Method for producing ethanolamine, polyethyleneimine and ammonia based on non-fossil energy

Abstract

Disclosed are: ethanolamine with a low molar fraction of deuterium, polyethyleneimine and ammonia; a process for the preparation of ethanolamine, polyethyleneimine and ammonia based on non-fossil energy; the use of the molar fraction of deuterium in hydrogen and a hydrogen-based downstream compound for tracking the source of production of hydrogen and a hydrogen-based downstream compound; and a method for tracking the source for producing hydrogen and a hydrogen-based downstream compound by determining the molar fraction of deuterium in the hydrogen and the hydrogen-based downstream compound; a use of the polyethyleneimine and a use of the polyethyleneimine; and to the use of these ethanolamine, preferably monoethanolamine and / or diethanolamine, or of the polyethyleneimine as a liquid or solid CO2 absorbent in CO2 capture processes.

Description

[0001] The present invention relates to: ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof) with a low molar fraction of deuterium, polyethyleneimine and ammonia; a method for preparing ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine and ammonia based on non-fossil energy; the use of the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen for tracking the source, in particular the energy source, of the hydrogen and downstream compounds based on hydrogen, wherein these compounds are preferably ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof) ), polyethyleneimine or ammonia; and a method for tracing the source of hydrogen and downstream hydrogen-based compounds, especially the energy source, by determining the molar fraction of deuterium in hydrogen and downstream hydrogen-based compounds, wherein these compounds are preferably ethanolamine (which is selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine or ammonia; the application of the polyethyleneimine and the use of the polyethyleneimine; and the use of these ethanolamines, preferably monoethanolamine and / or diethanolamine or the polyethyleneimine as liquid or solid CO2 absorbents in the CO2 capture process.

[0002] Ethanolamines are flammable, corrosive, colorless, viscous liquids produced by the reaction between ammonia and ethylene oxide (EO). Discovered many years ago, ethanolamines are key ingredients in many important product formulations, such as cosmetics and personal hygiene products, agricultural products, wood preservative chemicals, soaps and detergents, gas treatment agents. They can also be used to produce non-ionic detergents, emulsifiers and soaps, and in emulsion paints, polishes and cleaners. There are 3 types of ethanolamines: monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA). The formation of MEA, DEA, or TEA depends on whether the ammonia molecule reacts with one, two or three ethylene oxide molecules.

[0003] Polyethyleneimine (PEI) is a versatile polymer that can be used for various purposes such as, but not limited to, detergents, adhesives, water treatment agents and cosmetics. In addition, PEI is used in paper manufacturing and flocculation processes or as a raw material in the field of biotechnology.

[0004] Furthermore, PEI and MEA and / or DEA can be used as a capture agent for carbon dioxide (CO2). The amino groups in PEI react with CO2.

[0005] Ammonia is a key precursor in the preparation of MEA, which in turn is a key precursor in the preparation of PEI.

[0006] Since the development of the Haber-Bosch process for the preparation of ammonia, the vast majority of ammonia is produced by direct synthesis from hydrogen and nitrogen in the presence of a catalyst, especially an iron-containing catalyst. Particular care is required in providing the starting materials hydrogen and nitrogen. They should exhibit high purity and be substantially free of catalyst poisons such as carbon monoxide and sulfur compounds such as H2S and SO2. In modern processes, large amounts of hydrogen are thus provided from natural gas by steam reforming.

[0007] However, the petrochemical steam reforming process has its negative impacts in terms of its carbon footprint, including the consumption of large amounts of fossil-based natural resources and energy.

[0008] US2011 / 136097 relates to a method for determining the origin of a food, more specifically for determining the geographical and / or biological origin of a food containing alcohol or sugar by using, for example, specific isotope ratios of sugars from different plants, which serve as an isotopic "fingerprint" of a specific plant and are affected by climatic conditions and the region of origin.

[0009] However, the deuterium content utilized in the present invention is not a natural "fingerprint", but the discovery that the deuterium content of hydrogen obtained by electrolysis of water is lower than the deuterium content naturally present in hydrogen. Further, the geographical source area is not determined, but the production process of the hydrogen is determined.

[0010] US 6,495,609 relates to a method for recovering carbon dioxide from an ethylene oxide production process and using the recovered carbon dioxide as a carbon source for methanol synthesis. However, the hydrogen used in the method of US 6,495,609 is present in synthesis gas (such as natural gas) or refinery tail gas.

[0011] GB 2 464 691 A relates to the production of methanol from agricultural byproduct cellulose / lignin materials. In the first section of the synthesis plant, the cellulose / lignin byproducts remaining after the agricultural products are harvested are converted into carbon dioxide by thermal oxidation. In another section of the synthesis plant, hydrogen is produced by electrolysis and then reacted with carbon dioxide to produce methanol.

[0012] WO 2016 / 149507 A1 relates to the oxidative coupling of methane for obtaining a large number of different products. For example, claim 217 discloses a method for producing oxalate compounds.

[0013] US 7,119,231 B2 relates to a process for preparing alkanolamines by reacting ammonia with alkylene oxides in the presence of a catalyst in a reaction space to give monoalkanolamines or dialkanolamines or trialkanolamines or mixtures of two or three of these compounds. There is no suggestion about the deuterium content of the hydrogen-containing compounds employed in US 7,119,231 B2 or about the use of non-fossil energy sources.

[0014] FR 2 851 564 A1 relates to a process for preparing ethylene oxide and ethanolamine. As in FR 2 851 564 A1, there is no suggestion of the presence of deuterium in the hydrogen-containing compound or of the use of non-fossil energy sources.

[0015] US2008 / 0283411 A1 relates to a method for converting a carbon source and a hydrogen source into hydrocarbons. It is mentioned that the method and apparatus are useful for producing alternative energy to fossil fuels, storing renewable energy, sequestering carbon dioxide from the atmosphere, counteracting global warming, and storing carbon dioxide in liquid fuels.

[0016] WO 2015 / 102985 A1 relates to a process for preparing ethanolamine, which comprises reacting a water-ammonia solution with ethylene oxide. However, there is no suggestion in WO 2015 / 102985 A1 about the preparation of hydrogen by electrolysis, the use of renewable energy, and the presence of deuterium in the hydrogen-containing compounds disclosed in WO 2015 / 102985 A1.

[0017] DE 195 34 493 A1 relates to a process for preparing aziridines in the presence of a fine-particle shell catalyst. The aziridines are prepared by dehydrating alkanolamines in the presence of the catalyst. However, DE 195 34 493 A1 does not mention the electrolysis of water for preparing hydrogen, nor the deuterium content of the hydrogen-containing compounds mentioned in DE 195 34 493 A1, nor the use of renewable energy sources.

[0018] It is therefore an object of the present invention to provide environmentally friendly ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine and ammonia, and an environmentally friendly process for preparing them which uses as little fossil-based energy as possible.

[0019] This object is achieved by: ethanolamines selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, in which the molar fraction of deuterium is ≤100 ppm, preferably in the range of 10 to ≤98 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤90 ppm, based on the total hydrogen content; polyethyleneimine, which has a molar fraction of deuterium, based on the total hydrogen content, ≤110 ppm, preferably in the range of 10 to ≤105 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤92 ppm; and ammonia, in which the molar fraction of deuterium is ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content.

[0020] In another embodiment of the present invention, the object is achieved by a method for preparing ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, wherein the method comprises the following steps:

[0021] (a) providing hydrogen with a molar fraction of deuterium of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated at least partly from non-fossil energy sources,

[0022] (b) reacting the hydrogen from step (a) with nitrogen to form ammonia,

[0023] (c) reacting the hydrogen from step (a) with a carbon oxide, preferably carbon dioxide, to form methanol,

[0024] (d) converting the methanol from step (c) into ethylene and further into ethylene oxide,

[0025] (e) converting the ammonia from step (b) into ethanolamine in one or more steps using the ethylene oxide from step (d).

[0026] This object is further achieved by: a method for preparing polyethyleneimine, wherein the method comprises:

[0027] (f) separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the process according to any one of claims 1 to 7, or from the ethanolamine according to claim 8;

[0028] (g) converting monoethanolamine into ethyleneimine,

[0029] (h) polymerizing the ethyleneimine from step (g) to form polyethyleneimine; and

[0030] A method for preparing ammonia, wherein the method comprises the following steps:

[0031] (a) providing hydrogen with a molar fraction of deuterium of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content, by electrolysis based on electricity generated at least partly from non-fossil energy sources,

[0032] (b) reacting the hydrogen from step (a) with nitrogen to form ammonia.

[0033] Furthermore, it is important that the origin of hydrogen and downstream compounds obtained through clean energy can be tracked in a reliable manner.

[0034] This is especially to ensure:

[0035] The production of hydrogen and downstream compounds meets sustainability criteria.

[0036] Renewable properties will not be double counted.

[0037] Companies are increasingly focusing on sourcing green energy. Therefore, it is imperative to develop tracking systems for the origin of energy used in the production of hydrogen and downstream compounds.

[0038] This object is also achieved by: the use of the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen for tracing the source of the hydrogen and downstream compounds based on hydrogen, especially the energy source, wherein these compounds are preferably ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia; and a method for tracing the source of hydrogen and downstream compounds based on hydrogen, especially the energy source, by determining the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen, wherein these compounds are preferably ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia. Methods for determining the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen are known to those skilled in the art. A suitable method is described in the examples of the present application.

[0039] Another environmental benefit of the environmentally friendly ethanolamines and polyethyleneimines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the present invention is their use in carbon capture processes, since the ethanolamines and polyethyleneimines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the present invention are produced using as little fossil-based energy as possible, ideally no fossil-based energy, and indeed therefore increase CO2 emissions only as little as possible, ideally not at all.

[0040] Therefore, another embodiment of the present invention is the use of an ethanolamine or polyethyleneimine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the present invention as a liquid or solid CO2 absorbent in a CO2 capture process.

