particular the energy origin, of hydrogen and a downstream compound derived from hydrogen by determining the molar occupancy of hydrogen and deuterium in the downstream compound derived from hydrogen, wherein the compound is a surfactant as detailed herein.

[0556] In the context of this invention, "to trace" is synonymous with "to track" or "to track."

[0557] In the sense of this invention, the origin refers to the method of preparing the hydrogen used, particularly electrolysis, and / or the energy source, i.e., a non-fossil energy source. As mentioned above, it is expected that the electrification (power generation) of fossil fuel sources will be completely replaced by power generation using non-fossil resources in the near future. In this case, the hydrogen produced by electrolysis is hydrogen of non-fossil origin. Examples of non-fossil power sources are described above.

[0558] The present invention's method for tracing the origin, particularly the energy origin, of hydrogen and the downstream compounds described above may be used as a single tracing method or in combination with further tracing methods.

[0559] The inventive compounds available by the present invention include all such surfactants according to the outline provided herein, in particular as described in more specific detail.

[0560] Such surfactants are known to date from prior art, and some are commercially available.

[0561] Ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or their surfactants that can be derived from hydrogen, are all included in the present invention when produced using the present invention, that is, by replacing at least one element of the prior art method / starting material with an element of the present invention, for example, by replacing standard fossil-derived ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, triethanolamine, or hydrogen with a surfactant that can be produced by the present invention, or preferably as produced by it.

[0562] Such surfactants are structurally known. Many of them are listed in the following sections; specifically, those known to be able to be produced using at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or hydrogen, are specifically included in the present invention.

[0563] Since the methods for producing such surfactants are widely known, well-established, and therefore generally known to those skilled in the art, it may not be convenient to mention everything and to refer to or refer to the various methods of their production.

[0564] Furthermore, the method of the present invention can be used to produce any of the following surfactants listed in the following chapters, provided that, in such synthesis routes, at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or hydrogen is used in the method for producing such surfactants.

[0565] Surfactants usable in conjunction with the present invention The surfactants that can be produced by the present invention are, in principle, any surfactant; however, in such a synthesis route, at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or hydrogen, is used in the method for producing such surfactants.

[0566] Specifically, such surfactants are disclosed in any of the following disclosures: U.S. Patent Application Publication No. 2019 / 390142, International Publication No. 2020 / 264077, International Publication No. 2020 / 005476, International Publication No. 2023017061A1, International Publication No. 03 / 042262, Publication numbers 800542 and 800500, International Publication No. 99 / 05242, U.S. Patent No. 5,576,282, U.S. Patent No. 6,306,812 B1 and U.S. Patent No. 6,326,348 B1.

[0567] Surfactants include nonionic, anionic, and amphoteric surfactants, which are defined in more detail below:

[0568] Nonionic cleaning surfactants Nonionic cleaning surfactants (NIS) are surfactants that do not possess either positively or negatively charged functional groups. In contrast to anionic and cationic surfactants, nonionic surfactants do not ionize in solution.

[0569] NIS1 In one embodiment, the nonionic surfactant is selected from compounds of general formulas (NIS1a) and (NIS1b): [ka]

[0570] The variables in general formulas (NIS1a) and (NIS1b) are defined as follows: R1 is selected from C1-C23 alkyl and C2-C23 alkenyl, where alkyl and / or alkenyl are linear (straight-chain; n-) or branched; examples include n-C7H15, n-C8H17, n-C9H19, n-C11H23, n-C13H27, n-C15H31, n-C17H35, i-C9H19, and i-C12H25. R2 is selected from H, C1-C20 alkyl and C2-C20 alkenyl, where alkyl and / or alkenyl are linear (straight-chain; n-) or branched. R3 and R4 are each independently selected from C1-C16 alkyl groups, where alkyl is linear (straight-chain; n-) or branched; examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and isodecyl. R5 is selected from H and C1-C18 alkyl groups, where the alkyl group is either linear (straight-chain; n-) or branched. The integers of general formulas (NIS1a) and (NIS1b) are defined as follows: 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 1, preferably in the range of 5 to 100, more preferably 9 to 50.

[0571] The nonionic surfactants of general formulas (NIS1a) and (NIS1b) may have any structure, including block or random structures, and are not limited to the sequences shown in formulas (NIS1a) and (NIS1b).

[0572] Compounds according to formula (NIS1a) may be referred to herein as alkyl polyethylene glycol ethers (AEOs). Compounds according to formula (NIS1b) may be referred to herein as alkylphenol polyethylene glycol ethers (APEOs).

[0573] In one embodiment, the compound has the general formula (NIS1a), where R1 is n-C13H27, R2 and R5 are H, m is 3-20, and n and o are 0.

[0574] In one embodiment, the compound has the general formula (NIS1a), where R1 is a linear or branched C10 alkyl group, R2 and R5 are H, m is 3 to 14, and n and o are 0.

[0575] 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 to 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 to 80, and n and o are 0.

[0576] In one embodiment, the m of both nonionic cleaning surfactants is 25 to 80, preferably m is either 25 or 80. The NIS may be referred to herein as NIS1a1.

