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

Abstract

Ethanolamine, polyethyleneimine and ammonia having a low molar distribution of deuterium, a method for producing ethanolamine, polyethyleneimine and ammonia based on non-fossil energy, the molar distribution of deuterium in hydrogen and the use of hydrogen-based downstream compounds for tracing the origin of the preparation of hydrogen and hydrogen-based downstream compounds, and a method for tracing the origin of the preparation of hydrogen and hydrogen-based downstream compounds by determining the molar distribution of deuterium in hydrogen and the hydrogen-based downstream compounds based on hydrogen, the use and application of polyethyleneimine, and the use of ethanolamine, preferably monoethanolamine and / or diethanolamine, or polyethyleneimine as a liquid or solid CO2 absorbent in a CO2 capture process.

Description

Technical Field

[0001] The present invention relates to ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof having a low molar share of deuterium, polyethyleneimine and ammonia, and methods for producing monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine and ammonia based on non-fossil energy, the origin of hydrogen and downstream compounds based on hydrogen, in particular the use of the molar share of deuterium in hydrogen and downstream compounds based on hydrogen to trace the energy origin (the compounds are preferably selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia), and a method for tracing the origin of hydrogen and the downstream compounds based on hydrogen, in particular the energy origin, by determining the molar share of deuterium in hydrogen and the downstream compounds based on hydrogen (the compounds are preferably ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia), the use and application of polyethyleneimine, and the use of ethanolamine, preferably monoethanolamine and / or diethanolamine, or polyethyleneimine as a liquid or solid CO2 absorbent in a CO2 capture process.

[0002] Ethanolamine is a flammable, corrosive, colorless, viscous liquid produced by the reaction of ammonia and ethylene oxide (EO). Ethanolamine was identified many years ago and is an important component in the formulation of many important products such as cosmetics and personal hygiene products, agricultural products, chemical agents for wood preservation, soaps and detergents, and gas treatment agents. These can also be used in the manufacture of non-ionic detergents, emulsifiers and soaps, as well as emulsion paints, abrasives and cleaning agents. There are three types of ethanolamine: monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA). The formation of MEA, DEA, or TEA is determined by whether an 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 detergents, adhesives, water treatment agents, and cosmetics, among others. Furthermore, PEI is used in papermaking and the flocculation process, or as a raw material in the field of biotechnology.

[0004] Furthermore, PEI as well as MEA and / or DEA are useful as carbon dioxide (CO2) capture agents. The amino groups in PEI react with CO2.

[0005] Ammonia is an important precursor in the preparation of MEA, and MEA is an important precursor in the preparation of PEI.

Background Art

[0006] Since the development of the Haber-Bosch process for the preparation of ammonia, most ammonia has been produced by direct synthesis from hydrogen and nitrogen in the presence of a catalyst, especially an iron-containing catalyst. Special attention is required for the supply of the starting materials hydrogen and nitrogen. These 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, a significant amount of hydrogen is supplied by steam reforming and thus from natural gas.

[0007] However, the petrochemical steam reforming process involves the consumption of large amounts of fossil natural resources and energy, and has an adverse impact on its carbon footprint.

[0008] U.S. Patent No. 2011 / 136097 relates to a method for determining the origin of food, and more specifically, to a method for determining the geographical and / or biological origin of food containing alcohol or sugar by using a specific isotope ratio of, for example, sugars derived from different plants, which is affected by climate conditions and the place of origin, as the isotope “fingerprint” of a specific plant.

[0009] However, the deuterium content used in the present invention is based on the finding that the deuterium content of hydrogen obtained by electrolysis of water is lower than that of naturally occurring hydrogen, rather than a natural “fingerprint”. Furthermore, it is not the geographical origin that is determined, but the hydrogen production process.

[0010] U.S. Patent No. 6,495,609 relates to a method for recovering carbon dioxide from an ethylene oxide production process and using the recovered carbon dioxide as a carbon source for methanol synthesis. However, the hydrogen used in the process of U.S. Patent No. 6,495,609 is present in synthesis gas such as natural gas or refinery off-gas.

[0011] British Patent Application Publication No. 2464691 relates to the production of methanol from cellulosic / lignite materials of agricultural by-products. In the first section of the synthesis plant, the cellulosic / lignite by-products remaining after the harvest of agricultural products are converted to carbon dioxide by thermal oxidation. In another section of the synthesis plant, hydrogen gas is generated by electrolysis, which reacts with carbon dioxide to produce methanol.

[0012] International Publication No. 2016 / 149507 relates to the oxidative coupling of methane to obtain a number of different products. For example, Claim 217 discloses a method for producing an oxalic acid compound.

[0013] U.S. Patent No. 7,119,231 relates to a method for preparing alkanolamines by reacting ammonia and alkylene oxide in a reaction space in the presence of a catalyst to obtain a monoalkanolamine or a dialkanolamine or a trialkanolamine or a mixture of two or three of these compounds. There is no hint regarding the deuterium content of the hydrogen-containing compound used in U.S. Patent No. 7,119,231 or the use of non-fossil energy.

[0014] French Patent Application Publication No. 2851564 relates to a method for preparing ethylene oxide and ethanolamine. There is no hint regarding the presence of deuterium in the hydrogen-containing compound or the use of non-fossil energy as in French Patent Application Publication No. 2851564.

[0015] U.S. Patent Application Publication No. 2008 / 0283411 specification relates to a method for converting a carbon source and a hydrogen source into hydrocarbons. It is mentioned that this method and apparatus are useful for producing alternative energy sources to fossil fuels, storing renewable energy, isolating carbon dioxide from the atmosphere, combating global warming, and storing carbon dioxide in liquid fuels.

[0016] International Publication No. 2015 / 102985 relates to a method for preparing ethanolamine including reacting a water-ammonia solution and ethylene oxide. However, there is no hint regarding the preparation of hydrogen by electrolysis, the use of renewable energy, and the presence of deuterium in the hydrogen-containing compound disclosed in the International Publication No. 2015 / 102985 pamphlet.

[0017] German Patent Application Publication No. 19534493 relates to a method for preparing aziridine in the presence of a particulate shell catalyst. Aziridine is prepared by dehydrating alkanolamine in the presence of the catalyst. However, German Patent Application Publication No. 19534493 does not describe the electrolysis of water for the preparation of hydrogen, the deuterium content of the hydrogen-containing compounds described in the specification of German Patent Application Publication No. 19534493, nor the use of renewable energy.

Prior Art Documents

Patent Documents

[0018]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0019] Accordingly, an object of the present invention is to provide an environmentally friendly ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine and ammonia, and an environmentally friendly process for producing ethanolamine that uses fossil energy as little as possible.

Means for Solving the Problems

[0020] This object is achieved by an ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, wherein the molar share of deuterium is 100 ppm or less, preferably in the range of 10 to 98 ppm or less, more preferably in the range of 10 to 95 ppm or less, most preferably in the range of 10 to 90 ppm or less based on the total hydrogen content; for polyethyleneimine, the molar share of deuterium is 110 ppm or less, preferably in the range of 10 to 105 ppm or less, more preferably in the range of 10 to 95 ppm or less, most preferably in the range of 10 to 92 ppm or less based on the total hydrogen content; for ammonia, the molar share of deuterium is 100 ppm or less, preferably in the range of 10 to 95 ppm or less, more preferably in the range of 10 to 90 ppm or less, most preferably in the range of 10 to 80 ppm or less based on the total hydrogen content.

[0021] In a further embodiment of the present invention, this object is achieved by a method for producing an ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, said method comprising (a) providing hydrogen by electrolysis based on electricity generated at least partially from non-fossil energy, wherein the molar share of deuterium is 100 ppm or less, preferably in the range of 10 to 95 ppm or less, more preferably in the range of 10 to 90 ppm or less, most preferably in the range of 10 to 80 ppm or less based on the total hydrogen content; (b) reacting the hydrogen obtained in step (a) with nitrogen to form ammonia; (c) Reacting the hydrogen obtained in step (a) with a carbon oxide, preferably carbon dioxide, to form methanol; (d) Converting the methanol obtained in step (c) to ethylene and further to ethylene oxide; (e) Converting the ammonia obtained in step (b) and the ethylene oxide obtained in step (d) to ethanolamine in one or more steps; comprising.

[0022] This object is a method for preparing polyethyleneimine, wherein the method comprises: (f) Separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the method according to any one of claims 1 to 7, or from the ethanolamine according to claim 8; (g) Converting monoethanolamine to ethyleneimine; (h) Polymerizing the ethyleneimine obtained in step (g) to polyethyleneimine; comprising a method; and A method for producing ammonia, wherein the method comprises the following steps (a) By electrolysis based on electricity generated at least partially from non-fossil energy, providing hydrogen in which the molar share of deuterium is in the range of 100 ppm or less, preferably 10 to 95 ppm or less, more preferably 10 to 90 ppm or less, and most preferably 10 to 80 ppm or less based on the total hydrogen content; (b) Reacting the hydrogen obtained in step (a) with nitrogen to form ammonia; comprising a method is further achieved by.

[0023] Furthermore, it is important that the origin of the hydrogen and downstream compounds obtained by clean energy can be traced in a reliable way.

[0024] This is especially to ensure the following: ·Hydrogen and downstream compounds are produced in accordance with sustainability criteria. ·The renewable attributes are not double-counted.