[0041] The molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen is given in the present application in ppm based on the total hydrogen content, which is the mol-ppm content of deuterium based on the total hydrogen content (in hydrogen or in the compound in question, respectively).

[0042] The deuterium content of hydrogen and downstream hydrogen-based compounds is expressed herein as total molar hydrogen content (total deuterium 1 H and deuterium 2 The terms "deuterium content" and "molar fraction of deuterium" are used synonymously throughout this application.

[0043] 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 reactants is replaced by one of its isotopes. Formally, it is a reaction involving light (k L ) and weight (k H ) The rate constant k of the reaction of isotopically substituted reactants (isotopic configurations) L / k H This change in reaction rate is a quantum mechanical effect that results primarily from the fact that the heavier isotope has a lower vibrational frequency than its lighter counterpart. In most cases, this means that the energy input required to reach the transition state is higher for the heavier isotope, and therefore the reaction rate is slower.

[0044] Isotope rate changes are most significant when the relative mass change is greatest, since the effect is related to the vibrational frequency of the bonds affected. For example, replacing a hydrogen atom (H) with its isotope deuterium (D) represents a 100% increase in mass, whereas replacing a hydrogen atom with its isotope deuterium (D) represents a 100% increase in mass. 13 C instead 12 C, the mass increases by only 8%. The rate of reactions involving CH bonds is generally 6-10 times faster than that of the corresponding CD bonds, while 12 C reaction is only slightly higher than the corresponding 13 C reacts 4% faster.

[0045] The primary kinetic isotope effect is found when bonds to isotopic atoms are formed or broken. The secondary kinetic isotope effect is observed when bonds to isotopic atoms in the reactants are not broken or formed. The secondary kinetic isotope effect tends to be much smaller than the primary kinetic isotope effect; however, the secondary deuterium isotope effect can be as large as 1.4 per deuterium atom.

[0046] The process for preparing ethanolamine comprises steps (a) to (e) as mentioned above:

[0047] Step (a)

[0048] Step (a) involves providing hydrogen having a molar fraction of deuterium of less than 90 ppm based on the total hydrogen content by electrolysis based on electricity generated at least partly from non-fossil energy sources.

[0049] The electricity is generated at least in part from non-fossil resources.

[0050] The term "at least partly" means that part of the electricity can still be generated by fossil fuels, preferably natural gas, because the combustion of natural gas leads to much lower carbon dioxide emissions per megajoule of electricity generated compared to the combustion of coal. However, the part of the electricity generated by fossil fuels should be as low as possible, preferably ≤50%, preferably ≤30%, most preferably ≤20%, further most preferably ≤10%. In one embodiment, the electricity is generated only by non-fossil resources.

[0051] Depending on local legislation, various methods have been established for certifying and tracking the “energy mix”. Certificates such as the “Fossil Free Certificate Contract” are a common practice for tracking the ratio of non-fossil energy used in industrial processes and related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / )

[0052] Preferably, the electricity is at least partially generated by wind, solar (thermal, photovoltaic and concentrated solar), hydropower (tidal, wave, hydroelectric dams, in-river hydrodynamics), geothermal, ambient or industrial heat captured by heat pumps, bioenergy (biofuels, biomass), renewable portions of waste energy or nuclear energy (fission).

[0053] In another embodiment, the electricity is at least partially generated from renewable resources, preferably wind, solar (thermal, photovoltaic and concentrated solar), hydropower (tidal power, wave power, hydroelectric dams, in-river hydrodynamics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuels, biomass), or a renewable portion of waste.

[0054] The types of power resources mentioned above are generally known to those skilled in the art.

[0055] In a preferred embodiment of the method according to the invention, the electricity from non-fossil resources used in the electrolysis according to the invention can be generated at least partly by nuclear energy. Nuclear energy can be obtained by fission.

[0056] Fission occurs when a neutron enters the nucleus of a larger atom, forcing it to ignite and split into two smaller atoms - also called fission products. Additional neutrons are also released that can initiate a chain reaction. As each atom splits, a huge amount of energy is released. Uranium and plutonium isotopes are most commonly used for fission reactions in nuclear power reactors because they are easy to initiate and control. The energy released by fission in these reactors heats water into steam. The steam is used to spin turbines to produce carbon-free electricity.

[0057] In a preferred embodiment of the method of the present invention, the electricity used in the electrolysis is generated at least in part by wind power. Wind power can be used to operate wind turbines. The rated power of modern utility-scale wind turbines ranges from about 600kW to 9MW. The power that can be generated from the wind is a function of the cube of the wind speed, so as the wind speed increases, the power output increases up to the maximum output of a particular turbine. Areas with stronger and more constant winds, such as offshore and high altitude sites, are preferred locations for wind power plants.

[0058] In a further preferred embodiment of the method of the invention, the electricity used in the electrolysis is at least partially generated by solar energy, particularly preferably a photovoltaic system. Photovoltaic systems convert light into direct current (DC) by utilizing the photoelectric effect. Concentrated solar power (CSP) systems use lenses or reflectors and tracking systems to focus large areas of sunlight into small beams. CSP-Stirling currently has by far the highest efficiency of all solar technologies.

[0059] In a preferred embodiment of the inventive method, the electricity used in the electrolysis is at least partially generated by hydroelectric power. Hydroelectric power has many forms. Traditionally, hydroelectric power comes from building large hydroelectric dams and reservoirs. Small hydroelectric systems are hydroelectric devices that usually produce up to 50MW of power. They are often used on small rivers or on large rivers with low-impact development projects. The hydroelectric power station running on the river obtains energy from the river without creating large reservoirs. Water is typically transported (using channels, pipelines and / or tunnels) along the side of the valley until the water is higher than the valley bottom, at which time water can be allowed to fall through a penstock to drive a turbine.

[0060] Wave power, which captures the energy of sea surface waves, and tidal power, which converts the energy of tidal waves, are two forms of hydroelectric power with future potential.

[0061] In a further preferred embodiment of the method of the invention, the electricity used in the electrolysis is generated at least in part by geothermal energy. Geothermal energy is heat from below the surface of the earth. It is contained in rocks and fluids below the earth's crust and can be found as far away as the earth's hot lava, rock algae.

[0062] To generate electricity through geothermal energy, a well is dug up to a mile deep into an underground reservoir to capture steam and hot water, which can then be used to drive a turbine connected to a generator. There are three types of geothermal power plants: dry steam, flash steam, and binary.

[0063] Dry steam is the oldest form of geothermal technology and takes steam out of the ground and uses it to drive a turbine directly. Flash plants use high-pressure hot water entering cold, low-pressure water, while binary plants pass hot water through a secondary liquid with a lower boiling point, which turns into steam to drive a turbine.

[0064] In a further preferred embodiment of the method of the present invention, the electricity used in the electrolysis is at least partially produced by biomass. Biomass is a biological material derived from a living organism or a recently living organism. It most often refers to a material of plant or plant origin, which is specifically referred to as lignocellulosic biomass. As an energy source, biomass can be used directly to produce heat (e.g., heat from a fermentation process) or electricity via combustion, or indirectly after converting it into various forms of biofuels and gases. The conversion of biomass to biofuels can be achieved by different methods, which are roughly classified as: thermal, chemical and biochemical methods. As of 2012, wood is the largest biomass energy source; examples include forest residues (such as dead trees, branches and stumps), yard trimmings, wood chips, and even municipal solid waste. Industrial biomass can grow from various types of plants, including Miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a variety of tree species ranging from eucalyptus to oil palm (palm oil).

[0065] Plant energy is produced by crops grown specifically for use as fuel, which provide high biomass yields per hectare with low energy input. Grains can be used for liquid transport fuels, while straw can be burned to produce heat or electricity. Biomass can be converted into other usable energy forms, such as methane gas or transport fuels such as ethanol and biodiesel. Rotting garbage, as well as agricultural and human waste, all release methane gas - also known as landfill gas or biogas. Crops (such as corn and sugar cane) can be fermented to produce the transport fuel ethanol. Biodiesel (another transportation fuel) can be produced from surplus food such as vegetable oils and animal fats.

[0066] Bioenergy technologies convert renewable biomass fuels into heat or electricity using processes similar to those that use fossil fuels. There are three ways to capture the energy stored in biomass to produce bioenergy: combustion, bacterial decay, and conversion to gaseous or liquid fuels. Bioenergy can offset the need for carbon fuels burned in power plants, thereby reducing the carbon intensity of electricity generation. Unlike some forms of intermittent renewable energy, bioenergy can increase the flexibility of power generation and enhance the reliability of the grid.

[0067] The electrolysis in step (a) is typically the electrolysis of water.

[0068] Electrolysis of water is an environmentally friendly method for producing hydrogen because it uses renewable H2O and produces only pure oxygen as a byproduct.

[0069] According to the invention, electrolysis, typically water electrolysis, utilizes direct current (DC) as electricity at least partially from non-fossil energy sources.

[0070] It is now observed, as a key observation of the present application, that the deuterium atom content of hydrogen produced by the electrolysis of water is lower than that of hydrogen produced petrochemically (e.g., as contained in fossil-based synthesis gas), i.e., based on a total hydrogen content 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. The deuterium atom content in the hydrogen produced by electrolysis can be as low as 10 ppm. The remaining deuterium is mainly present in the form of DH rather than D2.

[0071] One suitable water electrolysis method is alkaline water electrolysis. Hydrogen production by alkaline water electrolysis is a mature technology up to the megawatt range at commercial levels. In alkaline water electrolysis, initially on the cathode side, two water molecules of an alkaline solution (KOH / NaOH) are reduced to one hydrogen molecule (H2) and two hydroxide ions (OH - The generated H2 is released from the cathode surface in gaseous form, and hydroxide ions (OH - ) migrate through the porous membrane to the anode under the influence of the electric field between the anode and the cathode, where they are discharged into half an oxygen molecule (O2) and one molecule of water (H2O). Alkaline electrolysis operates at relatively low temperatures such as 30°C-100°C with an alkaline aqueous solution (KOH / NaOH) as the electrolyte, with a concentration of about 20% to 30%. The membrane in the center of the electrolytic cell separates the cathode and the anode and also separates the generated gases from their corresponding electrodes, thereby avoiding mixing of the generated gases.