[0577] In one embodiment, the nonionic cleaning surfactant is selected from the general formula (NIS1a), where m is in the range of 3 to 11, preferably 10 or less, more preferably 7 or less; n and o are 0, R1 is a linear C9 to C17 alkyl, and R2 and R5 are H.

[0578] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), characterized in that R1 is n-C12H25, R2 and R5 are H, m is 3 to 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 to 30, preferably 7, and n and o are 0. The NIS may be referred to herein as NIS1a2.

[0579] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), and the nonionic cleaning surfactant is characterized in that R1 is n-C11H23, R2 and R5 are H, m is 4 to 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 to 10, and n and o are 0.

[0580] The aforementioned NIS may be referred to as NIS1a3 in this specification.

[0581] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), and one of the nonionic surfactants is characterized in that R1 is n-C9H19, R2 and R5 are H, m is 5 to 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 to 7, and n and o = 0. The NIS may be referred to herein as NIS1a4.

[0582] In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS1a), 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.

[0583] In one embodiment, the nonionic cleaning surfactant relates to the general formula (NIS1a), where R1 is a C3-C18 linear alkyl, R2 is H, and R3 and R4 are each independently - Methyl (n or o is 2-25), or - Ethyl (and n or o is 1-3), or - Propyl (and n or o is 1-3) Selected from, In the formula, m+n+o is equal to 5 to 50. In one embodiment, R5 is H. In one embodiment, R5 is selected from methyl, butyl, benzyl, and t-butyl. The NIS may be referred to herein as NIS1a6.

[0584] In one embodiment, the compound relates to the general formula (NIS1a), where R2 is H, m is 10 to 50, R3 is a linear or branched C8 to C12 alkyl group, n is 1 or 2, preferably 1, o is 0 or 1, and R5 is H.

[0585] In one embodiment, the compound relates to the general formula (NIS1a), where R2 is H, m is 10 to 50, R3 is a linear or branched C8 to C12 alkyl group, n is 1 or 2, preferably 1, o is 0 or 1, and R5 is H.

[0586] In one embodiment, the nonionic cleaning surfactant is selected from compounds of formula (NIS1a), where R1 is n-C8 alkyl, R2 is H, R3 is 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.

[0587] In one embodiment, the nonionic cleaning surfactant is selected from compounds of formula (NIS1a), where R1 is n-C8 alkyl, R2 is H, R3 is 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.

[0588] In one embodiment, the nonionic cleaning surfactant is selected from compounds of formula (NIS1a), where R1 is n-C8 alkyl, R2 is H, R3 is 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.

[0589] In one embodiment, a nonionic cleaning surfactant selected from compounds according to formula (NIS1a), wherein R1 is n-C8 alkyl, R2 is H, R3 is methyl, R4 is 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.

[0590] NIS2 In one embodiment, the nonionic cleaning surfactant is selected from compounds of general formula (NIS2), which may be referred to herein as alkyl polyglycosides (APGs): [ka] In the general formula (NIS2), R1 is selected from C1-C17 alkyls and C2-C17 alkenyls, where the alkyl and / or alkenyl is linear (straight-chain; n-) or branched; examples include n-C7H15, n-C9H19, n-C11H23, n-C13H27, n-C15H31, n-C17H35, i-C9H19, and i-C12H25. In the general formula (NIS2), R2 is selected from H, C1-C17 alkyl groups, and C2-C17 alkenyl groups, where the alkyl and / or alkenyl groups are linear (straight-chain; n-) or branched. In the general formula (NIS2), G1 is selected from monosaccharides with 4 to 6 carbon atoms, such as glucose and xylose. In the general formula (NIS2), the integer w is in the range of 1.1 to 4, and w is the average number.

[0591] In one embodiment, NIS2 is a capryl glucoside, which is a compound according to formula (NIS2) (wherein R1 is n-C6H13, R2 is H, G1 is glucose, and w is approximately 1).

[0592] In one embodiment, NIS2 is a lauryl glucoside, which is a compound according to formula (NIS2) (wherein R1 is n-C10H21, R2 is H, G1 is glucose, and w is approximately 1).

[0593] NIS3 In one embodiment, a nonionic cleaning surfactant selected from compounds of general formula (NIS3): [ka]

[0594] The variables in the general formula (NIS3) are defined as follows: AO is selected from ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof. R6 is selected from C5-C17 alkyl and C5-C17 alkenyl groups, where the alkyl and / or alkenyl groups are linear (straight-chain; n-) or branched. R7 is selected from H, C1-C18-alkyl groups, where alkyl is either linear (straight-chain; n-) or branched. The integer y in the general formula (NIS3) is a number in the range of 1 to 70, preferably 7 to 15.

[0595] NIS4 In one embodiment, the nonionic cleaning surfactant is NIS4, which includes sorbitan esters (NIS4a) and / or ethoxylated (NIS4b) or propoxylated (NIS4c) sorbitan esters. Non-limiting examples include products sold under the trademark names SPAN and TWEEN®.