[0025] Companies are increasingly focusing on the procurement of green energy. Therefore, it is necessary to develop a system for tracking the origin of the energy used in the preparation of hydrogen and downstream compounds.

[0026] This object is achieved by determining the molar share of deuterium in hydrogen and hydrogen-based downstream compounds (the compound is preferably ethanolamine, polyethyleneimine or ammonia selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof) and the molar share of deuterium in hydrogen and hydrogen-based downstream compounds, in order to track the origin, particularly the energy origin, of the hydrogen and the downstream compounds based on hydrogen (the compound is preferably ethanolamine, polyethyleneimine or ammonia selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof). A method for determining the molar share of deuterium in hydrogen and hydrogen-based downstream compounds is known to those skilled in the art. Suitable methods are described in the examples of the present application.

[0027] A further environmental advantage of the environmentally friendly ethanolamines and polyethyleneimines according to the invention, selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, is their use in the carbon capture process. This is because the ethanolamines and polyethyleneimines according to the invention are produced without using fossil energy as much as possible and ideally without using fossil energy, so as to minimize CO2 emissions and ideally make them zero.

[0028] Accordingly, a further embodiment of the present invention is the use of ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, or polyethyleneimine according to the present invention, as liquid or solid CO2 absorbents in the CO2 capture process.

[0029] The molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds is given in ppm in this application based on the total hydrogen content. This is the molar ppm content of deuterium based on the total hydrogen content (in hydrogen or in the compound under discussion, respectively).

[0030] The deuterium content of hydrogen and hydrogen-based downstream compounds is given in atom ppm in this application based on the total molar hydrogen content (total number of atoms of protium 1 H and deuterium 2 H). The terms "deuterium content" and "molar fraction of deuterium" are used synonymously throughout this application.

[0031] In physical organic chemistry, the kinetic isotope effect is the change in the reaction rate of a chemical reaction when one of the atoms in the reactant is replaced by one of its isotopes. Formally, this is the ratio of the rate constants k L of the reaction involving the light (k H ) and heavy (k L / k H ) isotope-substituted reactants (isotopologues). This change in reaction rate is mainly a quantum mechanical effect arising from the heavier isotopologues having lower vibrational frequencies compared to their lighter counterparts. In most cases, this means that the heavier isotopologues require a greater energy input to reach the transition state and thus have a slower reaction rate.

[0032] The isotope rate change is most pronounced when the relative mass change is greatest because the effect is related to the vibrational frequency of the bond being affected. For example, changing a hydrogen atom (H) to its isotope deuterium (D) represents a 100% increase in mass, 12 C to13 When replacing with C, the mass only increases by 8 percent. The rate of reactions involving C-H bonds is typically 6 to 10 times faster than the corresponding C-D bonds, but 12 the C reaction is only 4 percent faster than the corresponding 13 C reaction.

[0033] A primary kinetic isotope effect can be found when a bond to an isotopic atom is being formed or broken. A secondary kinetic isotope effect is observed when no bond to an isotopic atom in the reactant is being broken or formed. The secondary kinetic isotope effect tends to be much smaller than the primary kinetic isotope effect, although the secondary deuterium isotope effect can be as large as 1.4 per deuterium atom.

[0034] A method for producing ethanolamine, comprising the above steps (a) to (e): Step (a) Step (a) relates to the supply of hydrogen having a molar share of deuterium of less than 90 ppm, based on the total hydrogen content, by electrolysis based on electricity generated at least in part from non-fossil energy.

[0035] The electricity is generated at least in part from non-fossil resources.

[0036] The term "at least in part" means that since the combustion of natural gas results in much less carbon dioxide emissions per megajoule of electrical energy generated than the combustion of coal, a portion of the electricity can still be generated from fossil fuels, preferably natural gas. However, the proportion of electrical energy generated from fossil fuels should be as low as possible, preferably 50% or less, preferably 30% or less, most preferably 20% or less, and even more preferably 10% or less. In one embodiment, the electricity is generated only from non-fossil resources.

[0037] Various methods for the certification and tracking of "energy source mix" are set based on local laws. Certificates such as "Non-Fossil Fuel Certificate Contracts" are common practices for tracking the proportion of non-fossil energy used in industrial processes and related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / ).

[0038] Preferably, the electric power is at least partially generated from renewable resources, preferably wind power, solar energy (thermal, photovoltaic, concentrated solar power), hydroelectric power (tidal power, wave power, hydroelectric dams, in-river hydroelectric power), geothermal energy, ambient or industrial heat captured by heat pumps, bioenergy (biofuels, biomass), the renewable portion of waste energy sources, or nuclear energy (nuclear fission).

[0039] In a further embodiment, the electric power is at least partially generated from renewable resources, preferably wind power, solar energy (thermal, photovoltaic, concentrated solar power), hydroelectric power (tidal power, wave power, hydroelectric dams, in-river hydroelectric power), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuels, biomass), or the renewable portion of waste.

[0040] The types of electric power resources described above are generally known to those skilled in the art.

[0041] In a preferred embodiment of the method of the present invention, the electric power from non-fossil resources used in the electrolysis according to the present invention can be at least partially generated by nuclear energy. Nuclear energy can be obtained by nuclear fission.

[0042] Nuclear fission occurs when a neutron enters a larger atomic nucleus and excites it to split into two smaller atoms (also known as fission products). Further neutrons that can start a chain reaction are also released. 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.

[0043] In a preferred embodiment of the method of the present invention, the power used in the electrolysis is generated at least in part from wind power. Wind power can be used to operate wind turbines. Modern utility-scale wind turbines range in rated power output from about 600 kW to 9 MW. The power available from wind is a cube function of the wind speed, so as wind speed increases, the power output increases up to the maximum power output of a particular turbine. Areas where the wind is stronger and more constant, such as offshore and at high altitudes, are preferred locations for wind farms.

[0044] In a further preferred embodiment of the method of the invention, the power used for electrolysis is generated at least partially from solar power, particularly preferably from a photovoltaic system. Photovoltaic systems convert light into direct current (DC) by utilizing the photoelectric effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus a wide range of sunlight into a small beam. CSP Stirling has by far the highest efficiency of all solar energy technologies.

[0045] In a preferred embodiment of the method of the present invention, the electric power used in electrolysis is at least partially generated from hydroelectric power. There are many forms of hydroelectric power. Conventionally, hydroelectric power has been brought about by constructing large hydroelectric dams and reservoirs. Small hydroelectric systems are typically hydroelectric facilities that generate up to 50 MW of power. These are often used in small rivers or as less impactful developments in larger rivers. Run-of-river power plants obtain energy from rivers without forming large storage pools. Water is typically carried along the sides of river valleys (using channels, pipes, and / or tunnels) until it is higher than the valley bottom, and then it can be dropped through penstocks to drive turbines.

[0046] Wave power that captures the energy of ocean surface waves and tidal power that converts the energy of ocean currents are two forms of hydroelectric power with future potential.

[0047] In an even more preferred embodiment of the method of the present invention, the electric power used in electrolysis is at least partially generated from geothermal energy. Geothermal energy is the heat that occurs from beneath the Earth's surface. This is contained within the rocks and fluids beneath the Earth's crust and is found down to the extent of the Earth's hot molten rock, magma.

[0048] To generate electric power from geothermal energy, wells are drilled down to a depth of one mile into underground reservoirs to extract the steam and hot water present there. It can be used to drive turbines connected to generators. There are three types of geothermal power plants: dry steam, flash, and binary.

[0049] Dry steam is the oldest form of geothermal technology, which extracts steam from the ground and uses it to directly drive turbines. Flash plants use high-pressure hot water to low-temperature, low-pressure water, and binary plants pass hot water through a secondary liquid with a low boiling point to convert it to steam to drive turbines.

[0050] In one further preferred embodiment of the method of the present invention, the electric power used for electrolysis is at least partially generated from biomass. Biomass is biological material derived from living or recently living organisms. This most often refers to plant or plant-derived materials, especially those called lignocellulosic biomass. As an energy source, biomass can be used directly by combustion to generate heat (e.g., heat from fermentation processes) or electricity, or it can be used indirectly after converting biomass into various forms of biofuels and gases. The conversion of biomass into biofuels can be achieved by a variety of methods broadly classified into thermal, chemical, and biochemical methods. Wood was the largest biomass energy source in 2012; examples include forest residues - such as dead wood, branches and tree stumps -, yard trimmings, wood chips and even municipal waste. Industrial biomass can be grown from a number of plant species including a variety of tree species ranging from miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and eucalyptus to oil palm (palm oil).

[0051] Plant energy is generated by crops specially cultivated for use as fuels that provide high biomass yields per hectare with low input energy. Grains can be used for liquid transportation fuels and straw can be burned to generate heat or electricity. Biomass can be converted into other usable forms of energy, such as methane gas or transportation fuels, such as ethanol and biodiesel. Food waste, as well as agricultural waste and manure all emit methane gas, also called landfill gas or biogas. Crops, such as corn and sugarcane, can be fermented to produce the transportation fuel, ethanol. Another transportation fuel, biodiesel, can be produced from food leftovers, such as vegetable oils and animal fats.

[0052] Biopower technology converts renewable biomass fuels into heat and electricity using processes similar to those used for fossil fuels. To recover the energy stored in biomass and generate biopower, there are three methods: combustion, bacterial decomposition, and conversion to gas or liquid fuels. Biopower can offset the need for carbon fuels burned in power plants and thus reduce the carbon intensity of electricity generation. Unlike some intermittent renewable energies, biopower can enhance the flexibility of electricity generation and improve the reliability of the power grid.