[0072] An overview of hydrogen production by alkaline water electrolysis powered by renewable energy is given in J. Brauns and T. Turek, Processes, 8(2) (2020), p. 248.

[0073] In a further embodiment of the process of the invention, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variants of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).

[0074] PEM water electrolysis technology is similar to PEM fuel cell technology, where a solid polysulfonated membrane is used As electrolyte (proton conductor). These proton exchange membranes have many advantages, such as low gas permeability, high proton conductivity (0.1 ± 0.02Scm -1 ), low thickness (20-300 μm), and allows high-voltage operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most advantageous methods for converting renewable energy into high-purity hydrogen. PEM water electrolysis has great advantages, such as compact design, high current density (above 2 A cm -2 ), high efficiency, fast response, operation at low temperature (20°C-90°C), and production of ultrapure hydrogen. State-of-the-art electrocatalysts for PEM water electrolysis are highly active precious metals such as Pt / Pd for the hydrogen evolution reaction (HER) at the cathode and IrO2 / RuO2 for the oxygen evolution reaction (OER) at the anode.

[0075] One of the biggest advantages of PEM water electrolysis is its ability to operate at high current densities. This can result in reduced operating costs, especially for systems coupled to very dynamic energy sources such as wind and solar, where sudden surges in energy output would otherwise result in uncaptured energy. Polymer electrolytes allow PEM water electrolyzers to operate with very thin membranes (on the order of 100-200 μm) while still allowing high operating pressures, resulting in low ohmic losses caused primarily by conduction of protons across the membrane (0.1 S / cm), and compressed hydrogen output.

[0076] The PEM water electrolyzer utilizes a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while electrically insulating the electrodes. Under standard conditions, the enthalpy required to form water is 285.9 kJ / mol. Part of the energy required to sustain the electrolysis reaction is supplied by thermal energy, and the remainder is supplied by electrical energy.

[0077] The half-reaction occurring on the anode side of a PEM water electrolyser is generally referred to as the oxygen evolution reaction (OER). Here, liquid water reactant is supplied to a catalyst where it is oxidized into oxygen, protons, and electrons.

[0078] The half-reaction that occurs on the cathode side of a PEM water electrolyser is often referred to as the hydrogen evolution reaction (HER). Here, protons that have traveled across the membrane are reduced to gaseous hydrogen.

[0079] PEMs can be made of pure polymer membranes or composite membranes in which other materials are embedded in the polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA (e.g. DuPont product). Although There are ionomers with a fully fluorinated backbone like Teflon, but there are many other structural motifs of ionomers used to make proton exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

[0080] An overview of hydrogen production by PEM water electrolysis is given in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442-4454.

[0081] AEM water electrolysis technology uses low-cost catalytic materials (as in alkaline electrolysis) and a solid polymer electrolyte structure (as in PEM electrolysis technology). AEM electrolysis technology operates in an alkaline environment (pH of about 10), enabling the use of appropriate non-precious metal electrocatalysts (i.e., catalysts without platinum group metals = catalysts without PGMs) while adapting to a zero-gap structure. The membrane used in this type of electrolysis is a polymer membrane containing quaternary ammonium salts. It is relatively cheap and has low interaction with atmospheric CO2.

[0082] catalyst:

[0083] As an example of a hydrogen evolution reaction (HER) catalyst, a catalyst based on a Ni—Mo alloy material is suitable.

[0084] As examples of oxygen evolution reaction (OER) catalysts, highly active transition metal mixed oxides are suitable. Specific examples are CuxCo3_xO4, NiCo2O4:Fe and Ni-Fe alloys on Ni foam supports, such as PGM-free catalysts (Ni-Fe, Ni-Mo, Ni / (CeO2-La2O3) / C and CuxCo3_xO4).

[0085] Membranes and Ionomers:

[0086] Due to the development of stable functional groups on the polymer backbone, the chemical stability of AEMs under alkaline conditions has been significantly improved. This allows the use of such membranes at higher temperatures for long periods of time in AEM electrolysis. Suitable membranes and ionomers are known to those skilled in the art and are described, for example, in the reviews mentioned below. An example is the commercial membrane Tokuyama A201.

[0087] Membrane electrode assembly preparation and battery performance:

[0088] Physical and electrochemical characterization of membrane electrode assemblies prepared by either the catalyst coated substrate (CCS) or catalyst coated membrane (CCM) approaches indicate that CCM is preferred because the improvement in ionic conductivity far outweighs any improvement in electronic conductivity.

[0089] Liquid electrolyte: Pure water feed generally results in poor current density, while 1% K2CO3 or dilute KOH solution gives good results. Good electrolysis performance is achieved with 1% K2CO3 electrolyte. Therefore, it is preferred that the aqueous electrolyte contains 0.1 to 2 wt% K2CO3 or KOH.

[0090] An overview of hydrogen production by anion exchange membrane water electrolysis is given in HAMiller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0091] Besides alkaline water electrolysis (AEM and PEM), another commercially available electrolysis technology is solid oxide electrolysis (SOE).

[0092] SOEC (solid oxide electrolyzer) feeds water into the cathode and the water undergoes a water reduction reaction (WRR), which converts the water into hydrogen and oxide ions. This hydrogen is then made to reach a purification module to separate the hydrogen from the remaining water. Then, the oxide ions migrate from the cathode to the anode and they release electrons to the external circuit via the oxygen evolution reaction (OER) to become oxygen. Typically, the operating temperature of SOFC is 800°C to 1,000°C because high temperatures are required to thermally activate the migration of oxide ions and promote electrochemical reactions on both electrodes. Therefore, the overall efficiency is improved. SOEC is described, for example, in K.Kamlungsua et al., FUEL CELLS20 [Fuel Cell 20], 2020, No. 6, 644-649.

[0093] Preferably, the electrolysis in step (a) is water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0094] In another preferred embodiment, the electrolysis in step (a) is solid oxide water electrolysis (SOE).

[0095] It is known in the art that, with respect to the feed water in water electrolysis (e.g., polymer electrolyte membrane water electrolysis), the deuterium in the released hydrogen can be depleted. The depletion factor depends on the electrolysis conditions (water flow, current density). Since the average deuterium content (molar fraction of deuterium) of water is about 150 ppm based on the total hydrogen content, the molar fraction of deuterium (deuterium content) of the hydrogen provided in step (a) of the method of the present invention is based on the total hydrogen content ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, most preferably in the range of 10 to ≤80 ppm, or even lower.

[0096] Generally, any water source can be used in the preferred water electrolysis in step (a). However, since the hydrogen prepared in step (a) has a molar fraction of deuterium (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, most preferably in the range of 10 to ≤80 ppm, it is preferred to use water having a molar fraction of deuterium (deuterium content) of less than 160 ppm, based on the total hydrogen content.

[0097] Vienna Standard Mean Ocean Water (VSMOW) is an isotopic water standard defined by the International Atomic Energy Agency in 1968. Despite the somewhat misleading phrase "seawater", VSMOW refers to pure water (H2O) and does not include any salts or other substances normally found in seawater. VSMOW serves as a reference standard for comparing hydrogen and oxygen isotope ratios (primarily in water samples). Very pure, distilled VSMOW water is also used for high-precision measurements of the physical properties of water and for determining laboratory standards, as it is considered representative of "average ocean water" and, in fact, represents the water content of the Earth.

[0098] The isotopic composition of VSMOW water is specified as the ratio of the molar abundance of the rare isotope in question divided by the molar abundance of its most common isotope and is expressed as parts per million (ppm). 16 O (the most common isotope of oxygen with eight protons and eight neutrons) is more abundant in seawater than 17 O (with one extra neutron) is about 2,632 times more dominant. The isotopic ratios of VSMOW water are defined as follows:

[0099] 2 H / 1 H = 155.76 ± 0.1 ppm (ratio of 1 part / about 6420 parts)

[0100] 3 H / 1 H=1.85±0.36×;10 -11 ppm(1 part / approximately 5.41×; 10 16 The ratio of the parts is negligible due to the effects related to physical properties)

[0101] 18 O / 16 O = 2005.20 ± 0.43 ppm (ratio of 1 part / about 498.7 parts)

[0102] 17 O / 16 O = 379.9 ± 1.6 ppm (ratio of 1 part / about 2632 parts)

[0103] (See: https: / / en-academic.com / dic.nsf / enwiki / 753132)

[0104] More preferably, the water in step (a) has an average deuterium content of from 1 ppm (ultra-light water) to 156 ppm based on the total hydrogen content, most preferably from 2 ppm to 150 ppm based on the total hydrogen content.

[0105] Methods for depleting water of deuterium are known to the person skilled in the art. However, such methods are generally energy-consuming electrolytic methods, as described, for example, in CN 103848399A.

[0106] Therefore, in the case of using deuterium-depleted water, it is preferred to use deuterium-depleted water obtained from the following resources:

[0107] - Byproduct of "heavy water" (D2O) production (heavy water has applications in organic chemistry, drug development and nuclear reactors); (deuterium content is about 10-120 ppm)

[0108] - Alpine water; (deuterium content is about 120-150ppm)

[0109] -Surface river and lake water; (deuterium content is about 130-150ppm)

[0110] - Any water source with seasonally low deuterium content, such as water collected at low temperatures (cold winter water contains less deuterium than warm summer water); such as water obtained during winter time, such as water obtained from snow or ice; (deuterium content is about 120-150 ppm)

[0111] - Polar water and Antarctic glacial water (deuterium content is about 90-150ppm)

[0112] - Low-salinity seawater, such as low-salinity seawater near estuaries, desalinated seawater or brackish water and wastewater treatment effluent water; (deuterium content is about 130-155 ppm)

[0113] Step (b)

[0114] Step (b) involves reacting the hydrogen from step (a) with nitrogen to form ammonia,

[0115] The reaction of step (b) preferably follows the Haber-Bosch method.