[0596] NIS5 In one embodiment, one nonionic cleaning surfactant NIS5 is selected from 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-alkylglucosamine derivatives (NIS5g), such as glucamides (GA), fatty acid glucamides (FAGA), and combinations thereof.

[0597] Anionic cleaning surfactants Anionic cleaning surfactants (AS) refer to surfactants having a negatively charged ionic group. Anionic surfactants are not limited to, but include surface-active compounds that form a water-soluble compound by comprising a hydrophobic group and at least one water-soluble anionic group, usually selected from sulfates, sulfons, and carboxylates.

[0598] AS1 In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS1a) or (AS1b): [ka]

[0599] The variables in the general formulas (AS1a and AS1b) are defined as follows: R1 is selected from C1-C23 alkyl groups (such as 1-, 2-, 3-, and 4-C1-C23 alkyl groups) and C2-C23 alkenyl groups, where the alkyl and / or alkenyl groups are linear (straight-chain; n-) or branched, in the case of 2-, 3-, or 4-alkyl groups; examples include n-C7H15, n-C9H19, n-C11H23, n-C13H27, n-C15H31, n-C17H35, i-C9H19, and i-C12H25. R2 is selected from H, C1-C20 alkyl and C2-C20 alkenyl, where alkyl and / or alkenyl are linear (straight-chain; n-) or branched. R3 and R4 are each independently selected from C1-C16 alkyl groups, where alkyl is linear (straight-chain; n-) or branched; examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and isodecyl. A is selected from -RCOO-, -SO3-, and -RSO3-, where R is selected from linear (straight-chain; n-) or branched C1-C8 alkyl and C1-C4 hydroxyalkyl groups. The compound may also be called (fatty) alcohol / alkyl (ethoxy / ether) sulfate [(F)AES] when A- is -SO3-, and (fatty) alcohol / alkyl (ethoxy / ether) carboxylate [(F)AEC] when A- is -RCOO-. M+ is selected from H and salt-forming cations. Salt-forming cations can be monovalent or polyvalent; therefore, M+ is equal to 1 / v Mv+. Examples, but not limited to, include sodium, potassium, magnesium, calcium, ammonium, and ammonium salts of mono, di, and triethanolamines.

[0600] The integers in general formulas (AS1a) and (AS1b) are defined as follows: 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 1, preferably in the range of 9 to 50.

[0601] The anionic cleaning surfactants of general formulas (AS1a) and (AS1b) may have any structure, be block copolymers or random copolymers.

[0602] 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 0. M+ is preferably Na+. Such a compound may be called sodium lauryl sulfate.

[0603] In one embodiment, the anionic cleaning surfactant according to formula (AS1a) is a compound characterized by R1 being n-C11H23, R2 being H, A- being -SO3-, m, n, and o being 0; and M+ being preferably Na+, or by R1 being n-C18H37, R2 being H, A- being -SO3-, m, n, and o being 0; and M+ being preferably Na+. Such a compound may be referred to herein as AS1a1.

[0604] 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 to 5, preferably 3, and n and o are 0. M+ is preferably Na+. Such compounds as used herein may be called lauryl ether sulfate (LES), sodium lauryl ether sulfate (SLES), or AS1a2.

[0605] Further suitable anionic cleaning surfactants include C12-C18 sulfo fatty acid alkyl esters (such as C12-C18 sulfo fatty acid methyl esters), C10-C18 alkylaryl sulfonic acids (such as n-C10-C18 alkylbenzene sulfonic acid), and salts (M+) of C10-C18 alkylalkoxycarboxylates.

[0606] In all cases, M+ is selected from salt-forming cations. Salt-forming cations can be monovalent or polyvalent; therefore, M+ is equal to 1 / v Mv+. Examples, but not limited to, include sodium, potassium, magnesium, calcium, ammonium, and ammonium salts of mono, di, and triethanolamines.

[0607] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS1a), 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.

[0608] AS2 In one embodiment, a compound of general formula (AS2a) or (AS2b): [ka] (In the formula (AS2a), R1 is a linear or branched C10-C13 alkyl group; M+ is preferably Na+.) [ka] (In the formula (AS2b), R1 is a linear or branched C10-C13 alkyl group; n is 1 or 2; M+ is preferably Na+.) Anionic cleaning surfactants selected from the following.

[0609] Compounds relating to formula (AS2a) having a branched R1 may be referred to herein as BABS (branched alkylbenzene sulfonates). Compounds relating to formula (AS2a) where R1 is n-C10~C13 alkyl may be referred to herein as LAS (linear alkylbenzene sulfonates).

[0610] In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS2a), characterized in that R1 is n-C10H21, and the other surfactant is characterized in that R1 is n-C13H27. The two anionic cleaning surfactants may be sodium salts and may be referred to herein as AS2a.

[0611] 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 alkene sulfonate (60-65%) and hydroxyalkane sulfonate (35-40%).