[0053] The electrolysis in step (a) is generally the electrolysis of water.

[0054] Electrolysis of water is an environmentally friendly method for producing hydrogen because it uses renewable H2O and produces only pure oxygen as a by-product.

[0055] According to the present invention, the electrolysis, which is generally water electrolysis, utilizes direct current (DC) from at least partially non-fossil energy resources as power.

[0056] Here, as an important finding of the present application, it is observed that by electrolysis of water, the deuterium atom content of hydrogen is lower than that of petrochemically produced hydrogen as contained in, for example, fossil fuel-based synthesis gas, that is, 100 ppm or less, preferably in the range of 10 to 95 ppm or less, more preferably in the range of 10 to 90 ppm or less, and most preferably in the range of 10 to 80 ppm or less based on the total hydrogen content. The deuterium atom content in hydrogen produced by electrolysis can be as low as 10 ppm. The remaining deuterium mainly exists in the form of D-H rather than D2.

[0057] One suitable water electrolysis method is alkaline water electrolysis. Hydrogen production by alkaline water electrolysis is a well-established technology up to the megawatt level for commercial applications. In alkaline water electrolysis, first, at the cathode side, two water molecules in an alkaline solution (KOH / NaOH) form one hydrogen molecule (H2) and two hydroxyl ions (OH -) is reduced to. The generated H2 is dissipated from the cathode surface in gaseous form, and the hydroxyl ions (OH - ) move through the porous diaphragm to the anode under the influence of the electric field between the anode and the cathode, where they are discharged into half a molecule of oxygen (O2) and one molecule of water (H2O). Alkaline electrolysis operates at a lower temperature, for example 30 - 100 °C, using an alkaline aqueous solution (KOH / NaOH) as the electrolyte, and the concentration of the electrolyte is about 20% - 30%. The diaphragm at the center of the electrolytic cell separates the cathode and the anode, and similarly separates the generated gases from each electrode, avoiding the mixing of the generated gases.

[0058] An overview of hydrogen production by alkaline water electrolysis using renewable energy as the power source is described in J. Brauns and T. Turek in Processes, 8(2)(2020), pp. 248.

[0059] In a further embodiment of the method of the present invention, hydrogen is supplied by the electrolysis of a polymer electrolyte membrane. Variations of polymer electrolyte membrane water electrolysis include proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).

[0060] PEM water electrolysis technology is similar to PEM fuel cell technology in which a solid polysulfonated membrane (Nafion®, fumapem®) is used as the electrolyte (proton conductor). These proton exchange membranes have many advantages, such as low gas permeability, high proton conductivity (0.1 ± 0.02 S cm -1 ), a thin thickness (20 - 300 μm), and enable high-pressure operation. From the perspectives of sustainability and environmental impact, PEM water electrolysis is one of the most preferred methods for converting renewable energy into high-purity hydrogen. PEM water electrolysis has significant advantages, such as a compact design, a high current density (2 A cm -2have high efficiency, high-speed response, operation at low temperatures (20 - 90 °C), and production of ultra-high purity hydrogen. Prior art electrode catalysts for PEM water electrolysis are highly active noble 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.

[0061] One of the greatest advantages of PEM water electrolysis is the ability to operate at high current densities. This can reduce the operating costs of systems connected to highly dynamic energy sources, such as wind and solar power, which produce energy that is not captured by sudden spikes in energy output. The polymer electrolyte enables the PEM water electrolysis device to operate with a very thin membrane (about 100 - 200 μm), while still allowing for high operating pressures, resulting in low ohmic losses caused mainly by proton conduction (0.1 S / cm) across the membrane and compressed hydrogen output.

[0062] PEM water electrolysis devices utilize a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while electrically insulating the electrodes. Under standard conditions, the enthalpy required for water formation is 285.9 kJ / mol. Part of the energy required for the continuous electrolysis reaction is supplied by thermal energy, and the remainder is supplied through electrical energy.

[0063] The half-reaction that occurs on the anode side of a PEM water electrolysis device is generally called the oxygen evolution reaction (OER). Here, liquid water reactants are supplied to the catalyst, where they are oxidized into oxygen, protons, and electrons.

[0064] The half-reaction that occurs on the cathode side of a PEM water electrolysis device is generally called the hydrogen evolution reaction (HER). Here, protons that have moved through the membrane are reduced to gaseous hydrogen.

[0065] PEMs can be made from either pure polymer membranes or composite membranes in which other materials are embedded in a polymer matrix. One of the most common commercially available PEM materials is the fluoropolymer PFSA (e.g., Nafion® from DuPont). Nafion® is an ionomer with a perfluorinated backbone like Teflon, but there are many other structural motifs used to make ionomers for proton exchange membranes. Many use polycyclic aromatic polymers, others use partially fluorinated polymers.

[0066] An overview of hydrogen production by PEM water electrolysis is presented in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pages 4442 - 4454.

[0067] AEM water electrolysis technology employs low - cost catalyst materials as in the case of alkaline electrolysis and a solid polymer electrolyte structure as in the case of PEM electrolysis technology. AEM electrolysis technology operates in an alkaline environment (pH around 10), enabling the use of moderate non - noble metal electrode catalysts (i.e., platinum - group metal - free catalysts = PGM - free catalysts) while accommodating a zero - gap structure. The membranes used in this type of electrolysis are polymer membranes containing quaternary ammonium salts. These are relatively inexpensive and have low interaction with CO2 in the atmosphere.

[0068] Catalysts: As an example of a hydrogen evolution reaction (HER) catalyst, a catalyst based on a Ni - Mo alloy material is suitable.

[0069] As an example of an oxygen evolution reaction (OER) catalyst, highly active transition metal mixed oxides are suitable. Specific examples are CuxCo3_xO4 on Ni foam, NiCo2O4:Fe and Ni - Fe alloys, e.g., PGM - free catalysts (Ni - Fe, Ni - Mo, Ni / (CeO2 - La2O3) / C and CuxCo3_xO4).

[0070] Membranes and ionomers: The chemical stability of AEMs under alkaline conditions has been significantly improved by the development of stabilized functional groups on the polymer backbone. As a result, such membranes can be used at high temperatures and 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 cited below. One example is the commercially available membrane Tokuyama A201.

[0071] Fabrication of Membrane Electrode Assemblies and Cell Performance: The evaluation of the physical and electrochemical properties of membrane electrode assemblies fabricated by either the catalyst coated substrate (CCS) or catalyst coated membrane (CCM) method suggests that the CCM is preferred because the improvement in ionic conductivity far exceeds the improvement in electronic conductivity.

[0072] Liquid Electrolyte: In the case of pure water supply, the current density is generally low, while good results are obtained with 1% K2CO3 or dilute KOH solutions. Good electrolysis performance is achieved using a 1% K2CO3 electrolyte. Therefore, the aqueous electrolyte preferably contains 0.1 - 2 wt% of K2CO3 or KOH.

[0073] An overview of hydrogen production by anion exchange membrane water electrolysis is shown in H. A. Miller et al., Sustainable Energy Fuels, 2020, 4, 2114 - 2133.

[0074] In addition to alkaline water electrolysis, AEMs, and PEMs, a further commercially available electrolysis technology is solid oxide electrolysis (SOE).

[0075] A SOEC (Solid Oxide Electrolysis Cell) supplies water to the cathode, where the water undergoes a water reduction reaction (WRR) to convert the water into hydrogen gas and oxide ions. This hydrogen gas is then carried to a purification module to separate the hydrogen gas from the remaining water. Subsequently, the oxide ions move from the cathode to the anode, releasing electrons into the external circuit and becoming oxygen gas through an oxygen evolution reaction (OER). Usually, the operating temperature of an SOFC is 800 - 1,000 °C, which is because high temperatures are required to thermally activate the movement of oxide ions and promote the electrochemical reactions at both electrodes, resulting in an improvement in overall efficiency. SOEC is described, for example, in K. Kamlungsua et al., FUEL CELLS 20, 2020, No. 6, 644 - 649.

[0076] Preferably, the electrolysis in step (a) is water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0077] In a more preferred embodiment, the electrolysis in step (a) is solid oxide water electrolysis (SOE).

[0078] In water electrolysis, such as polymer electrolyte membrane water electrolysis, it is known in the art that the deuterium in the generated hydrogen gas may decrease relative to the feed water. The reduction factor depends on the electrolysis conditions (water flow, current density). Since the average deuterium content (mole fraction of deuterium) of water is about 150 ppm based on the total hydrogen content, the hydrogen provided in step (a) of the method of the present invention has a mole fraction (deuterium content) of deuterium of 100 ppm or less, preferably in the range of 10 - 95 ppm or less, more preferably in the range of 10 - 90 ppm or less, most preferably in the range of 10 - 80 ppm or less, or even lower, based on the total hydrogen content.

[0079] Generally, in the preferred water electrolysis in step (a), any water source can be used. However, the hydrogen prepared in step (a) has a deuterium molar share (deuterium content) in the range of less than 100 ppm, preferably in the range of 10 to 95 ppm, more preferably in the range of 10 to 90 ppm, and most preferably in the range of 10 to 80 ppm, based on the total hydrogen content. Therefore, it is preferable to use water having a deuterium molar share (deuterium content) of less than 160 ppm based on the total hydrogen content.