[0116] The catalysts commonly used in the Haber-Bosch process usually fall into one of two categories: molten iron catalysts and supported metal catalysts. Fused iron catalysts are derived from iron oxides, of which there are three possibilities: Fe2O3, Fe3O4, and Fe 1-x O, which are known as hematite, magnetite and wüstite respectively.In industry, these iron catalysts will be multiply promoted by promoters such as K2O, BaO, KOH, CaO, MgO and Al2O3 present in small amounts of small weight percentages.

[0117] Supported metal catalysts are catalysts composed of metal catalyst materials (usually ruthenium or cobalt for ammonia synthesis reactions) present on the surface of a support material (usually activated carbon or metal oxides). Typically, the weight percentage of the metal catalyst is about 2%-10%.

[0118] Other catalysts that may be used are nickel, and nitride catalyst systems or electride, hydride, nitride, hydride oxynitride promoted Ru, Fe, Co and Ni catalysts.

[0119] The above mentioned catalysts can be used both in conventional centralized large-scale Haber-Bosch ammonia synthesis plants and in distributed small-scale ammonia production via the same process.

[0120] In one embodiment of the present invention, step (b) is carried out at a pressure in the range of 50 to 350 bar (absolute), preferably 150 to 300 bar (absolute).

[0121] In one embodiment of the present invention, step (b) is carried out at a temperature ranging from 300°C to 600°C, preferably from 400°C to 500°C.

[0122] The overall kinetic isotope effect is cumulative, since it will also be present in all subsequent production steps downstream in the value chain. By carrying out step (b), ammonia is formed. The deuterium content is even lower than that corresponding to the distribution obtained by classical petrochemical routes.

[0123] Step (c)

[0124] Step (c) involves reacting the hydrogen from step (a) with a carbon oxide, preferably carbon dioxide, to form methanol.

[0125] Suitable carbon oxides are carbon monoxide, carbon dioxide or a mixture of the two, with carbon dioxide being preferred.

[0126] The process conditions for the hydrogenation of carbon monoxide or a mixture of carbon monoxide and carbon dioxide are known per se, for example low-pressure synthesis, medium-pressure synthesis and high-pressure synthesis.

[0127] i) Low pressure synthesis

[0128] The low-pressure synthesis is usually carried out at a pressure between 50 and 100 bar. The temperature is usually between 220° C. and 300° C. As catalysts, catalysts based on Cu, Zn and Al2O3 (e.g. CuO / ZnO / Al2O3) are usually used. The low-pressure synthesis is the most preferred synthesis for preparing methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0129] ii) Medium pressure synthesis

[0130] Medium-pressure synthesis is generally carried out at pressures between 100 and 250 bar. The temperature is generally up to 300° C. As catalysts, catalysts based on Zn / Cr 2 O 3 or Zn—Cu catalysts are generally used.

[0131] iii) High-pressure synthesis The high-pressure synthesis is usually carried out at a pressure between 250 and 350 bar. The temperature is usually 320° C. to 380° C. As catalyst, catalysts based on zinc-chromium oxide are usually used. This process is less preferred for the production of methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0132] The current world energy system is still mainly based on the use of fossil fuels, and although the use of renewable energy sources has increased, it will continue in the medium and short term. The extensive use of fossil fuels in industry and transportation generates large CO2 emissions. Since the object of the present invention is to provide environmentally friendly ethanolamines, polyethyleneimines and ammonia and environmentally friendly methods for preparing them, it is preferred to prepare methanol by reacting the hydrogen from step (a) with the carbon dioxide in step (c) according to the process of the present invention.

[0133] In a preferred embodiment, the carbon dioxide provided in step (c) is captured from industrial flue gases or ambient air.All available capture technologies can be used.

[0134] An overview of commercial CO2 capture technologies is given in Koytsoumoa et al., The Journal of Supercritical Fluids, Vol. 132, February 2018, pp. 3-16.

[0135] Capturing CO2 is most cost-effective at point sources, such as large carbon-based energy facilities, industries with high CO2 emissions (e.g. cement production, ammonia synthesis, steelmaking), natural gas processing, synthetic fuel plants, and fossil fuel-based hydrogen production plants. Extracting CO2 from the air is possible, although the lower concentration of CO2 in the air compared to combustion sources complicates the engineering and therefore makes the process more expensive.

[0136] In some preferred embodiments, the carbon dioxide provided in step (b) is captured from industrial flue gas.

[0137] The main industrial sources of CO2 are power plants based on the combustion of fossil fuels, oil refineries, biogas desulfurization (e.g. fermentation) and the production of chemicals. Related chemical production processes are, for example, naphtha cracking of C1-C4 olefins and C6 aromatics as well as downstream chemicals such as, in particular, ammonia and other CO2-intensive products). In addition, the production of industrial paper, food, cement, minerals and iron and steel can be mentioned as examples.

[0138] In post-combustion capture, CO2 is removed after the combustion of fossil fuels (this is the scenario to be applied to fossil fuel power plants). CO2 is captured from flue gases at power stations or other point sources. Absorption or washing of carbon with amines are the main capture technologies. It is the only carbon capture technology used in industry so far. Suitable post-carbon capture methods are, for example, absorption (chemical absorption, physical absorption), adsorption (chemical absorption, physical adsorption), membrane processes, biological processes and cryogenic processes.

[0139] Pre-conversion capture means capturing the CO2 produced as an undesirable co-product of the intermediate reaction of the conversion process. Some examples include the production of ammonia and coal gasification in power plants. In ammonia production, the CO2 produced together with hydrogen during steam reforming must be removed before ammonia synthesis can occur - absorption in monoethanolamine (MEA) and / or diethanolamine (DEA) is commonly used for these purposes. Similarly, in an integrated gasification combined cycle (IGCC) power plant, CO2 must be separated from hydrogen. This is typically achieved using physical solvents such as selexol and rectisol. Note that when applied to power plants, pre-conversion capture is also called pre-combustion capture.

[0140] Oxy-fuel combustion technology involves the combustion of carbonaceous fuels in a pure oxygen stream instead of air. Since the oxidant (O2) does not contain other components in air (such as nitrogen), the CO2 concentration in the flue gas will be very high, while the water vapor content can be easily removed.

[0141] CO2 is adsorbed to the MOF (metal-organic framework) by physical or chemical adsorption based on the porosity and selectivity of the MOF, leaving a CO2-depleted gas stream. The CO2 is then stripped from the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA), allowing the MOF to be reused.

[0142] In some other preferred embodiments, the carbon dioxide provided in step (b) is captured from ambient air.

[0143] Direct air capture (DAC) is the process of capturing carbon dioxide (CO2) directly from ambient air and producing a concentrated stream of CO2 for sequestration or utilization or the production of carbon-neutral fuels. Carbon dioxide removal is achieved when ambient air is contacted with a chemical medium (typically an aqueous alkaline solvent or adsorbent). These chemical media are then stripped of CO2 by the application of energy (i.e., heat), resulting in a CO2 stream that can be dehydrated and compressed, while regenerating the chemical media for reuse.

[0144] In Chen, Lackner et al., Angew. Chem. Int. Ed. [International Edition of Applied Chemistry] 2020, 59, 6984-7006, "Sorbents for the Direct Capture of CO2 from Ambient Air", the main types of adsorbents designed to capture CO2 from ambient air are described, which are classified by the following adsorption mechanisms: physical adsorption, chemical adsorption, and water swing adsorption.

[0145] In Kommalapati et al., Energy Technol. 2017, 5, 822-833, the use of polyethyleneimines in carbon dioxide capture and separation is described.

[0146] Diluted CO2 can be separated efficiently 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 change of water. Other materials that can be used are metal organic frameworks (or MOFs). Membrane separation of CO2 relies on semipermeable membranes.

[0147] In one embodiment of the invention, ethanolamine and / or polyethyleneimine according to the invention in a mixture of monoethanolamine, diethanolamine and triethanolamine or each, preferably in a mixture of monoethanolamine (MEA) and diethanolamine (DEA) is employed in a method for capturing CO2. The ethanolamine and polyethyleneimine according to the invention in a mixture of monoethanolamine, diethanolamine and triethanolamine or each, does only as little as possible, in a preferred embodiment does not add to the CO2 emissions and therefore does as little as possible, preferably does not contribute to the CO2 emissions themselves.

[0148] Therefore, in another embodiment, the present invention relates to the use of ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, preferably ethanolamine in a mixture of monoethanolamine (MEA) and diethanolamine (DEA) or polyethyleneimine according to the present invention as liquid and solid CO2 absorbents in CO2 capture processes.

[0149] Suitable carbon capture methods are mentioned above and are known in the art.

[0150] In step (c), carbon dioxide and hydrogen are reacted to form methanol.

[0151] The process conditions for hydrogenating carbon dioxide are known per se. Different process approaches are being developed for the synthesis of methanol by hydrogenating CO2: (1) heterogeneous catalysis, (2) homogeneous catalysis, (3) electrochemistry, and (4) photocatalysis (see R. Guil-López, Materials 2019, 12, 3902; doi: 10.3390 / ma12233902). Preferably, the synthesis of methanol by hydrogenating carbon dioxide is carried out in the presence of a heterogeneous catalyst.

[0152] Typically, methanol production is carried out in a synthetic converter, such as a fixed bed catalytic reactor.

[0153] The average temperature in the reactor is generally in the range from 150° C. to 300° C. The average pressure in the reactor is generally in the range from 50 to 150 bar (absolute).