[0612] AS3 In one embodiment, the anionic cleaning surfactant is selected from compounds of general formula (AS3), which may also be called an N-acyl amino acid surfactant: [ka]

[0613] The variables in the general formula (AS3) are defined as follows: R6 is selected from linear (straight-chain; n-) or branched C6-C22 alkyl groups and linear (straight-chain; n-) or branched C6-C22 alkenyl groups, such as oleyl groups. R7 is selected from H and C1-C4 alkyl groups. R8 is selected from H, methyl, -(CH2)3NHC(NH)NH2, -CH2C(O)NH2, -CH2C(O)OH, -(CH2)2C(O)NH2, -(CH2)2C(O)OH, (imidazole-4-yl)-methyl, -CH(CH3)C2H5, -CH2CH(CH3)2, -(CH2)4NH2, benzyl, hydroxymethyl, -CH(OH)CH3, (indole-3-yl)-methyl, (4-hydroxyphenyl)-methyl, isopropyl, -(CH2)2SCH3, and -CH2SH. R9 is selected from -COOX and -CH2SO3X, where X is selected from Li+, Na+, and K+.

[0614] In one embodiment, AS3 is a monocarboxylate and dicarboxylate of N-acylated glutamic acid (e.g., sodium, potassium, ammonium, and ammonium salts of mono, di, and triethanolamine), for example, 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; carboxylates of N-acylated alanine (e.g., sodium, potassium, and ammonium salts of mono, di, and triethanolamine) Selected from: sodium cocoyl alaninate and triethanolamine lauroyl alaninate; carboxylate salts of N-acylated glycines (e.g., sodium, potassium, ammonium, and ammonium salts of mono, di, and triethanolamines), e.g., sodium cocoyl glycinate and potassium cocoyl glycinate; carboxylate salts of N-acylated sarcosines (e.g., sodium, potassium, ammonium, and ammonium salts of mono, di, and triethanolamines), e.g., sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, sodium oleoyl sarcosinate, and ammonium lauroyl sarcosinate.

[0615] AS4 In one embodiment, the anionic cleaning surfactant is selected from the group 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, behenic acid, oleic acid, and (hydrated) erucic acid. M+ is selected from salt-forming cations. Salt-forming cations can be monovalent or polyvalent; therefore, M+ is equal to 1 / v Mv+.

[0616] Examples include, but are not limited to, sodium, potassium, magnesium, calcium, ammonium, and ammonium salts of mono, di, and triethanolamines.

[0617] In one embodiment, AS4h is a sulfuric acid, sulfonic acid, or carboxylic acid salt (M+) derived from a natural fatty acid (AS4b), such as taro (mainly C14-C18), coconut oil (mainly C12-C14), palm kernel oil (mainly C8-C18), olive oil (mainly C16-C18), or canola oil (mainly C18). Such anionic surfactant contains different amounts of sulfates, sulfonates, 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, depending on the natural fatty acid from which the soap is derived.

[0618] AS5 In one embodiment, the anionic cleaning surfactant is of formula (AS5): [ka] (In the formula, R1 is selected from sulfated fatty acid methyl esters (where R1 is one of the fatty acids C6-C16 or -CH2COOH, and M+ is preferably Na+).

[0619] 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 (mainly C14-C18), coconut oil (mainly C12-C14), palm kernel oil (mainly C8-C18), olive oil (mainly C16-C18), or canola oil (mainly C18). The MES may be referred to herein as AS5a.

[0620] In one embodiment, AS5a is a C12-C18 fatty acid methyl ester sulfonate. Preferably, AS5a is a coconut oil methyl ester sulfonate.

[0621] In one embodiment, the anionic cleaning surfactant is a monoester sulfosuccinic acid (which may be referred to herein as AS5b) or a diester of sulfosuccinic acid (which may be referred to herein as AS5c).

[0622] Amphoteric cleaning surfactant Amphoteric cleaning surfactants, depending on the pH, This refers to surfactants that can be cationic, zwitterionic, or anionic.

[0623] AMS1 In one embodiment, the amphoteric cleaning surfactant is selected from compounds of general formula (AMS1), which may also be called modified amino acids (proteinogenic and non-proteinogenic): [ka]

[0624] The variables in the general formula (AMS1) are defined as follows: R8 is selected from H, C1-C4 alkyl, and C2-C4 alkenyl, where it is alkyl and / or linear (straight-chain; n-) or branched. R9 is selected from C1-C22 alkyl, C2-C22 alkenyl, C10-C22 alkylcarbonyl, and C10-C22 alkenylcarbonyl. R10 is selected from H, methyl, -(CH2)3NHC(NH)NH2, -CH2C(O)NH2, -CH2C(O)OH, -(CH2)2C(O)NH2, -(CH2)2C(O)OH, (imidazole-4-yl)-methyl, -CH(CH3)C2H5, -CH2CH(CH3)2, -(CH2)4NH2, benzyl, hydroxymethyl, -CH(OH)CH3, (indole-3-yl)-methyl, (4-hydroxyphenyl)-methyl, isopropyl, -(CH2)2SCH3, and -CH2SH. Rx is selected from H and C1-C4 alkyl groups.