[0080] Vienna Standard Mean Ocean Water (VSMOW) is an isotope standard water defined by the International Atomic Energy Agency in 1968. Although the somewhat misleading expression "ocean water" is used, VSMOW refers to pure water (H2O) and does not contain salts or other substances commonly found in ocean water. VSMOW mainly functions as a reference standard for comparing the isotope ratios of hydrogen and oxygen in water samples. Since very pure distilled VSMOW water is considered to substantially represent the "mean ocean water" that represents the water content of the Earth, it is also used for high-precision measurement of the physical properties of water and for defining laboratory standards.

[0081] The isotope composition of VSMOW water is specified as the ratio of the molar abundance of the rare isotope in question to the molar abundance of its most common isotope and is expressed in parts per million (ppm). For example, 16 O (the most common isotope of oxygen with 8 protons and 8 neutrons) is present in seawater 17 about 2,632 times more than 2 H / 1 H = 155.76 ± 0.1 ppm (a ratio of about 1 part in 6420) 3 H / 1 H = 1.85 ± 0.36 × 10 -11 ppm (a ratio of about 1 part in 5.41 × 10 16 parts, ignoring operations related to physical properties) 18 O / 16O = 2005.20 ± 0.43 ppm (at a ratio of about 1 part per about 498.7 parts) 17 O / 16 O = 379.9 ± 1.6 ppm (at a ratio of about 1 part per about 2632 parts) (See https: / / en - academic.com / dic.nsf / enwiki / 753132)

[0082] More preferably, the average deuterium content of the water in step (a) is 1 ppm based on the total hydrogen content (ultra - light water to 156 ppm, most preferably 2 ppm to 150 ppm based on the total hydrogen content).

[0083] Methods for reducing deuterium in water are known to those skilled in the art. However, the process is generally an electrolysis process that consumes energy, as described, for example, in the specification of Chinese Patent Application Publication No. 103848399.

[0084] Therefore, when using deuterium - reduced water, it is preferable to use deuterium - reduced water obtained from the following resources. - By - products of "heavy water" (D2O) production (heavy water is used in organic chemistry, drug development, and nuclear reactors); (deuterium content about 10 - 120 ppm) - Water from mountains; (deuterium content about 120 - 150 ppm) - Surface water of rivers and lakes; (deuterium content about 130 - 150 ppm) - Any water source with a seasonally low deuterium content, for example, water taken at low temperatures (cold water in winter has a lower deuterium content than warm water in summer); for example, water taken from snow or ice in winter; (deuterium content is about 120 - 150 ppm) - Polar water and Antarctic glacial meltwater (deuterium content about 90 - 150 ppm) - Low - salinity seawater, such as near river mouths, desalinated water, brackish water, and treated wastewater drainage, etc.; (deuterium content about 130 - 155 ppm)

[0085] Step (b) Step (b) relates to reacting the hydrogen obtained in step (a) with nitrogen to form ammonia.

[0086] The reaction of step (b) preferably follows the Haber-Bosch process.

[0087] The catalysts commonly used in the Haber-Bosch process are generally classified into one of two categories: molten iron and supported metal catalysts. Molten iron catalysts are derived from iron oxides, which can be one of three possibilities: Fe2O3, Fe3O4, and Fe 1-x O (known as hematite, magnetite, and wustite respectively). Industrially, these iron catalysts will be multi-promoted with promoters present in small amounts of a few weight percent, such as K2O, BaO, KOH, CaO, MgO, and Al2O3.

[0088] Supported metal catalysts are catalysts composed of a metal catalyst material (usually ruthenium or cobalt for ammonia synthesis reaction) supported on the surface of a carrier material (usually activated carbon or metal oxide). Generally, the weight percentage of the metal catalyst is about 2 - 10%.

[0089] Other catalysts that can be used are nickel, and nitride catalyst systems or electrides, hydrides, nitrides, oxyhydride-promoted Ru, Fe, Co, and Ni catalysts.

[0090] The above catalysts can be used in both conventional centralized large-scale Haber-Bosch ammonia synthesis plants and decentralized small-scale ammonia production by the same process.

[0091] In one embodiment of the present invention, step (b) is carried out at a pressure in the range of 50 - 350 bar (absolute pressure), preferably 150 - 300 bar (absolute pressure).

[0092] In one embodiment of the present invention, step (b) is carried out at a temperature in the range of 300 - 600 °C, preferably 400 - 500 °C.

[0093] The overall isotope effect is cumulative because it exists in all subsequent manufacturing steps downstream of the value chain. By performing step (b), ammonia is formed. The deuterium content is even lower than that corresponding to the distribution obtained by the conventional petrochemical route.

[0094] Step (c) Step (c) relates to reacting the hydrogen obtained in step (a) with a carbon oxide, preferably carbon dioxide, to form methanol.

[0095] Suitable carbon oxides are carbon monoxide, carbon dioxide or a mixture of both, with carbon dioxide being preferred.

[0096] Process conditions for the hydrogenation of carbon monoxide or a mixture of carbon monoxide and carbon dioxide are known per se and include, for example, low-pressure synthesis, medium-pressure synthesis and high-pressure synthesis.

[0097] i) Low-pressure synthesis Low-pressure synthesis is generally carried out at a pressure between 50 and 100 bar. The temperature is generally between 220 and 300 °C. As a catalyst, a catalyst based on Cu, ZnO, Al2O3 (for example, CuO / ZnO / Al2O3) is generally used. Low-pressure synthesis is the most preferred synthesis for preparing methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0098] ii) Medium-pressure synthesis Medium-pressure synthesis is generally carried out at a pressure between 100 and 250 bar. The temperature is generally up to 300 °C. As a catalyst, a Zn / Cr2O3-based catalyst or a Zn-Cu-based catalyst is generally used.

[0099] iii) High-pressure synthesis High-pressure synthesis is generally carried out at a pressure between 250 and 350 bar. The temperature is generally between 320 and 380 °C. As a catalyst, a catalyst based on zinc oxide-chromium oxide is generally used. This method is not very preferred for the production of methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0100] The current world energy system is still mainly based on the use of fossil fuels, and although the use of renewable energy sources is increasing, it will continue in the medium and short term. The extensive use of fossil fuels in industry and transportation results in large amounts of CO2 emissions. Since it is an object of the present invention to provide environmentally friendly ethanolamine, polyethyleneimine and ammonia and environmentally friendly methods for producing them, it is preferable to prepare methanol by reacting the hydrogen obtained in step (a) according to the method of the present invention with carbon dioxide in step (c).

[0101] In a preferred embodiment, the carbon dioxide supplied in step (c) is captured from industrial flue gas or ambient air. All available capture technologies can be used.

[0102] An overview of commercially available CO2 capture technologies is described in Koytsoumoa et al., The Journal of Supercritical Fluids, Volume 132, February 2018, Pages 3-16.

[0103] CO2 capture is most cost-effective at point sources, such as large carbon-based energy facilities, industries with large CO2 emissions (such as cement manufacturing, ammonia synthesis, steelmaking), natural gas processing, synthetic fuel plants and fossil fuel-based hydrogen production plants. Although it is possible to extract CO2 from the air, the low concentration of CO2 in the air compared to combustion sources makes the technology more complex and thus the method more expensive.

[0104] In some preferred embodiments, the carbon dioxide supplied in step (b) is captured from industrial flue gas.

[0105] The main industrial sources of CO2 are power plants based on the combustion of fossil fuels, oil refining, biogas sweetening (e.g., fermentation), and the manufacture of chemicals. Related chemical manufacturing processes include, for example, the production of C1-C4 olefins and C6 aromatic compounds, as well as downstream chemicals, such as naphtha cracking for ammonia and other CO2-intensive products in particular). Further examples include industrial paper, food, cement, minerals, and steel production.

[0106] In post-combustion capture, CO2 is removed after the combustion of fossil fuels - this is a scheme applied to fossil fuel power plants. CO2 is captured from the flue gas of power plants or other point sources. Absorption, or carbon scrubbing with amines, is the dominant capture technology. This is the only carbon capture technology that has been used industrially so far. Suitable post-carbon capture methods include, for example, absorption (chemical, physical), adsorption (chemical, physical), membrane processes, biological processes, and cryogenic processes.

[0107] Pre-conversion capture means capturing CO2 generated as an unwanted by-product of intermediate reactions in the conversion process. Some examples include ammonia production in power plants and coal gasification. In ammonia production, the CO2 generated simultaneously with hydrogen during steam reforming needs to be removed before ammonia synthesis can be carried out, and for these purposes, absorption into monoethanolamine (MEA) and / or diethanolamine (DEA) is commonly used. Similarly, in integrated gasification combined cycle (IGCC) power plants, it is necessary to separate CO2 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.

[0108] Oxy-fuel combustion technology involves burning carbonaceous fuels in a stream of pure oxygen instead of air. Since the oxidant (O2) does not contain other components (such as nitrogen) in the air, the CO2 concentration in the flue gas is very high, but the water vapor content can be easily removed.

[0109] CO2 is adsorbed onto the MOF (metal-organic framework) through physical or chemical adsorption based on the porosity and selectivity of the MOF, leaving a gas stream poor in CO2. Then, temperature swing adsorption (TSA) or pressure swing adsorption (PSA) can be used to strip the CO2 from the MOF and the MOF can be reused.

[0110] In some other preferred embodiments, the carbon dioxide supplied in step (b) is captured from ambient air.