[0154] An overview of suitable heterogeneous catalyst systems is given by Kristian Stangeland, Hailong Li and Zhixin Yu, Energy, Ecology and Environment, Vol. 5, pp. 272-285 (2020). This process requires a multicomponent catalyst system. The interaction between the components is essential for the high activity and selectivity of the catalyst for CO2 to methanol. This has been demonstrated by many catalyst systems consisting of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., Al2O3, ZnO, ZrO2, In2O3). These complex systems can contain mixtures of metal phases, alloy phases, and metal oxide phases. The most promising catalyst systems for large-scale industrial processes are currently Cu-based catalysts and In-based catalysts due to their excellent catalytic properties. Suitable catalysts are, for example, copper-zinc-alumina.

[0155] By carrying out step (c), methanol (CH3) is formed by reacting a carbon oxide, preferably carbon dioxide, with the hydrogen from step (a). The deuterium content is even lower than that corresponding to the distribution obtained by classical petrochemical routes.

[0156] Step (d)

[0157] In step (d) the methanol from step (c) is converted into ethylene and further into ethylene oxide.

[0158] Preferably, the ethylene oxide in step (d) is obtained by:

[0159] (d1) Methanol to olefins process, in which ethylene is obtained, followed by

[0160] (d2) Epoxidation of ethylene.

[0161] Step (d1)

[0162] Typically, ethylene is produced from methanol in the methanol to olefins process (MTO process).

[0163] The MTO process is an acid catalyzed reaction. Preferred catalysts are zeolites, such as zeolites containing silica and alumina (eg ZSM-5) and silicon alumina phosphate zeolite catalysts (SAPO) (eg SAPO-34).

[0164] The reaction is usually carried out at a temperature of 300° C. to 600° C. The pressure is usually 0.1 to 0.3 MPa.

[0165] The process is preferably carried out in a fluidized catalytic reactor.

[0166] The ratio of propylene to ethylene can be adjusted by selecting appropriate process conditions and can vary from 0.77 in ethylene production mode and 1.33 in propylene production mode.

[0167] Examples of commercial MTO technology licensors are UOP Corporation (eg, UOP Advanced MTO process), Energy Technology Co. Ltd. (DMTO process), and China Petrochemical Corporation (Sinopec) (SMTO process).

[0168] A more detailed description can be found, for example, in "Ethylene", by Adam Chan of Nexant, TECH 2018-1, July 2018, pp. 100-109.

[0169] Step (d2)

[0170] In step (d2) ethylene from step (d1) is converted into ethylene oxide.

[0171] The direct oxidation process is preferably carried out in the gas phase (eg with oxygen or air) in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0172] Step (d2) is generally carried out at a temperature of 230 to 270° C. The pressure is preferably in the range of 10 to 30 bar.

[0173] In a preferred embodiment, step (d2) is carried out by gas phase selective ethylene oxidation (ethylene epoxidation), which is typically carried out in a fixed bed tubular reactor with a supported Ag / Al2O3 catalyst at 230°C-270°C and 10-30 bar.

[0174] Preferred catalysts for the process in step (d2) are silver-based catalysts, such as

[0175] - a supported Re / Cs / Ag / Al2O3 catalyst preferably operated with excess C2H4 / O2; or

[0176] - Alkali metal (Na, Cs) promoted supported Ag / Al2O3 catalyst preferably operated with excess O2 / C2H4.

[0177] It has been found that oxides of Mo and S also promote the supported Re / Cs / Ag / Al2O3 system for EO formation. Therefore, the supported Re / Cs / Ag / Al2O3 system may additionally contain oxides of Mo and / or S as promoters.

[0178] Additionally, C2H4Cl2 can also be added to deposit Cl on the catalyst, which acts as a promoter.

[0179] Described examples can be found, for example, in "Ethylene Oxide", by Mia Monconduit and Karen Jobes of IHS Markit, Chemical Economics Handbook, December 22, 2020, pp. 14-16.

[0180] Step (e)

[0181] In step (e), the ammonia from step (b) is converted in one or more steps with the ethylene oxide from step (d) into an ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof.

[0182] The reaction product obtained in step (e) generally comprises monoethanolamine, diethanolamine and triethanolamine.

[0183] The preparation in step (e) is preferably carried out in the presence of water, usually in a closed loop process requiring only a small amount of fresh water feed. However, ethanolamine can also be prepared by the reaction of ammonia and ethylene oxide in an anhydrous process. An anhydrous process preferably employs a fixed bed catalyst, such as an organic ion exchange resin or a thermally more stable acidic inorganic clay or zeolite.

[0184] In the preferred process, the reaction occurs in the aqueous phase and the reactor pressure is generally sufficient to prevent vaporization of the ammonia and ethylene oxide at the reaction temperature.

[0185] The ammonia concentration in the water is preferably between 50% and 100%.

[0186] The reaction pressure in the aqueous phase reaction is generally up to 160 bar, preferably from 90 to 130 bar (absolute).

[0187] The reaction temperature in the aqueous phase reaction is generally up to 150°C, preferably 40°C to 130°C.

[0188] Typically, an excess of up to 40 mol of ammonia is used per mol of ethylene oxide in the aqueous phase reaction.

[0189] Unconsumed ammonia and water are generally separated from the product in a distillation line downstream of the reactor and recycled.

[0190] The product distribution of the three ethanolamines can be controlled by appropriate selection of the ammonia:ethylene oxide ratio.

[0191] Although the above reaction can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, in order to obtain monoethanolamine, post-treatment by distillation is usually required to remove diethanolamine and triethanolamine.

[0192] In the preparation of polyethyleneimines described in the following steps (f), (g) and (h), monoethanolamine is required, which is usually separated from the ethanolamines which are usually obtained in steps (a) to (e) of the process according to the invention by distillation as a mixture of monoethanolamine, diethanolamine and triethanolamine (see following step (f)).

[0193] However, in case the ethanolamine according to the invention is used for an application different from the preparation of polyethyleneimine, separation of monoethanolamine may not be necessary. In carbon capture, for example, a mixture of monoethanolamine and diethanolamine may be employed and only the triethanolamine must be separated (usually by distillation).

[0194] Ethanolamines are a family of chemicals that act as surfactants and emulsifying ingredients in personal care products, cleaning products and industrial applications.

[0195] Further applications of the ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the invention are for example:

[0196] Personal Care Products

[0197] Ethanolamines like MEA and especially TEA act as cleaning agents or surfactants in personal care products and cosmetics. In these types of products, ethanolamines help remove dirt and oil from the skin by dissolving grease and blending other important ingredients. Since ethanolamines do not impart a strong odor, they are often ingredients in products like hair dyes. Ethanolamines (like MEA) help adjust the pH of the product to keep it from degrading when stored in a container, so it will last longer.

[0198] Home Care and Industrial Cleaning Products

[0199] Ethanolamines such as MEA are common ingredients in cleaning products (like floor and tile cleaners) and laundry detergents. As surfactants in these products, ethanolamines help remove dirt, grease, and stains.

[0200] DEA is a common ingredient in industrial cleaning products such as engine degreasers and industrial strength detergents due to its ability to break down oil and grease.

[0201] Industrial Applications

[0202] MEA acts as a plasticizer to help make plastics pliable and soft. Chemical manufacturing plants use MEA to remove carbon dioxide from ammonia gas in the production of synthetic ammonia.

[0203] As a chemical intermediate, DEA is used in agricultural chemicals to make pesticides, where it helps improve the ability of the pesticide to dissolve in water. In the production of waxes, polishes, and coating products, DEA acts as an emulsifier to help ingredients mix and helps prevent other materials from corroding.

[0204] Due to their emulsifying properties, MEA and DEA can also be used in industrial applications such as chemical manufacturing and gas processing. In gas processing processes for refineries and natural gas streams, MEA and DEA help remove contaminants from gasoline.

[0205] TEA is used as a surfactant in agrochemicals to help disperse pesticides into crops, which then helps repel insects from the crops. As an oil demulsifier, TEA helps separate oil from water and other substances. In cement additives, TEA helps promote the curing and / or hardening of cement. It is also a corrosion inhibitor in steel and zinc materials used in building and construction.

[0206] Therefore, the present invention further relates to the use of the ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof in any of the above-mentioned applications.

[0207] The carbon capture agent, surfactant, emulsifier, detergent, pH adjuster, plasticizer, gas desulfurization agent, anticorrosion additive and cement additive contain at least one ethanolamine selected from monoethanolamine, diethanolamine and triethanolamine according to the present invention.

[0208] Described examples can be found, for example, in "Ethanolamines", by Mia Monconduit and Tison Keel, IHS Markit, Chemical Economics Handbook, February 14, 2020, pp. 19-20.

[0209] The present invention further relates to ethanolamines selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, in which the molar fraction of deuterium is ≤100 ppm, preferably in the range of 10 to ≤98 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤90 ppm, based on the total hydrogen content.

[0210] The ethanolamines according to the invention, which are selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, are characterized by a low molar fraction of deuterium.

[0211] The ethanolamine (which is selected from monoethanolamine, diethanolamine, triethanolamine and a mixture thereof) is preferably prepared by a process comprising at least step (a) according to the present invention. More preferably, the ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and a mixture thereof is prepared by the present invention comprising steps (a) to (e).

[0212] The present invention further relates to a process for preparing polyethyleneimine, wherein the process comprises:

[0213] (f) separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the process according to the invention or from the ethanolamine according to the invention;

[0214] (g) converting monoethanolamine into ethyleneimine,

[0215] (h) polymerizing the ethyleneimine from step (g) to form polyethyleneimine.

[0216] Step (f):

[0217] Step (f) comprises separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the process according to the invention, or from the ethanolamine according to the invention.

[0218] Although reaction step (e) can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, separation is usually required to remove diethanolamine and triethanolamine in order to obtain monoethanolamine. The post-treatment is generally known in the art and is usually carried out by distillation.

[0219] Examples of methods for producing monoethanolamine described can be found, for example, in “Ethanolamines and Propanolamines” by Martin Ernst, Johann-Peter Melder, Franz Ingo Berger and Christian Koch, Ullmann's Encyclopedia of Industrial Chemistry, 2022, pp. 4-6.