[0625] AMS2 In one embodiment, an amphoteric cleaning surfactant selected from compounds of general formula (AMS2a), (AMS2b), or (AMS2c), which may also be called betaines and / or sulfobetaines (AMS2): [ka]

[0626] The variables in general formulas (AMS2a), (AMS2b), and (AMS2c) are defined as follows: R11 is selected from linear (straight-chain; n-) or branched C7-C22 alkyl groups and linear (straight-chain; n-) or branched C7-C22 alkenyl groups. R12 is independently selected from linear (straight-chain; n-) C1-C4 alkyl groups. R13 is selected from C1-C5 alkyl and hydroxy C1-C5 alkyl groups; for example, 2-hydroxypropyl. The salt is selected from carboxylate salts and sulfonates. The integer r in the general formulas (AMS2a), (AMS2b), and (AMS2c) is in the range of 2 to 6.

[0627] In one embodiment, AMS2b is cocamidopropyl betaine.

[0628] A MS3 In one embodiment, an amphoteric cleaning surfactant selected from compounds of general formula (AMS3), which may also be called an alkylamphocarboxylate: [ka]

[0629] The variables in the general formula (AMS3) are defined as follows: R11 is selected from C7-C22 alkyl and C7-C22 alkenyl, where the alkyl and / or alkenyl is linear (straight-chain; n-) or branched, preferably linear. R14 is selected from -CH2C(O)O-M+, -CH2CH2C(O)O-M+, and -CH2CH(OH)CH2SO3-M+. R15 is selected from H and -CH2C(O)O-. The integer r in the general formula (AMS3) is in the range of 2 to 6.

[0630] In one embodiment, the alkylamphocarboxylate salt is selected from sodium cocoamphoacetate, sodium lauroamphoacetate, sodium capryloamphoacetate, disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, and disodium capryloamphodipropionate.

[0631] AMS4 In one embodiment, the amphoteric cleaning surfactant is selected from compounds of general formula (AMS4), which may also be called amine oxides (AO): [ka]

[0632] The variables in the general formula (AMS4) are defined as follows: R16 is selected from C8-C18 alkyl, hydroxy C8-C18 alkyl, acylamidopropoyl, and C8-C18 alkylphenyl groups; where alkyl and / or alkenyl are linear (straight-chain; n-) or branched. R17 is selected from C2-C3 alkylenes, hydroxy C2-C3 alkylenes, and mixtures thereof. R18: Each residue can be independently selected from C1-C3 alkyl and hydroxy C1-C3; the R15 groups may form a cyclic structure by being linked to each other, for example, by an oxygen or nitrogen atom. The integer X in the general formula (AMS4) is in the range of 0 to 5, preferably 0 to 3, and most preferably 0.

[0633] In one embodiment, an amine oxide selected from C10-C18 alkyldimethylamine oxides and C8-C18 alkoxyethyl dihydroxyethylamine 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, taludimethylamine oxide, and dimethyl-2-hydroxyoctadecylamine oxide.

[0634] In one embodiment, the amine oxide is cocamidylpropyl dimethylamine oxide, sometimes called cocamidopropylamine oxide.

[0635] Use and cleaning composition, and use of surfactants and cleaning compositions containing surfactants Alkoxylated diamines, oligoamines, and polyamines, as well as alkoxylated polyethyleneimines, will hereafter be referred to as "inventive compounds," and may also be referred to as "one or more compounds of the present invention."

[0636] The use of the surfactant of the invention as disclosed and defined herein and the products / formulations / compositions containing the same are the same as those known in the art; such use of the surfactant of the invention and the products / formulations / compositions containing the same are, in particular, the same as those disclosed in any of the following disclosures, namely, U.S. Patent Application Publication No. 2019 / 390142, International Publication No. 2020 / 264077, International Publication No. 2020 / 005476, International Publication No. 2023017061A1, International Publication No. 03 / 042262, Publication Nos. 800542 and 800500, International Publication No. 99 / 05242, U.S. Patent No. 5,576,282, U.S. Patent No. 6,306,812B1 and U.S. Patent No. 6,326,348 Disclosed in Specification B1—too many, too few—in particular those listed in the preceding chapter; such surfactants have many known uses, including pharmaceutical applications, oilfield applications, detergents, agricultural chemicals, printing, electronics, metalworking and manufacturing, lacquers and paints, automobile production, and any typical uses in which such surfactants are currently or have been used in the past, all of which are encompassed in the present invention.

[0637] In any of these disclosures relating to the state of the art in the art and known uses and applications, surfactants can be partially or completely re...

Claims

1. A method for preparing ethylene oxide or propylene oxide, comprising the following steps: (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting the methanol of step (b) to ethene and / or propene, (d) A step of reacting the ethene and / or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide. Includes, The carbon dioxide in step (b) above is at least partially recovered from industrial exhaust gases, air, ocean water, or other natural water sources, or obtained from biological processes, such as fermentation processes from waste or biomass. and / or A method wherein the hydrogen in step (b) is obtained, at least in part, by hydrolysis, preferably by electrolysis, and the hydrolysis, preferably the electrolysis, uses energy, preferably at least in part, produced from non-fossil resources.