[0111] Direct air capture (DAC) technology is a method of directly capturing carbon dioxide (CO2) from ambient air and producing a concentrated stream of CO2 for the sequestration or utilization or production of carbon-neutral fuels. When ambient air contacts a chemical medium, typically an aqueous alkaline solvent or an adsorbent, carbon dioxide removal is achieved. Then, the CO2 is stripped from these chemical media through the application of energy (i.e., heat) to obtain a CO2 stream that can undergo dehydration and compression, while simultaneously regenerating the chemical medium for reuse.

[0112] Chen, Lackner et al., Angew. Chem. Int. Ed. 2020, 59, 6984 - 7006, "Sorbents for the Direct Capture of CO2 from Ambient Air" describes the main types of adsorbents designed to capture CO2 from ambient air, classified by the adsorption mechanism (physical adsorption, chemical adsorption, and moisture swing adsorption).

[0113] Kommalapati et al., Energy Technol. 2017, 5, 822 - 833 describes the application of polyethyleneimine in the capture and separation of carbon dioxide.

[0114] Lean CO2 can be efficiently separated using an anion exchange polymer resin called Marathon MSA that absorbs air CO2 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 substances that can be used are metal-organic frameworks (or MOFs). Membrane separation of CO2 relies on semipermeable membranes.

[0115] In one embodiment of the invention, ethanolamines in a mixture of monoethanolamine, diethanolamine and triethanolamine, or in each of monoethanolamine, diethanolamine and triethanolamine, preferably ethanolamine in a mixture of monoethanolamine (MEA) and diethanolamine (DEA), and / or polyethyleneimine according to the invention are used in a process for capturing CO2. The ethanolamines of the invention in a mixture or each of monoethanolamine, diethanolamine and triethanolamine and polyethyleneimine minimize CO2 emissions and in a preferred embodiment do not increase them at all, and thus contribute as little as possible, preferably not at all, to the CO2 emissions themselves.

[0116] Accordingly, in a further embodiment, the 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 invention as liquid and solid CO2 absorbents in a CO2 capture process.

[0117] Suitable carbon capture processes are described above and are known in the art.

[0118] In step (c), carbon dioxide and hydrogen are reacted to form methanol.

[0119] The process conditions for the hydrogenation of carbon dioxide are known per se. For the synthesis of methanol by the hydrogenation of CO2, various process approaches: (1) heterogeneous catalytic reaction, (2) homogeneous catalytic reaction, (3) electrochemical reaction, and (4) photocatalytic reaction, have been developed (see R. Guil-Lopez, Materials 2019, 12, 3902; doi: 10.3390 / ma12233902). Preferably, the synthesis of methanol by the hydrogenation of carbon dioxide is carried out in the presence of a heterogeneous catalyst.

[0120] Generally, the production of methanol is carried out in a synthesis converter, such as a fixed-bed catalytic reactor.

[0121] The average temperature inside the reactor is generally in the range of 150 - 300 °C. The average pressure inside the reactor is generally 50 - 150 bar (absolute pressure).

[0122] An overview of suitable heterogeneous catalyst systems is presented by Kristian Stangeland, Hailong Li & Zhixin Yu, Energy, Ecology and Environment volume 5, pages 272 - 285 (2020). This method requires a multi-component catalyst system. The interaction between components is essential for the high activity and selectivity of the catalyst from CO2 to methanol. This has been demonstrated by a number of catalyst systems composed of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., Al2O 3、 ZnO, ZrO2, In2O3). These composite 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 performance. A suitable catalyst is, for example, copper-zinc-alumina.

[0123] By carrying out step (c), methanol CH3 is formed by reacting the hydrogen obtained in step (a) with a carbon oxide, preferably carbon dioxide. The deuterium content is even lower than that corresponding to the distribution obtained by conventional petrochemical routes.

[0124] Step (d) In step (d), the methanol obtained in step (c) is converted to ethylene and further to ethylene oxide.

[0125] Preferably, the ethylene oxide in step (d) is (d1) obtained from the methanol - to - olefins process where ethylene is produced, and then (d2) epoxidation of ethylene is obtained by.

[0126] Step (d1) Generally, ethylene is produced from methanol in the process of converting methanol to olefins (MTO process).

[0127] The MTO process is an acid - catalyzed reaction. Preferred catalysts are zeolites containing silica and alumina (e.g., ZSM - 5) and zeolites such as silicon aluminophosphate zeolite catalysts (SAPO) (e.g., SAPO - 34).

[0128] This reaction is generally carried out at a temperature of 300 - 600 °C. The pressure is generally 0.1 - 0.3 MPa.

[0129] This process is preferably carried out in a fluidized - bed catalytic reactor.

[0130] 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 from 1.33 in propylene - production mode.

[0131] Examples of commercially available MTO technology licensors are UOP (e.g., UOP Advanced MTO process), Energy Technology Co., Ltd. (DMTO process), and Sinopec (SMTO process).

[0132] A more detailed description can be found, for example, in “Ethylene” by Adam Chan, Nexant, TECH 2018-1, July 2018, pp. 100-109.

[0133] Step (d2) In step (d2), the ethylene from step (d1) is converted to ethylene oxide.

[0134] The direct oxidation process is preferably carried out in the gas phase using, for example, oxygen or air, in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0135] Step (d2) is usually carried out at a temperature of 230-270 °C. The pressure is preferably in the range of 10-30 bar.

[0136] In a preferred embodiment, step (d2) is carried out by gas-phase selective ethylene oxidation (ethylene epoxidation) typically in a fixed-bed tubular reactor loaded with an Ag / Al2O3 catalyst at 230-270 °C and 10-30 bar.

[0137] Preferred catalysts for the process of step (d2) are silver-based catalysts as follows - preferably a supported Re / Cs / Ag / Al2O3 catalyst that acts with an excess of C2H4 / O2; or - preferably an alkali metal (Na, Cs)-promoted supported Ag / Al2O3 catalyst that acts with an excess of O2 / C2H4.

[0138] Oxides of Mo and S have also been found to promote the supported Re / Cs / Ag / Al2O3 system for EO formation. Thus, the supported Re / Cs / Ag / Al2O3 system may further contain oxides of Mo and / or S as promoters.

[0139] Furthermore, C2H4Cl2 can be added to deposit Cl on the catalyst, which acts as a promoter.

[0140] Examples of descriptions can be found, for example, in "Ethylene Oxide" by Mia Monconduit and Karen Jobes, IHS Markit, Chemical Economics Handbook, December 22, 2020, pp. 14-16.

[0141] Step (e) In step (e), the ammonia obtained in step (b) is converted in one or more steps using the ethylene oxide obtained in step (d) into an ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof.

[0142] The reaction product obtained in step (e) generally contains monoethanolamine, diethanolamine, and triethanolamine.

[0143] The preparation of step (e) is preferably carried out in a closed cycle process using generally only a small supply of fresh water in the presence of water. However, it is also possible to prepare ethanolamine by reacting ammonia with ethylene oxide in an anhydrous process. The anhydrous process preferably uses a fixed bed catalyst, such as an organic ion exchange resin or a thermally more stable acidic inorganic clay or zeolite.

[0144] In a preferred process, the reaction is carried out in an aqueous phase, and the pressure in the reactor is usually large enough to prevent the vaporization of ammonia and ethylene oxide at the reaction temperature.

[0145] The ammonia concentration in water is preferably between 50 and 100%.

[0146] The reaction pressure in the aqueous phase reaction is generally up to 160 bar, preferably 90 - 130 bar (absolute pressure).

[0147] The reaction temperature in the aqueous phase reaction is usually up to 150 °C, preferably 40 - 130 °C.

[0148] Generally, in the aqueous phase reaction, up to 40 moles of excess ammonia per mole of ethylene oxide are used.

[0149] The unconsumed ammonia and water are generally separated from the product in the distillation line downstream of the reactor and recycled.

[0150] The product distribution of the three types of ethanolamines can be controlled by appropriately selecting the ammonia:ethylene oxide ratio.

[0151] The above reaction can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, but in order to obtain monoethanolamine, usually post-treatment by distillation is required to remove diethanolamine and triethanolamine.

[0152] In the preparation of polyethyleneimine described in the following steps (f), (g) and (h), monoethanolamine is required, which is generally separated from the ethanolamines generally obtained as a mixture of monoethanolamine, diethanolamine and triethanolamine in steps (a) to (e) of the process according to the invention by distillation (see step (f) below).

[0153] However, when using the ethanolamine according to the invention for uses different from the preparation of polyethyleneimine, separation of monoethanolamine may not be necessary. In carbon capture, for example, a mixture of monoethanolamine and diethanolamine can be used, and only triethanolamine generally needs to be separated by distillation.

[0154] Ethanolamines are a family of chemicals that function as surfactants and emulsifying components in personal care products, cleaning products and industrial applications. Further uses of ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the invention are, for example, as follows.

[0155] Personal care products Ethanolamines such as MEA and especially TEA function as detergents or surfactants in personal care products and cosmetics. In these types of products, ethanolamines dissolve fats and oils and blend with other important components to help remove dirt and oil from the skin. Since ethanolamines do not emit a strong odor, they are commonly used as ingredients in products such as hair dyes. Ethanolamines such as MEA adjust the pH of the product to prevent the product from deteriorating when stored in a container, thus extending the product's lifespan.