[0220] Step (g):

[0221] In step (g), monoethanolamine is converted to ethyleneimine (aziridine).

[0222] Suitable methods for preparing ethyleneimine from monoethanolamine are generally known in the art.

[0223] The preferred commercial process is catalytic gas phase dehydration, see for example US 4,841,061 for suitable examples of catalyst compositions and see for example US 4,966,980 for the corresponding ethyleneimine gas phase process conditions.

[0224] In this process, ethyleneimine is prepared by dehydrating monoethanolamine at temperatures generally in the range from 350° C. to 450° C., generally under reduced pressure in the range from 30 to 500 mbar (abs.).

[0225] The process is usually carried out in the presence of a catalyst having weakly basic and acidic sites, for example based on Si-Cs-P or Si-Rb-P. An overview of this production technology and the best catalyst compositions with high yields (up to 80 mol%), selectivity and activity is found in: Applied Catalysis A: General 221 (2001) 209-217; Acid-base catalysis: On the example of ethylenimine production; Hideaki Tsuneki; Nippon Shokubai Co. Ltd., Functions and Materials Research Laboratory, Suita 564-8512, Japan. The process is prone to catalyst deactivation by coking and sintering and loss of active components due to high processing temperatures despite short contact times. To improve catalyst life, a catalyst regeneration cycle with, for example, trimethyl phosphate treatment can be employed as described in: Applied Catalysis A: General 331 (2007) 95-99; Deactivation and regeneration of ethylenimine production catalyst; Hideaki Tsuneki, Kimio Ariyoshi; Nippon Catalyst Co., Ltd., Functions and Materials Research Laboratory, Suita Electric Co., Ltd. 564-8512, Japan.

[0226] Catalytic gas phase dehydration processes are usually carried out in the gas phase in a flow tube reactor.

[0227] The product mixture obtained is usually separated by quenching followed by multi-stage distillation to give high-purity ethyleneimine, and the unreacted monoethanolamine is fed back to the reactor.

[0228] Another preferred commercial process is liquid phase dehydration via the Wenker process 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 with sulfuric acid to produce 2-aminoethyl hydrogen sulfate as an intermediate. Dehydration is achieved by the subsequent addition of sodium hydroxide, usually under pressure and at elevated temperature, 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).

[0229] The liquid phase ethyleneimine process can be generally carried out in batch or continuous mode, typically in very high yields of 85-90 mol %, giving after distillation high purity ethyleneimine having excellent properties desired for example for high molecular weight polyethyleneimine and other derivatives.

[0230] Step (h)

[0231] In step (h), the ethyleneimine from step (g) is polymerized to polyethyleneimine.

[0232] Suitable processes for preparing polyethyleneimines by polymerizing ethyleneimine (aziridine) are known to those skilled in the art.

[0233] Polyethyleneimines are preferably prepared by cationic ring-opening polymerization of ethyleneimine in the presence of Broensted acid, Lewis acid, halogenated alkane or carbon dioxide. Examples are given in US 2,182,306 and US 3,203,910 and US 2001 / 0039318.

[0234] As another reference for additional examples of polyethylene synthesis, it is referred to “Aziridines andazetidines: 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.

[0235] The polymerization can be carried out, for example, in a batch process 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° C. to 100° C., and ethyleneimine is continuously added while stirring the reaction mixture.

[0236] The polyethyleneimine obtained is usually a branched or hyperbranched polyethyleneimine.

[0237] The polyethyleneimine obtained preferably has a weight average molecular weight M in the range of 500 to 2,000,000 g / mol, preferably in the range of 500 to 100,000 g / mol. w .

[0238] The degree of branching of the polyethyleneimine is preferably in the range of 0.45 to 0.75, more preferably 0.5 to 0.7, most preferably 0.55 to 0.7. 13 C NMR spectroscopy was determined in D2O. The degree of branching was calculated as (D+T) / (D+T+L). In this formula, D refers to dendritic (or tertiary) amine groups, L (linear) refers to secondary amine groups, and L (linear) refers to primary amine groups.

[0239] The polyethyleneimines of the invention are characterized by a low molar fraction of deuterium, which is in the range of ≤110 ppm, preferably in the range of 10 to ≤105 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤92 ppm, based on the total hydrogen content.

[0240] The present invention further relates to polyethyleneimines in which the molar fraction of deuterium is ≤110 ppm, preferably in the range of 10 to ≤105 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤92 ppm, based on the total hydrogen content.

[0241] The polyethyleneimine is preferably prepared by a process comprising at least step (a) according to the present invention. More preferably, the polyethyleneimine is prepared by a process comprising steps (a) to (h) according to the present invention.

[0242] The polyethyleneimines according to the invention are characterized by a low molar fraction of deuterium. They have a deuterium fraction that differs from petrochemically produced polymers and ethanolamines produced by petrochemical methods (ie based on fossil energy).

[0243] The key feature of the ethanolamines and polyethyleneimines of the present invention selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof is the low deuterium molar fraction. The low deuterium molar fraction is mainly introduced by step (a) of the process according to the present invention. Therefore, the ammonia prepared by reacting the hydrogen from step (a) with nitrogen is also characterized by a low deuterium molar fraction.

[0244] Therefore, the present invention further relates to a process for preparing ammonia, wherein the process comprises the following steps:

[0245] (a) providing hydrogen with a molar fraction of deuterium (deuterium content) of less than 90 ppm based on the total hydrogen content by electrolysis based on electricity generated at least partly from non-fossil energy, preferably renewable resources,

[0246] (b) reacting the hydrogen from step (a) with nitrogen to form ammonia.

[0247] Steps (a) and (b) are the same steps as described above.

[0248] The invention further relates to ammonia in which the molar fraction of deuterium is ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content.

[0249] By means of the present invention, environmentally friendly ethanolamines (which are selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine and ammonia are provided, as well as an environmentally friendly process for preparing them, wherein the process uses as little fossil energy as possible.

[0250] It has been found that the environmentally friendly compounds prepared, namely ethanolamines selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimines and ammonia, are characterized by a particularly low molar fraction of deuterium.

[0251] As mentioned above, it is important that the origin of hydrogen and downstream compounds obtained through clean energy sources can be tracked in a reliable manner.

[0252] Today, most hydrogen is produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

[0253] However, so far, it is not possible to distinguish hydrogen obtained by steam reforming, partial oxidation and coal gasification (i.e., from fossil resources) from hydrogen obtained by electrolysis. As discussed above, hydrogen obtained by electrolysis is preferably obtained by using non-fossil energy sources. It is expected that electrification (electricity generation) of fossil sources will be completely replaced by electricity generation from non-fossil resources in the near future.

[0254] Thus, the inventors have found a way to trace the origin of hydrogen and downstream products of hydrogen, preferably ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimines, ammonia and hydrogen (via the deuterium molar fraction of said compounds). Downstream products based on hydrogen, preferably ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof) based on hydrogen obtained by electrolysis, polyethyleneimines, ammonia and hydrogen itself can be distinguished from ethanolamines (selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimines, ammonia and hydrogen prepared by fossil energy-based processes (i.e. made by petrochemical processes) by their deuterium molar fraction.

[0255] Furthermore, by using carbon oxides such as carbon monoxide and preferably carbon dioxide together with hydrogen instead of petrochemical synthesis gas in the subsequent synthesis pathways of ethanolamines (which are selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine and ammonia, it was found that the molar fraction of deuterium in these compounds is uniquely low with excellent traceability.

[0256] The present invention therefore relates to the use of the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen for tracking the source of hydrogen and downstream compounds based on hydrogen, in particular the source of energy, wherein these compounds are preferably ethanolamines (which are selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine or ammonia.

[0257] The invention further relates to a method for tracing the origin of hydrogen and downstream hydrogen-based compounds, in particular the energy source, by determining the molar fraction of deuterium in the hydrogen and downstream hydrogen-based compounds, wherein these compounds are preferably ethanolamines (which are selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine or ammonia.

[0258] The downstream products based on hydrogen are generally products prepared by using hydrogen, preferably ethanolamine (which is selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof), polyethyleneimine, ammonia and methanol. The preparation of downstream products and other downstream products based on hydrogen is known in the art.

[0259] Within the meaning of the present invention, tracking is synonymous with tracing.

[0260] In the sense of the present invention, the source is the method for producing hydrogen, in particular electrolysis and / or the energy source, i.e. non-fossil energy, employed. As mentioned above, it is expected that electrification (electricity generation) of fossil sources will be completely replaced by electricity generation from non-fossil resources in the near future. The hydrogen produced by electrolysis is in this case hydrogen of non-fossil origin. Examples of non-fossil energy sources are mentioned above.

[0261] The method of the present invention for tracing the source of hydrogen and the above-mentioned downstream compounds, in particular the source of energy, can be used as a single tracing (tracking) method or in combination with another tracing (tracking) method.

[0262] Suitable molar deuterium fractions of hydrogen-based compounds obtained by electrolysis, in particular by the process according to the invention, in particular ethanolamines selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia and hydrogen itself are mentioned in the present application.

[0263] Due to their polyamine structure, polyethyleneimine (PEI) polymers are able to protonate, chelate, and react, making them very attractive in a variety of applications.

[0264] As mentioned above, PEI can be used to reduce greenhouse gas emissions in CO 2 capture, for example in the form of gas separation membranes for CO 2 capture and for H 2 purification from gas mixtures such as CO 2 / N 2 and H 2 / N 2 .

[0265] Further examples of typical applications of PEI are:

[0266] -Wet strength additives in the paper industry to improve the strength of paper products.