2. A method for preparing ethanolamines, wherein the method comprises steps (b), (c), and (d) of the method according to claim 1, and consequently comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting methanol in step (b) to ethylene, (d) A step of forming ethylene by reacting the ethylene from step (c) with oxygen, (e) A step of converting the ammonia from step (a) into ethanolamines together with the ethylene oxide from step (d) in one or more steps. Includes, A method wherein the hydrogen in step (a) and / or step (b) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably the electrolysis, uses energy that is at least in part derived from non-fossil resources.

3. A method for preparing polyethyleneimine, wherein the method comprises steps (a), (b), (c), (d), and (e) of the method according to claim 2, and consequently comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) A step of converting methanol in step (b) to ethylene, (d) A step of forming ethylene oxide by reacting the ethylene from step (c) with oxygen, (e) A step of converting the ammonia from step (a) into ethanolamines together with the ethylene oxide from step (d) in one or more steps, (f) A step of separating monoethanolamine from the ethanolamines obtained in step (e); (g) A step of converting the monoethanolamine from step (f) to ethyleneimine, preferably by catalytic gas-phase synthesis. and (h) A step of polymerizing the ethyleneimine obtained in step (g) above into polyethyleneimine. Includes, A method wherein the hydrogen in step (a) and / or step (b) is obtained at least in part by hydrosplitting, preferably by electrolysis, and the hydrosplitting, preferably the electrolysis, uses energy that is at least in part derived from non-fossil resources.

4. The method according to any one of claims 1 to 3, wherein in all steps (a) to (h), energy in the form of heating energy and / or electricity is used, and at least a portion of the energy used in steps (a), (b), (c), (f) and (g), preferably the energy used in steps (a) to (h), is derived from non-fossil resources.

5. The method according to any one of claims 1 to 4, wherein the energy generated from the non-fossil resources is selected from the group consisting of solar energy (thermal, photovoltaic and centralized), wind power, hydroelectric power (tidal, wave, hydroelectric dams, river fluid dynamics), geothermal energy, heat recovered by heat pumps, bioenergy (biofuels, biomass), renewable parts of waste, nuclear power, and mixtures thereof.

6. The method according to any one of claims 1 to 5, wherein the hydrogen is obtained by water electrolysis, preferably by PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

7. The method according to any one of claims 1 to 6, wherein carbon dioxide is utilized in step (b), and the carbon dioxide is preferably recovered in part from industrial exhaust gas or from air.

8. The method according to any one of claims 1 to 7, wherein the ethylene in step (c) is preferably obtained by a methanol-to-olefin process using a zeolite catalyst.

9. The method according to any one of claims 1 to 8, wherein the ethylene oxide in step (d) is preferably obtained by epoxidation of ethylene with a silver-based catalyst.

10. i) 20 wt% to <100 wt% ethylene oxide units and / or propylene oxide units, ii) At least one alkylene oxide unit in an amount of 0 wt% to 30 wt%, which is different from ethylene oxide and propylene oxide units. iii) Zerevitinoff: At least one initiator unit having an active hydrogen atom, in an amount of >0 wt% to 80 wt%, (Here, the sum of the units listed in i), ii), and iii) is 100 wt%) A method for preparing an alkoxylated compound, comprising: The method according to claim 1 includes steps (b), (c), and (d), and consequently, the following steps: (b) A step of forming methanol by reacting hydrogen with carbon dioxide, (c) A step of converting the methanol of step (a) to ethene and / or propene, (d) A step of reacting the ethene and / or propene from step (b) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and (e0) A step of forming the alkoxylated compound by reacting the ethylene oxide and / or propylene oxide obtained in step (d) and at least one alkylene oxide, optionally different from ethylene oxide and propylene oxide, with at least one initiator unit having a Zerevitinoff active hydrogen atom in one or more steps. Includes, A method wherein at least part of the carbon dioxide in step (b) is recovered from industrial exhaust gases, air, ocean water, or other natural water sources, or obtained from a biological process, such as a fermentation process from waste or biomass.

11. The method according to claim 10, wherein the hydrogen in step (b) is obtained in part by hydrolysis, preferably by electrolysis, and the hydrolysis, preferably by electrolysis, uses energy which is preferably produced in part from non-fossil resources.

12. A method for producing an alkoxylated diamine, oligoamine, and polyamine or alkoxylated polyethyleneimine (any of these, individually or in combination, a “compound”), wherein the method comprises steps (a), (b), (c), and (d) of the method described in claim 2, and consequently comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) and (d) and the methanol in step (b) above is converted to ethylene and / or propylene, and further converted to ethylene oxide and / or propylene oxide together with oxygen or an oxidizing agent. e1) A step of converting the ethylene oxide and / or propylene oxide of step (d) and at least one alkylene oxide, optionally different from ethylene oxide and propylene oxide, into an alkoxylated diamine, oligoamine and polyamine or alkoxylated polyethyleneimine, respectively, in one or more steps using known methods. Includes, A method wherein the hydrogen from steps (a) and (b) has a molar content of deuterium of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated in part from non-fossil energy.