[0156] Household and industrial cleaning products Ethanolamines such as MEA are commonly used ingredients in cleaning products such as floor and tile cleaners and laundry detergents. As surfactants in these products, ethanolamines help remove dirt, fats and oils, and stains.

[0157] DEA is a commonly used ingredient in industrial cleaning products such as engine degreasers and industrial detergents due to its ability to break down fats and oils.

[0158] Industrial uses MEA acts as a plasticizer and helps make plastics flexible and soft. In chemical manufacturing plants, MEA is used to remove carbon dioxide from ammonia gas in the production of synthetic ammonia.

[0159] As a chemical intermediate, DEA is used in pesticides to manufacture insecticides and helps enhance the ability of the insecticides to dissolve in water. In the manufacture of waxes, abrasives and coating products, DEA acts as an emulsifier that helps the components blend and helps prevent other materials from corroding.

[0160] Due to their emulsifying properties, MEA and DEA can also be used in industrial applications such as chemical manufacturing and gas treatment. In oil refineries and gas treatment processes for natural gas streams, MEA and DEA help remove contaminants from gasoline.

[0161] TEA is used as a surfactant in pesticides to help the pesticides disperse on crops and then help drive insects away from the crops. As a demulsifier for petroleum, TEA helps separate oil from water and other substances. In cement additives, TEA helps promote the setting and / or hardening of cement. It is also a corrosion inhibitor for steel and zinc materials used in construction and building.

[0162] Accordingly, the present invention further relates to the use of the ethanolamines of the present invention selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof in any one of the above applications.

[0163] A carbon capture agent, surfactant, emulsifier, detergent, pH adjuster, plasticizer, gas sweetening agent, corrosion inhibitor and cement additive comprising at least one ethanolamine selected from monoethanolamine, diethanolamine and triethanolamine according to the present invention.

[0164] Examples of the description can be found, for example, in "Ethanolamines" by Mia Monconduit and Tison Keel, IHS Markit, Chemical Economics Handbook, 14 February 2020, pp. 19 - 20.

[0165] The present invention further relates to ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof, wherein the molar fraction of deuterium is 100 ppm or less, preferably in the range of 10 to 98 ppm or less, more preferably in the range of 10 to 95 ppm or less, and most preferably in the range of 10 to 90 ppm or less, based on the total hydrogen content.

[0166] The ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof according to the present invention is characterized by a low deuterium molar fraction.

[0167] The ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof is preferably prepared by a method including at least step (a) according to the present invention. More preferably, the ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof is prepared according to the present invention including steps (a) to (e).

[0168] The present invention further relates to a method for preparing polyethyleneimine, the method comprising (f) separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the method according to the present invention or from the ethanolamine according to the present invention, and (g) converting monoethanolamine to ethyleneimine, and (h) polymerizing the ethyleneimine obtained in step (g) to polyethyleneimine. The present invention relates to a method comprising the above steps.

[0169] Step (f): Step (f) includes separating monoethanolamine from the ethanolamine obtained in steps (a) to (e) of the method according to the present invention or from the ethanolamine according to the present invention.

[0170] Reaction step (e) can be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia. However, in order to obtain monoethanolamine, separation is usually necessary to remove diethanolamine and triethanolamine. Said post-treatment is generally known in the art and is usually carried out by distillation.

[0171] Examples of the description of the monoethanolamine production process 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.

[0172] Step (g): In step (g), monoethanolamine is converted to ethyleneimine (aziridine).

[0173] Suitable methods for preparing ethyleneimine from monoethanolamine are generally known in the art.

[0174] A preferred commercial process is catalytic gas-phase dehydration. For suitable examples of the catalyst composition, see U.S. Patent No. 4,841,061, and for the respective ethyleneimine gas-phase process conditions, see U.S. Patent No. 4,966,980.

[0175] In this process, ethyleneimine is generally prepared by dehydrating monoethanolamine at a temperature of 350 - 450 °C and generally under a reduced pressure of 30 - 500 mbar (absolute pressure).

[0176] This process is generally carried out in the presence of a catalyst having a weakly basic site and an acidic site (for example, based on Si-Cs-P or Si-Rb-P). An overview of this manufacturing technique and the optimal catalyst composition with high yields (up to 80 mol%), selectivity, and activity can be found in Applied Catalysis A: General 221 (2001) 209-217; Acid-base catalysis: On the example of ethylenimine production; Hideaki Tsuneki; Nippon Shokubai Co., Ltd., Functions and Materials Research Laboratory, Suita City 564-8512, Japan. Due to the high processing temperature despite the short contact time, this process is prone to catalyst deactivation by coking and sintering, as well as loss of active components. To improve the catalyst life, a catalyst regeneration cycle by, for example, trimethyl phosphate treatment can be used as described in Applied Catalysis A: General 331 (2007) 95-99; Deactivation and regeneration of ethylenimine production catalyst; Hideaki Tsuneki, Kimio Ariyoshi; Nippon Shokubai Co., Ltd., Functions and Materials Research Laboratory, Suita City 564-8512, Japan.

[0177] The catalytic gas-phase dehydration process is usually carried out in the gas phase in a flow tube reactor.

[0178] The resulting product mixture is usually separated by quenching followed by multi-stage distillation to obtain high-purity ethylenimine, and the unreacted monoethanolamine is returned to the reactor.

[0179] Another preferred commercial process is the liquid-phase dehydration by the Wenker process, first described in H. Wenker, J. Am. Chem. Soc. 57 (1935) 2328. This technique is generally a two-step process in which monoethanolamine is generally reacted with sulfuric acid to form 2-aminoethyl hydrogen sulfate as an intermediate product. Usually, by subsequent addition of sodium hydroxide, dehydration is usually achieved under pressure and high temperature as described in H. Kindler, W. Sanne, R. Sinn, A. Wittwer, Chem. Ing. Tech. 37 (1965) 400 and German Patent No. 1302658, 1971 (R. Sinn, W. Sanne, H. Kindler; BASF Aktiengesellschaft).

[0180] The liquid-phase ethyleneimine process is generally carried out in batch or continuous mode, and the yield is usually very high at 85 - 90 mol%, and high-purity ethyleneimine with excellent properties required for, for example, high-molecular-weight polyethyleneimine and other derivatives can be obtained after distillation.

[0181] Step (h) In step (h), the ethyleneimine obtained in step (g) is polymerized to polyethyleneimine.

[0182] Processes suitable for the preparation of polyethyleneimine by polymerization of ethyleneimine (aziridine) are known to those skilled in the art.

[0183] Polyethyleneimine is preferably prepared by cationic ring-opening polymerization of ethyleneimine in the presence of a Bronsted acid, a Lewis acid, a haloalkane or carbon dioxide. Examples are described in U.S. Patent No. 2,182,306 and U.S. Patent No. 3,203,910 and U.S. Patent Application Publication No. 2001 / 0039318.

[0184] Additional references, including further examples for polyethylene synthesis, include "Aziridines and azetidines: building blocks for polyamines by anionic and cationic ring-opening polymerization" Gleede, T.; Reisman, L.; Rieger, E.; Mbarushimana, P.C.; Rupar, P.A.; Wurm, F.R.; Polymer Chemistry 2019, 10, 3257.

[0185] The polymerization can be carried out, for example, in a batch process by placing water and 1,2-dichloroethane as a catalyst in a reaction vessel, heating the mixture to a temperature of 70 - 100 °C, and continuously adding ethyleneimine while stirring the reaction mixture.

[0186] The resulting polyethyleneimine is generally a branched or hyperbranched polyethyleneimine.

[0187] The resulting polyethyleneimine preferably has a weight average molecular weight M in the range of 500 - 2,000,000 g / mol, preferably in the range of 500 to 100,000 g / mol. w It has.

[0188] The degree of branching of the polyethyleneimine is measured by 13C NMR spectroscopy in D2O and is preferably in the range of 0.45 - 0.75, more preferably in the range of 0.5 - 0.7, and most preferably in the range of 0.55 - 0.7. The degree of branching is calculated as (D + T) / (D + T + L). In this formula, D refers to dendritic (or tertiary) amine groups, L (linear) refers to secondary amino groups, and T (terminal) refers to primary amino groups. 13 The polyethyleneimine of the present invention is characterized by a low molar share of deuterium, which is in the range of 110 ppm or less, preferably in the range of 10 - 105 ppm or less, more preferably in the range of 10 to 95 ppm or less, and most preferably in the range of 10 to 92 ppm or less, based on the total hydrogen content.

[0189] ​

[0190] The present invention further relates to a polyethyleneimine in which the molar share of deuterium is 110 ppm or less, preferably in the range of 10 to 105 ppm or less, more preferably in the range of 10 to 95 ppm or less, and most preferably in the range of 10 to 92 ppm or less, based on the total hydrogen content.

[0191] The polyethyleneimine is preferably prepared by a method including at least step (a) according to the present invention. More preferably, the polyethyleneimine is prepared by the method of the present invention including steps (a) to (h).

[0192] The polyethyleneimine according to the present invention is characterized by a low deuterium molar share. They exhibit a different deuterium share from petrochemically produced polymers and ethanolamines produced by petrochemical processes, i.e., based on fossil energy.

[0193] An important feature of ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof and the polyethyleneimine of the present invention is a low deuterium molar share. The low deuterium molar distribution is mainly introduced by step (a) of the method according to the present invention. Therefore, ammonia prepared by reacting hydrogen obtained in step (a) with nitrogen is also characterized by a low deuterium molar share.