[0267] -Use in detergents and cosmetics

[0268] -Adhesion promoter for printing inks and adhesives

[0269] -Primer in coating applications to improve adhesion to various substrates such as glass, wood, plastic and metal

[0270] - Flocculants to precipitate colloidal particles from water

[0271] -Removal of heavy metal ions (such as Cu 2+ , Pb 2+ Cr 6+ 、Cd 2+ )

[0272] -Green foaming agent for polyurethane

[0273] - Chelating agents with the ability to complex metal ions such as zinc and zirconium

[0274] - Antimicrobial coating: PEI can be applied to surfaces as an antimicrobial coating. It has been shown to be active against a wide range of microorganisms including bacteria, viruses and fungi

[0275] -Textile industry: PEI can be used as a cross-linking agent in the textile industry to improve the durability and strength of fabrics

[0276] - Food packaging: PEI can be used as a coating for food packaging materials to improve their barrier properties and extend the shelf life of food.

[0277] Other applications of PEI are in the biological and medical fields:

[0278] -Gene transfection agents for biomedical applications

[0279] - Mucosal adjuvants for various vaccines

[0280] -Design of immobilized enzyme biocatalysts

[0281] - Use in laboratory biology, especially tissue culture

[0282] - Attachment promoter for weakly anchored cells in cell culture

[0283] -Gene delivery: PEI can be used as a gene delivery agent in gene therapy. It has been shown to effectively deliver plasmid DNA into cells and can be used for both in vitro and in vivo applications

[0284] -Protein purification: PEI can also be used as a protein purification agent. It can selectively bind to proteins and is particularly useful for purifying negatively charged proteins.

[0285] - Biomedical implants: PEI can be used as a coating for biomedical implants to improve their biocompatibility and reduce the risk of rejection by the body.

[0286] Therefore, the present invention further relates to the use of the polyethyleneimine according to the invention in any of the applications mentioned above.

[0287] The present invention further relates to CO2 capture agents, gas separation membranes, in particular for CO2 capture and for H2 purification from gas mixtures such as CO2 / N2 and H2 / N2, wet strength additives in the paper industry, detergents, cosmetics, adhesion promoters, in particular for printing inks and adhesives, primers in coating applications, flocculants for precipitating colloidal particles from water, chelating agents, in particular for heavy metal ions in sewage, green foaming agents for polyurethanes, antimicrobial coatings, crosslinking agents in the textile industry, coatings for food packaging materials, gene transfection agents for biomedical applications, mucosal adjuvants for various vaccines, immobilized enzyme biocatalysts, attachment promoters for weakly anchored cells in cell culture, gene delivery agents in gene therapy, purifying agents for proteins, coatings for biomedical implants, which contain or consist of at least one polyethyleneimine according to the present invention.

[0288] The present invention is further illustrated by working examples.

[0289] Examples

[0290]

[0291] I Hydrogen Production

[0292] Experimental setup and methods: electrolyzer design and hydrogen production conditions

[0293] 1) Polymer electrolyte membrane / proton exchange membrane electrolysis (PEM)

[0294] Electrolytic Cell

[0295] Water electrolysis was performed using a circular commercial PEM electrolyzer (model ZE 200, Sylatech Analysetechnik GmbH, 0.007 m2 active area). The cell stack was sealed with an O-ring and wrapped with thermal insulation fabric to achieve isothermal operating conditions. The cell stack was assembled by HIAT GmbH with the catalytically active coating materials iridium (19 g / m2) and platinum (8 g / m2). 117 standard membrane (supplier DuPont, dry thickness 180 μm). Water distribution at the anode half-cell was achieved with a titanium mesh. A porous transport layer with sintered titanium fiber material was used before the polymer electrolyte membrane for controlled flow, while a porous graphite plate was located on the cathode side.

[0296] Experimental conditions

[0297] Water with controlled temperature is supplied to the anode compartment at a constant flow rate of 9.5 g / h. The cell pressure on the cathode side and the anode side is controlled with a PC valve. See the table for experimental conditions such as temperature and pressure settings. The hydrogen and oxygen released in the half-cell are separated in a two-stage separator setup with an intermediate condenser cooled with 20°C cooling water. The condensed water flows back to the separation tank. The anode tank-water is recycled, and on the cathode, the separated water is discharged. The remaining gas moisture is separated by a desiccant dryer, thereby ensuring complete separation of moisture in the electrolysis gas flow. Small gas samples of dehydrated cathode hydrogen are periodically taken out from the continuous flow with an autosampler for the following hydrogen analysis.

[0298] 2) Alkaline electrolytic cell (AEC)

[0299] Electrolytic Cell

[0300] Alkaline water electrolysis was carried out with a circular AEC electrolyser (type Electro MP Cell, supplier ElectroCell Europe A / S, 0.01 m2 electrode area). Nickel 2.4068 material was used as electrodes and separated by a commercial standard Zirfon Perl UTP 500 membrane (open-pore polyphenylene sulfide fabric symmetrically coated with a polymer / zirconium oxide mixture; thickness 500 micrometers; 0.023 m2 active area; supplier Agfa-Gevaert NV) in a zero-gap cell configuration.

[0301] Experimental conditions

[0302] Alkaline water (32wt% potassium hydroxide, industrial standard grade) with controlled temperature is supplied to the anode and cathode compartments at a constant flow rate of 27.8kg / h. The cell pressure on the cathode side and the anode side is balanced by PC valve control. See the table for experimental conditions such as temperature and pressure settings. The hydrogen and oxygen released in the half-cell are separated in a two-stage separator setting with an intermediate condenser cooled with 20°C cooling water. The condensed water flows back to the separation tank. The anode and cathode pool-water are recycled. The remaining gas moisture is separated by a desiccant dryer to ensure complete separation of moisture in the electrolysis gas flow. Small gas samples of dehydrated cathode hydrogen are periodically taken out from the continuous flow with an automatic sampler for the following hydrogen analysis.

[0303] 3) Anion exchange membrane / alkaline electrolyte membrane electrolysis (AEM)

[0304] Electrolytic Cell

[0305] AEM experiments were performed in a commercial, fully automated 2.4 kW EL 4.0 cell supplied by Enapter GmbH, 10117 Berlin, with a 1 wt % potassium hydroxide (standard grade) electrolyte solution.

[0306] Testing Station

[0307] The EL 4.0 electrolyser was operated with 1 wt% potassium hydroxide (industrial standard grade) solution as recommended by the supplier, and the hydrogen production rate under operating conditions (see table for experimental conditions such as temperature and pressure settings) was 480 l / h at about 400 ml water consumption. The evolved hydrogen was treated with a desiccant dryer to ensure complete separation of the water in the electrolyzed gas stream, resulting in <0.03 wt% water in the hydrogen stream. Small gas samples of the dehydrated cathode hydrogen were taken regularly from the continuous stream with an autosampler for the following hydrogen analysis.

[0308] 4) Solid Oxide Electrolysis Cell (SOE)

[0309] A solid oxide cell stack from Elcogen-Elco Stack (Elcogen OY, Vantaa 01510, Finland) was used and the E3000 unit was operated in reverse mode at 700 °C and 35 A electrolysis current; the anode functional composition was NiO / YSZ due to the supplier. The cathode was of LSC type [La(Sr)CoO3]: this principle is also described in Novel high performance solid oxide fuel cells with bulk ionic conductivity dominated thin film electrolytes - ScienceDirect; D. et al., Journal of Power Sources, Vol. 218, 15 November 2012, pp. 157-162.

[0310] The hydrogen stream was used without further purification / dryer. The remaining gas moisture was separated by a desiccant dryer, thus ensuring complete separation of the moisture in the electrolysis gas stream. Small gas samples of the dehydrated cathode hydrogen were periodically taken from the continuous stream with an autosampler for the hydrogen analysis described below.

[0311] The results of hydrogen production are shown in Table 1.

[0312] Experimental setup and methods: "D content (deuterium content) in samples"

[0313] The following method description is suitable for determining the deuterium molar fraction (deuterium content) of gaseous and liquid samples based on the total hydrogen content. The isotopic H / D fraction analysis is based on mass spectrometry. Two different methods are used: Method A for gaseous samples and Method B for liquid samples.

[0314] In order to determine the "D content in gas and liquid samples", it is crucial not to contaminate the samples, for example by ambient moisture or other ambient components containing hydrogen or deuterium. Therefore, gas-tight materials and seals have to be used with clean sample containers to avoid any cross-contamination. Therefore, before filling and sealing the sample container, the sample container has to be flushed with a gas or liquid flow to be analyzed for at least 20 times the volume of the sample container. This is also valid for the experimental setup of the gas sampler and the mass spectrometer. Special care must be taken to avoid cross-contamination, for example by condensation of moisture. The analysis setup from sampling to mass spectrometry is verified with known reference samples.

[0315] Method A) Gas Sample

[0316] Total deuterium of HD and D2 in hydrogen samples was determined via ultra-high resolution quadrupole mass spectrometry using a Hiden DLS-20 (Hiden Analytical Ltd., Warrington, Cheshire, UK) analyzer setup. The general method setup is described in CCKlepper, T.M. Biewer, U. Kruezi, S. Vartanian, D. Douai, D.L. Hillis, C. Marcus, Extending helium partial pressure measurement technology to JET DTE2 and ITER; Rev. Sci. Instrum., 87(11)(2016); doi:10.1063 / 1.4963713. For hydrogen samples, threshold ionization mass spectrometry mode (TIMS) was used as described in: S. Davies, JA Rees, DL Seymour; Threshold ionisation mass spectrometry (TIMS); A complementary quantitative technique to conventional mass resolved mass spectrometry; Vacuum, 101 (2014), pp. 416-422; doi: 10.1016 / j.vacuum.2013.06.004. The sensitivity was + / - 1 ppm.

[0317] Method B) Liquid samples

[0318] The analysis of liquid samples (ammonia, monoethanolamine (MEA) and polyethyleneimine (PEI)) was performed via isotope ratio monitoring gas chromatography / mass spectrometry (IRMS). Therefore, a DELTA V PLUS CF-IRMS mass spectrometer was used. This mass spectrometer with a magnetic sector with continuous throughput DELTA V PLUS CF-IRMS was used to measure the isotope ratio of 2H / 1H.