13. A method for producing an alkoxylated polyethyleneimine ("compound"), wherein the method comprises steps (a), (b), (c), (d), (e), (f), (g), and (h) of the method according to claim 3, and consequently comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) and (d) steps of converting the methanol from step (b) to ethylene and / or propylene, preferably ethylene, and further converting it with oxygen to ethylene oxide and / or propylene oxide, preferably ethylene oxide, (e) A step of converting the ammonia from step (a) into ethanolamines together with the ethylene oxide from step (d) in one or more steps, and (f) A step to separate monoethanolamine from the ethanolamines obtained in step (e), (g) A process of converting monoethanolamine to ethyleneimine, (h) A step of polymerizing the ethyleneimine of step (g) to polyethyleneimine; and (i) A step to obtain alkoxylated polyethyleneimines by alkoxyling the polyethyleneimine of step (g) with ethylene oxide and / or propylene oxide, preferably ethylene oxide, and optionally other alkylene oxides and / or lactones or other further components. Includes, The hydrogen from steps (a) and (b) is electrolyzed based on electricity generated at least partially from non-fossil energy, and has a molar content of deuterium in the range of ≤100 ppm, preferably 10 to ≤95 ppm, more preferably 10 to ≤90 ppm, and most preferably 10 to ≤80 ppm, relative to the total hydrogen content. A method wherein step (g) is preferably carried out in the gas phase or the liquid phase.

14. A method for producing a surfactant, wherein such surfactant comprises at least one structural unit derived from ethylene oxide, methanol, ammonia, or ethanolamine, or is produced from hydrogen, and the method comprises steps (a), (b), (c), (d), (e) and (f) of the method according to claim 3, and consequently comprises the following steps: (a) A step of forming ammonia by reacting hydrogen with nitrogen, (b) A step of forming methanol by reacting hydrogen with carbon oxides, preferably carbon dioxide, (c) and (d) a step of converting the methanol in step (b) to ethylene, and further converting it to ethylene oxide together with oxygen, (e) A step of converting the ammonia from step (a) into ethanolamines together with the ethylene oxide from step (d) in one or more steps, and (f) A step of separating monoethanolamine, diethanolamine and triethanolamine from the ethanolamines obtained in step (e), (g0) A step of converting any of the products of steps a), b), c), d), and e) into a surfactant containing at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine, and triethanolamine, or hydrogen, by at least one known method step. This process includes obtaining a surfactant that contains less deuterium in total hydrogen content compared to chemically identical surfactants obtained solely from fossil-derived sources. A method wherein the hydrogen from steps (a) and (b) is electrolyzed based on electricity generated at least partially from non-fossil energy, and has a molar content of deuterium in the range of ≤100 ppm, preferably 10 to ≤95 ppm, more preferably 10 to ≤90 ppm, and most preferably 10 to ≤80 ppm, based on the total hydrogen content.

15. A polyethyleneimine obtainable by the method described in any one of claims 3 to 9.

16. Ethanolamines obtainable by the method described in any one of claims 1 to 9.

17. Polyethyleneimine obtained by the method described in claim 15 or any one of claims 3 to 9, or ethanolamines obtained by the method described in claim 16 or any one of claims 1 to 9, CO ２ CO2 recovery methods ２ Used as an absorbent.

18. An alkoxylated compound obtainable by the method described in claim 10 or 11.

19. An alkoxylated compound obtainable by the method described in claim 18 or claim 10 or 11, which satisfies the biodegradability requirements specified in OECD 301B.

20. A surfactant obtainable by the method described in claim 14.

21. Use of alkoxylated compounds obtained by the method described in claim 18 or 19 or by the method described in claim 10 or 11 in home care products, cosmetics, pharmaceutical products, food products, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, lubricating greases, thermal conductive fluids, metalworking oils and transmission fluids, defoamers, softeners, rheological modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking oils, pesticides such as insecticides, textile and leather additives, bioprocessing, fuel performance packaging and poly(urethane) adhesives.

22. A compound comprising an alkoxylated diamine, oligoamine, or polyamine or alkoxylated polyethyleneimine (any of these, individually or in combination, "compound") wherein such compound is at least partially derived from hydrogen from a non-fossil source, the molar occupancy of deuterium is lower in such compound compared to the same chemical compound derived solely from a fossil source, and such alkoxylated compound may contain in its chain other monomers derived from such alkylene oxides, preferably ethylene oxide, wherein such other monomers are preferably selected from lactones and / or other alkylene oxides other than or added to ethylene oxide.

23. An alkoxylated polyethyleneimine ("compound") wherein the polyethyleneimine has a molar deuterium 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, based on the total hydrogen content.

24. Preferably in a composition, more preferably in a composition which is a fabric home care product, a cleaning composition, or an industrial and facility cleaning product, use of the surfactant described in claim 20 or the compound described in claim 22 or 23, or a compound that is available by or preferably obtained by the method described in claim 12 or 13, or a surfactant that is available by or preferably obtained by the method described in claim 14.