[0194] Therefore, the present invention further relates to a method for producing ammonia, the method comprising: (a) providing hydrogen in which the molar share (deuterium content) of deuterium is less than 90 ppm based on the total hydrogen content by electrolysis based on electricity generated at least partially from non-fossil energy, preferably renewable resources; (b) reacting the hydrogen obtained in step (a) with nitrogen to form ammonia. comprises.

[0195] Steps (a) and (b) are the same steps as described above.

[0196] The present invention further relates to ammonia in which the molar share of deuterium is 100 ppm or less, preferably in the range of 10 to 95 ppm or less, more preferably in the range of 10 to 90 ppm or less, and most preferably in the range of 10 to 80 ppm or less, based on the total hydrogen content.

[0197] The present invention provides environmentally friendly ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine and ammonia, and an environmentally friendly process for producing the same, wherein the process uses fossil energy as little as possible.

[0198] The environmentally friendly preparation compounds, namely ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine and ammonia, have been found to be characterized by particularly low deuterium molar shares.

[0199] As described above, it is important that the origin of hydrogen and downstream compounds obtained by clean energy can be traced in a reliable manner.

[0200] Currently, most hydrogen is produced from fossil fuels by steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavy hydrocarbons, and coal gasification.

[0201] However, until now, it has not been possible to distinguish hydrogen obtained by steam reforming, partial oxidation and coal gasification, i.e., hydrogen obtained from fossil resources, from hydrogen obtained by electrolysis. As described above, hydrogen obtained by electrolysis is preferably obtained by using a non-fossil energy source. In the near future, it is expected that the electrification (power generation) of fossil resources will be completely replaced by power generation from non-fossil resources.

[0202] Accordingly, the present inventors have found a method for tracing the origin of hydrogen and downstream products of hydrogen, preferably ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine, ammonia and hydrogen, by means of the deuterium molar share of said compounds. Downstream products based on hydrogen, preferably ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine, ammonia based on hydrogen obtained by electrolysis and hydrogen itself can be distinguished from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine, ammonia and hydrogen prepared by a process based on fossil energy, i.e. produced by a petrochemical process, by their deuterium molar share.

[0203] Furthermore, it has been found that by using carbon oxides such as carbon monoxide and preferably carbon dioxide together with hydrogen instead of petrochemical synthesis gas in the subsequent synthesis routes of ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine and ammonia, the molar share of deuterium in these compounds is very low and has excellent traceability.

[0204] Accordingly, the present invention relates to the use of the deuterium molar share in hydrogen and downstream compounds based on hydrogen for tracing the origin, in particular the energy origin, of hydrogen and downstream compounds based on hydrogen, said compounds being preferably ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia.

[0205] The present invention further relates to a method for tracing the origin, in particular the energy origin, of hydrogen and the downstream compounds based on hydrogen by determining the molar share of deuterium in hydrogen and the downstream compounds based on hydrogen, said compounds being preferably ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia.

[0206] Downstream products based on hydrogen are generally products prepared by using hydrogen, preferably ethanolamine, selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine, ammonia and methanol. The preparation of downstream products as well as other downstream products based on hydrogen is known in the art.

[0207] Tracing is, in the meaning of the present invention, synonymous with tracking.

[0208] In the meaning of the present invention, origin means the production method of the hydrogen used, in particular electrolysis and / or the energy origin, i.e. a non-fossil energy source. As described above, it is expected that in the near future, the electrification (power generation) of fossil resources will be completely replaced by power generation using non-fossil resources. The hydrogen produced by electrolysis is, in this case, hydrogen of non-fossil origin. Examples of non-fossil power sources have been described above.

[0209] The method of the present invention for tracing the origin, in particular the energy origin, of hydrogen and the downstream compounds described above can be used as a single tracing method or in combination with further tracing methods.

[0210] In the present application, reference is made to suitable deuterium molar shares of hydrogen-based compounds obtained on the basis of hydrogen produced by electrolysis, in particular obtained by the method of the present invention, in particular ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethyleneimine or ammonia, as well as hydrogen itself.

[0211] Due to its polyamine structure, polyethyleneimine (PEI) polymer is capable of protonation, chelation and reaction and is very attractive in various applications.

[0212] As mentioned above, PEI is useful for reducing greenhouse gas emissions in CO2 capture, for example in the form of gas separation membranes for CO2 capture and in the purification of H2 from gas mixtures such as CO2 / N2 and H2 / N2.

[0213] Further examples of typical uses of PEI are as follows: - Wet strength additives in the paper industry to improve the strength of paper products - Use in detergents and cosmetics - Adhesion promoters for printing inks and adhesives - Primers for coating applications to improve adhesion to various substrates such as glass, wood, plastics and metals - Flocculants for precipitating colloidal particles from water - Removal of heavy metal ions from sewage (e.g., Cu 2+ 、Pb 2+ 、Cr 6+ 、Cd 2+) - Green blowing agents for polyurethanes - Chelating agents having the ability to complex metal ions such as zinc and zirconium - Antibacterial coatings: PEI can be used as an antibacterial coating on the surface. PEI has been shown to be active against a wide range of microorganisms including bacteria, viruses and fungi - Fiber industry: PEI can be used as a crosslinking agent in the fiber industry to improve the durability and strength of fabrics. - 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.

[0214] Further uses of PEI are in the biological and medical fields: - Gene transfection agent for biomedical applications - Mucosal adjuvant for various vaccines - Design of immobilized enzyme biocatalysts - Use in laboratory biology, especially tissue culture - Adhesion promoter for weakly immobilizing cells in cell cultures - Gene delivery: PEI can be used as a gene delivery agent in gene therapy. It has been shown to efficiently deliver plasmid DNA into cells and can be used for both in vitro and in vivo applications - Protein purification: PEI can also be used as a protein purification agent. PEI can selectively bind to proteins and is particularly useful for the purification of negatively charged proteins. - 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.

[0215] Accordingly, the present invention further relates to the use of the polyethyleneimine of the present invention in any one of the above uses.

[0216] The present invention further relates to a CO2 capture agent comprising or consisting of at least one polyethyleneimine according to the present invention, in particular a gas separation membrane for CO2 capture and H2 purification from gas mixtures such as CO2 / N2 and H2 / N2, a wet strength additive in the paper industry, detergents, cosmetics, in particular an adhesion promoter for printing inks and adhesives, a primer in coating applications, a flocculant for precipitating colloidal particles from water, in particular a chelating agent for heavy metal ions in sewage, a green blowing agent for polyurethanes, an antibacterial coating, a crosslinking agent in the fiber 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 adhesion promoter for weakly immobilizing cells in cell culture, a gene delivery agent in gene therapy, a protein purification agent or a coating for biomedical implants.

Embodiments for Carrying Out the Invention

[0217] The present invention is further illustrated by the following examples. Examples Experimental Results - Overview

[0218]

Table 1

[0219] I Hydrogen Production Experimental Setup and Method: Electrolysis Cell Design and Hydrogen Production Conditions

[0220] 1) Polymer Electrolyte Membrane / Proton Exchange Membrane Electrolysis (PEM) Electrolytic cell Water electrolysis was carried out using a circular commercially available PEM electrolysis cell (model ZE 200, Sylatech Analysetechnik GmbH, effective area 0.007 m 2) Sealed the cell stack with O-rings and wrapped it with a heat-insulating cloth for isothermal operating conditions. A Nafion® 117 standard membrane (supplied by DuPont, dry thickness 180 microns) was coated with iridium (19 g / m2 ) and platinum (8 g / m 2 ) was assembled by HIAT GmbH. The water distribution in the anode half-cell was realized using a titanium mesh. A porous transport layer using a sintered titanium fiber material was used to control the flow in front of the polymer electrolyte membrane, and a porous graphite plate was placed on the cathode side.

[0221] Experimental conditions Temperature-controlled water was supplied to the anode compartment at a constant flow rate of 9.5 g / h. The cell pressures on the cathode and anode sides were controlled with a PC valve. For experimental conditions such as temperature and pressure settings, refer to the table. The hydrogen and oxygen gases generated in the half-cell were separated in a two-stage separation device configuration with an intermediate condenser cooled by cooling water at 20°C. The condensed water flowed back to the separator tank. The cell-water of the anode was recirculated, while the separated water was discharged at the cathode. The remaining gas moisture was separated by a desiccant dryer to ensure complete separation of the moisture in the electrolysis gas stream. Small gas samples of the dehydrated cathode hydrogen gas were taken at regular intervals from the continuous flow using an autosampler for the hydrogen gas analysis described below.

[0222] 2) Alkaline electrolysis cell (AEC) Electrolytic cell Alkaline water electrolysis was carried out using a circular AEC electrolysis cell (model Electro MP Cell, supplier ElectroCell Europe A / S, electrode area 0.01 m 2 ). As the electrodes, nickel 2.4068 material was used, and a commercially available standard Zirfon Perl UTP 500 membrane (open mesh polyphenylene sulfide fabric symmetrically coated with a mixed polymer / zirconium oxide; thickness 500 microns; active area 0.023 m 2 ; supplier Agfa-Gevaert N.V.) was used for separation.