[0319] Measuring D / H in continuous He flow mode requires complete removal of low energy 4He+ from the HD+ ion beam at m / z 3). The method is described in: RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 13, 1226-1230 (1999), WA Brandt et al. Sensitivity is within + / - 3 ppm.

[0320] II Production of ammonia, ethylene oxide (EO), ethanolamine and polyethyleneimine (PEI)

[0321] Ammonia, ethylene oxide and ethanolamine as the pure components monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA) or mixtures of MEA, DEA and / or TEA are prepared by means of a catalytic synthesis process on an industrial scale as described above.

[0322] By using electrolytic hydrogen based on non-fossil energy in both ammonia and methanol synthesis, the core of this value chain, the only material hydrogen in the downstream produced EO, MEA, DEA and TEA actually originates from electrolytic hydrogen with a low deuterium content. This is a big difference especially for ammonia, since fossil-based production methods rely on synthesis gas made from fossil natural gas and additional large amounts of steam. This steam reforming step is not required for the non-fossil ammonia route based on pure hydrogen and nitrogen.

[0323] In all discussed large-scale commercial production methods using non-fossil hydrogen, no significant additional amount of hydrogen species is introduced in the "input / output" process material balance. This is required in order to minimize the output of undesirable wastewater or other liquid and gaseous discharge streams and to ensure high yields and purity according to product specifications.

[0324] If ambient air is used for the direct oxidation of ethylene in EO production, ambient moisture does not participate in the catalytic reaction and is therefore purged along with nitrogen and other inert gases. The EO product itself therefore consists virtually only of hydrogen, a material derived from ethylene. Ethylene made from methanol from hydrogen and carbon oxides by MTO or similar processes has nearly the same deuterium concentration as the hydrogen source.

[0325] In case water is used as a processing aid for stripping / washing / cleaning or quenching / condensing process internal streams in, for example, ammonia, methanol, ethylene oxide and / or ethanolamine synthesis steps, this water is always operated with minimal purge in an almost completely closed loop, thus ensuring that cross contamination with deuterium is negligible.

[0326] If hydrogen species are introduced in a continuous industrial process, these feed streams are always small compared to the output stream of the desired product, meaning at least 2 orders of magnitude smaller or in other words <1% of the output stream. Therefore, for the ethylene (MTO based ethylene), ammonia and ethanolamine process steps, the increase in deuterium content was calculated using a worst case factor of 1.01 for each.

[0327] For ethyleneimine (EI) synthesis, as described, two different approaches are of commercial interest. The liquid phase dehydration "Wenker process" is carried out in aqueous dilution with fresh water and molar amounts of sulfuric acid and caustic. Therefore, the "acidic N-hydrogens" of ethyleneimine are virtually completely exchanged with the deuterium content of the aqueous feed mixture. This means that 1 / 5 of the molar fraction of deuterium can be assumed to have a VSMOV baseline concentration (155.76 ppm), but the remaining 4 / 5 hydrogen species maintain the low deuterium content of the ethanolamine source due to the strong nature of the C-H bond. Therefore, the formula D-content (EI) = 1 / 5*D-content (VSMOV) + ​​4 / 5*D-content (MEA) is used.

[0328] The catalytic gas phase dehydration process does not introduce any significant amount of hydrogen species in addition to the MEA feedstock and produces >98% concentrated ethyleneimine monomer in the final sequence of distillation work-up steps.

[0329] As with upstream catalytic processes, any loss of hydrogen species from, for example, partially acidic catalysts is irrelevant in the material mass balance with industrially relevant high space-time yields.

[0330] However, ethyleneimine itself is not a relevant commercial end product due to its harmful toxicity and extreme reactivity. Polyethyleneimine (PEI) products are prepared by cationic ring-opening polymerization of ethyleneimine (EI) in aqueous solution with an initiator as described above and fresh water in order to achieve removal of the strong exotherm generated by the polymerization. Polymerization without significant water dilution cannot be safely controlled on a large scale. Therefore, common PEI products in industry are usually polymerized in batch or semi-batch mode, where the temperature is controlled at, for example, 30% or 50% aqueous final concentration. This means that the "acidic N-hydrogens" from ethyleneimine are actually completely exchanged with the deuterium content of the fresh water used in the polymerization step. Since this HD exchange on the "acidic N-hydrogens" can only occur once, the results of the deuterium content are actually the same: two polyethyleneimines based on the liquid phase or gas phase dehydration EI monomer method have the same deuterium content, which is approximately the formula D-content (PEI) = 1 / 5*D-content (VSMOV) + ​​4 / 5*D-content (MEA).

[0331] In Table 2, the deuterium (D) content in hydrogen, ammonia, monoethanolamine (MEA) and polyethyleneimine (PEI) based on fossil resources (FR) (comparative example) and non-fossil resources (NFR) (examples of the invention) is shown. The products from FR (comparative example) are conventional petrochemical products from BASF SE. The deuterium content from the products from NFR is calculated as described above using the D content of hydrogen from Examples I) to VI) as starting materials for both ammonia and ethylene synthesis pathways (see Table 1).

[0332]

Claims

1. Ethanolamines selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, wherein the molar fraction of deuterium is ≤100 ppm, preferably in the range of 10 to ≤98 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤90 ppm, based on the total hydrogen content.

2. A process for preparing the ethanolamine according to claim 1, wherein the ethanolamines are selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, wherein the process comprises the following steps: (a) providing hydrogen with a molar fraction of deuterium based on a total hydrogen content of ≤ 100 ppm by electrolysis based on electricity generated at least partly from non-fossil energy sources, (b) reacting the hydrogen from step (a) with nitrogen to form ammonia, (c) reacting the hydrogen from step (a) with a carbon oxide, preferably carbon dioxide, to form methanol, (d) converting the methanol from step (c) into ethylene and further into ethylene oxide, (e) converting the ammonia from step (b) into ethanolamine in one or more steps using the ethylene oxide from step (d).

3. The method according to claim 2, wherein: The electricity is generated at least in part by wind, solar (thermal, photovoltaic and concentrated solar power), hydropower (tidal power, wave power, hydroelectric dams, in-river hydrodynamics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuels, biomass), renewable portions of waste, or nuclear energy (fission).

4. The method according to claim 2 or 3, wherein: Step (a) is water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

5. The method according to any one of claims 2 to 4, wherein: In step (c) carbon dioxide is employed which is preferably captured from industrial flue gases or ambient air.

6. The method according to any one of claims 2 to 5, wherein: The ethylene oxide in step (d) is obtained by: (d1) Methanol to olefins process, preferably in the case of zeolite catalysts, wherein ethylene is obtained, followed by (d2) Epoxidation of ethylene, preferably in the presence of a silver-based catalyst.

7. The method according to any one of claims 2 to 6, wherein: Ammonia from step (b), ethylene oxide from step (d) and react in one or more steps to form a reaction product comprising monoethanolamine, diethanolamine and triethanolamine.

8. Polyethyleneimines having a molar fraction of deuterium of ≤110 ppm, preferably in the range of 10 to ≤105 ppm, more preferably in the range of 10 to ≤95 ppm, most preferably in the range of 10 to ≤92 ppm, based on the total hydrogen content.

9. A method for preparing the polyethyleneimine according to claim 8, wherein the method comprises: (f) separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the process according to any one of claims 2 to 7 or the ethanolamine according to claim 1; (g) converting monoethanolamine into ethyleneimine, (h) polymerizing the ethyleneimine from step (g) to form polyethyleneimine.

10. The method according to claim 9, wherein: Step (g) is carried out in the gas phase or the liquid phase.

11. Ammonia, wherein the molar fraction of deuterium is ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, most preferably in the range of 10 to ≤80 ppm, based on the total hydrogen content.

12. A process for producing ammonia according to steps (a) and (b) as claimed in any one of claims 2 to 4.

13. Use of the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen for tracing the source of the production of hydrogen and downstream compounds based on hydrogen, wherein these compounds are preferably ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia.

14. A method for tracing the origin of the production of hydrogen and downstream compounds based on hydrogen by determining the molar fraction of deuterium in hydrogen and downstream compounds based on hydrogen, wherein these compounds are preferably ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia.

15. Use of the polyethyleneimine according to claim 8 as or in a CO2 capture agent, a gas separation membrane, a wet strength additive in the paper industry, a detergent, a cosmetic, an adhesion promoter for printing inks and adhesives, a primer in coating applications, a flocculant for precipitating colloidal particles from water, a chelating agent for heavy metal ions in sewage, a green foaming agent for polyurethane, an antimicrobial coating, a cross-linking agent in the textile industry, a coating for food packaging materials, a gene transfection agent for biomedical applications, a mucosal adjuvant for various vaccines, an immobilized enzyme biocatalyst, an attachment promoter for weakly anchored cells in cell culture, a gene delivery agent in gene therapy, a purification agent for proteins, or a coating for biomedical implants.

16. CO2 capture agents, gas separation membranes, wet strength additives in the paper industry, detergents, cosmetics, adhesion promoters for printing inks and adhesives, primers in coating applications, flocculants for precipitating colloidal particles from water, chelating agents for heavy metal ions in sewage, green foaming agents for polyurethanes, antimicrobial coatings, crosslinking agents in the textile industry, coatings for food packaging materials, gene transfection agents for biomedical applications, mucosal adjuvants for various vaccines, immobilized enzyme biocatalysts, attachment promoters for weakly anchored cells in cell culture, gene delivery agents in gene therapy, purification agents for proteins, or coatings for biomedical implants, comprising or consisting of at least one polyethyleneimine according to claim 8.

17. Use of ethanolamine, preferably monoethanolamine and / or diethanolamine, according to claim 1 or polyethyleneimine according to claim 8 as liquid or solid CO2 absorbent in a CO2 capture process.

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