25. The use according to claim 23, wherein the composition contains at least one compound at a concentration of about 0.1% to about 20% by weight relative to the total weight of the composition or product, or the composition contains at least one surfactant at a concentration of about 0.1% to about 50% by weight relative to the total weight of the composition or product.

26. The use according to claim 23 or 24, wherein the composition is in liquid or semi-liquid form.

27. The following requirements: a. Contains at least one enzyme, b. Contains approximately 1% to 70% by weight of a surfactant system. c. At least one further cleaning aid, preferably at least one polymer, more preferably at least one graft polymer comprising at least one polymer side chain linked by radical polymerization of a polyalkylene oxide and at least one monomer selected from vinyl esters, vinyl lactams and optionally vinylamines, or a polymer side chain obtained from radical polymerization of at least one monomer including acrylic acid, methacrylic acid and its salts on an oligosaccharide or polysaccharide, in an effective amount. and d. To exhibit improved cleaning performance, preferably in primary cleaning. Furthermore, if the composition contains a surfactant that is or preferably obtained by the method described in claim 14, e. Exhibits primary cleaning characteristics. A use according to any one of claims 23 to 25, further satisfying at least one of the following: The surfactant may also be partially or completely included in the surfactant system for use.

28. A composition that is a laundry detergent, cleaning composition or fabric home care product, comprising at least one compound according to claim 22 or 23, or a compound available or preferably obtained by the method of claim 12 or 13, or a surfactant available or preferably obtained by the method of claim 14, wherein the at least one compound is contained in a concentration of preferably about 0.1% to about 20% by weight relative to the total weight of the composition or product, or, if the composition contains a surfactant available or preferably obtained by the method of claim 14, the at least one compound is contained in a concentration of about 0.1% to about 50% by weight relative to the total weight of the composition or product, wherein at least one of a) to c) is optionally included. a. Preferably, at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases, and peroxidases, more preferably at least two of the aforementioned types, and if an enzyme is included, preferably at least one enzyme stabilization system is also included. b. A surfactant system containing approximately 1% to 70% by weight. c. At least one effective amount of further cleaning aid, preferably at least one polymer, more preferably at least one polymer, based on a polymer side chain linked by radical polymerization of a polyalkylene oxide and at least one monomer selected from vinyl esters, vinyl lactams and optionally vinylamines, or at least one graft polymer comprising a polymer side chain obtained from radical polymerization of at least one monomer, including acrylic acid, methacrylic acid and its salts, on an oligosaccharide or polysaccharide. Includes, Furthermore, in the primary cleaning (i.e., stain removal), improved cleaning performance is optionally demonstrated. and / or if the composition contains a surfactant that is or preferably obtained by the method of claim 14, the color transfer prevention properties, A composition in which the surfactant may also be partially or completely included in the surfactant system.

29. The composition according to claim 28, which is in liquid or semi-liquid form, preferably a concentrated liquid detergent formulation, a single-use laundry detergent formulation, a liquid dishwashing detergent formulation, or a solid dishwasher formulation, more preferably a liquid laundry detergent formulation. The composition optionally further contains at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2 ppm to 5%, more preferably 0.1 to 2%, based on weight. A composition comprising, optionally, 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, and more preferably 0.01 to 0.6%, based on the weight of the composition.

30. Polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, available or obtained by methods using exclusively fossil-derived hydrogen, have a reduced fossil-derived hydrogen content, and consequently, have an overall reduced cradle-to-gate product carbon footprint compared to polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, available or obtained by methods using any one of claims 3 to 9, available or obtained by methods using any one of claims 1 to 9, available or obtained by methods using claim 10 or 11, surfactants available or obtained by methods using claim 14, alkoxylated diamines, oligoamines and polyamines according to claim 22, and alkoxylated polyethyleneimines according to claim 23, wherein the fossil-derived hydrogen content is reduced, and consequently, the overall product carbon footprint from cradle to gate is reduced compared to polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, available or obtained by methods using exclusively fossil-derived hydrogen.

31. Polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which are available or obtainable by the use of carbon dioxide that is at least partially recovered from industrial exhaust gases, air, ocean water or other natural water, or obtained from biological processes, and which have an overall reduced product carbon footprint from cradle to gate compared to these polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which are available or obtainable by the use of carbon dioxide that is at least partially recovered from industrial exhaust gases, air, ocean water or other natural water, or obtained from biological processes, and which are available or obtainable by the method of any one of claims 3 to 9, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which are available or obtainable by the method of any one of claims 1 to 9, which are available or obtainable by the method of claim 10 or 11, which are available or obtainable by the method of claim 14, which have an overall reduced product carbon footprint from cradle to gate compared to polyethyleneimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethyleneimines, which are available or obtainable by the use of carbon dioxide that is at least partially recovered from industrial exhaust gases, air, ocean water or other natural water, or obtained from biological processes.

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