[0223] Experimental conditions The temperature-controlled alkaline water (32 wt% potassium hydroxide, technical standard grade) was supplied to the anode and cathode compartments at a constant flow rate of 27.8 kg / h. The cell pressures on the cathode side and the anode side were equalized via PC valve control. For experimental conditions such as temperature and pressure settings, please refer to the table. The hydrogen and oxygen gases generated within the half-cell were separated in a two-stage separation device configuration equipped with an intermediate condenser cooled by 20°C cooling water. The condensed water flowed back to the separator tank. The cell-water of the anode and cathode was recirculated. The remaining gas moisture was separated by a desiccant dryer to ensure complete separation of the moisture in the electrolytic gas stream. Small gas samples of the dehydrated cathode hydrogen gas were collected at regular intervals from the continuous flow using an autosampler for the hydrogen gas analysis described below.

[0224] 3) Anion Exchange Membrane / Alkaline Electrolyte Membrane Electrolysis (AEM) Electrolytic cell The AEM experiments were carried out with a commercially available fully automated 2.4 kW EL 4.0 cell supplied by Enapter GmbH, 10117 Berlin, and an electrolyte of 1 wt% potassium hydroxide (standard grade).

[0225] Test station As recommended by the supplier, the EL 4.0 electrolyzer was operated using a 1 wt% potassium hydroxide (technical standard grade) solution, and the hydrogen production rate under the operating conditions (for experimental conditions such as temperature and pressure settings, please refer to the table) was 480 l / h with about 400 ml of water consumption. The generated hydrogen gas was treated by a desiccant dryer to ensure complete separation of the moisture in the electrolytic gas stream, and the moisture in the hydrogen gas stream was less than 0.03 wt%. Small gas samples of the dehydrated cathode hydrogen gas were collected at regular intervals from the continuous flow using an autosampler for the hydrogen gas analysis described below.

[0226] 4) Solid Oxide Electrolysis Cell (SOE) The E3000 unit was operated in reverse mode at 700 °C and an electrolysis current of 35 A using a solid oxide cell stack manufactured by Elcogen - Elco Stack (Elcogen OY, Vantaa 01510 Finland). The anode functional composition by the supplier is NiO / YSZ. The cathode is of the LSC type [La(Sr)CoO3]: The principle is also described in Novel high - performance solid oxide fuel cells with bulk ionic conductance dominated thin - film electrolytes - ScienceDirect; D. Stover et al, Journal of Power Sources; Volume 218, 15 November 2012, Pages 157 - 162.

[0227] The hydrogen stream was used without further purification / drying. The remaining gas moisture was separated by a desiccant dryer to ensure complete separation of the moisture in the electrolysis gas stream. Small gas samples of the dehydrated cathode hydrogen gas were taken at regular intervals from the continuous flow using an autosampler for the hydrogen gas analysis described below.

[0228] The results of hydrogen production are shown in Table 1.

[0229] Experimental setup and method: "D content (deuterium content) in the sample" The following method description applies to the determination of the molar share of deuterium based on the total hydrogen content (deuterium content) of gas and liquid samples. Isotope H / D sharing analysis is based on mass spectrometry. Two different methods, Method A for gas samples and Method B for liquid samples, are used.

[0230] In order to determine the "D content in gas and liquid samples", it is very important, for example, not to contaminate the sample with ambient humidity or other ambient components containing hydrogen or deuterium. Therefore, it is necessary to use airtight materials and seals together with a clean sample container to avoid cross-contamination. Therefore, before filling and sealing the sample container, it is necessary to flush at least 20 times the volume of the sample container with the gas or liquid flow to be analyzed. The same applies to the experimental settings of the gas sampler and the mass spectrometer. For example, utmost care must be taken to avoid cross-contamination due to condensation of humidity. The analysis settings from sampling to mass spectrometry are verified using known reference samples.

[0231] Method A) Gas sample The total deuterium from HD and D2 in the hydrogen gas sample was determined by ultra-high resolution quadrupole mass spectrometry using the Hiden DLS-20 (Hiden Analytical Ltd., Warrington, Cheshire, UK) analyzer settings. General method settings are described in C.C. Klepper, 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. The threshold ionization mass spectrometry (TIMS) mode described in S. Davies, J.A. Rees, D.L. 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 was used for the hydrogen gas sample. The sensitivity is + / -1 ppm.

[0232] Method B) Liquid sample Analysis of liquid samples (ammonia, monoethanolamine (MEA) and polyethyleneimine (PEI)) was performed by isotope ratio monitoring gas chromatography / mass spectrometry (IRMS). For this purpose, a DELTA V PLUS CF-IRMS mass spectrometer was used. This mass spectrometer equipped with a magnetic sector with continuous flux DELTA V PLUS CF-IRMS was used to measure the isotope ratio of 2H / 1H.

[0233] For the measurement of D / H in continuous He flow mode, it is necessary to completely remove low-energy 4He+ ions from the HD+ ion beam at m / z 3). This method is described in RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun.Mass Spectrom.13,1226-1230(1999), W.A. Brandt et al. The sensitivity is within + / -3 ppm.

[0234] II Production of ammonia, ethylene oxide (EO), ethanolamine and polyethyleneimine (PEI) Ammonia, ethylene oxide and monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA) as pure components or ethanolamine as a mixture of MEA, DEA and / or TEA are prepared using the catalytic synthesis process on an industrial scale as described above.

[0235] By using non-fossil-based energy for electrolytic hydrogen in both ammonia synthesis and methanol synthesis at the core of this value chain, the only substance in the downstream-produced EO, MEA, DEA, TEA, hydrogen, actually comes from electrolytic hydrogen with a low deuterium content. This is a significant difference, especially in the case of ammonia, since the fossil-based production process relies on syngas produced from fossil natural gas and a large amount of steam. This steam reforming step is not necessary for the non-fossil ammonia route based on pure hydrogen and nitrogen.

[0236] In all large-scale commercial production processes using non-fossil hydrogen, no significant additional amount of hydrogen species is introduced into the mass balance of the "input / output" process. This is necessary to minimize the output of undesirable wastewater or other liquid and gas effluent streams and to ensure a high yield with the purity according to the product specifications.

[0237] When ambient air is used for the direct oxidation of ethylene in EO production, the ambient moisture is purged together with nitrogen and other inert gases because it does not participate in the catalytic reaction. Therefore, the EO product itself actually consists only of the material hydrogen derived from ethylene. Ethylene produced from methanol derived from hydrogen and carbon oxides in an MTO or similar process has approximately the same deuterium concentration as the hydrogen source.

[0238] When water is used as a processing aid for stripping / scrubbing / washing or quenching / condensing of the internal flow in a process, for example, in ammonia, methanol, ethylene oxide and / or ethanolamine synthesis steps, this water is always operated in a nearly closed cycle with a minimum purge to ensure that the secondary contamination by deuterium is minimal.

[0239] When hydrogen species are introduced into a continuous industrial process, these feed streams are always less than, at least two orders of magnitude smaller than, or in other words, less than 1% of the output stream of the target product. Therefore, a worst-case calculated increase factor of 1.01 for the deuterium content was used for each of the ethylene (MTO-based), ammonia and ethanolamine process steps.

[0240] In the case of ethyleneimine (EI) synthesis, as described, two different routes are commercially relevant. The liquid-phase dehydration "Wenker process" is carried out with fresh water and aqueous dilution with molar amounts of sulfuric acid and caustic. Thus, the "acidic N-hydrogen" of ethyleneimine is substantially completely exchanged with the deuterium content of the aqueous feed mixture. It can be assumed that 1 / 5 of the mole fraction of deuterium has the VSMOV baseline concentration (155.76 ppm), while the remaining 4 / 5 of the hydrogen species maintain the low deuterium content of the ethanolamine source due to the strong nature of the C-H bond. Thus, the formula D-content (EI) = 1 / 5 * D-content (VSMOV) + 4 / 5 * D-content (MEA) is used.

[0241] The catalytic gas-phase dehydration process produces a concentrated ethyleneimine monomer of over 98% in the final sequence of the distillation work-up step without introducing large amounts of hydrogen species separately from the MEA feedstock.

[0242] Similar to the upstream catalytic process, for example, the bleed of hydrogen species from a partially acidic catalyst is not relevant to the mass balance of the substance with an industrially appropriate high space-time yield.

[0243] However, ethyleneimine itself is not suitable as a relevant commercial end product due to its harmful toxicity and extreme reactivity. Polyethyleneimine (PEI) products are produced by cationic ring-opening polymerization of ethyleneimine (EI) in an aqueous solution containing an initiator and fresh water as described above to remove the strong exotherm of polymerization. Polymerization that is not significantly diluted with water cannot be controlled safely on a large scale. Therefore, industrially common PEI products are usually polymerized in batch or (oder) semi-batch mode while controlling the temperature, for example, at a final aqueous solution concentration of 30 or 50%. This means that the "acidic N-hydrogen" from ethyleneimine is substantially completely exchanged with the deuterium content of the fresh water used in the polymerization step. Since the H-D exchange on this "acidic N-hydrogen" occurs only once, the results regarding the deuterium content are substantially the same: both polyethyleneimines based on either the liquid or gas-phase dehydrated EI monomer process have the same deuterium content approximated by the equation D-content (PEI) = 1 / 5 * D-content (VSMOV) + 4 / 5 * D-content (MEA).

[0244] Table 2 shows the deuterium (D) content in hydrogen, ammonia, monoethanolamine (MEA), and polyethyleneimine (PEI) based on fossil resources (FR) (comparative examples) and non-fossil resources (NFR) (examples of the present invention). The products of FR (comparative examples) are conventional petrochemical products of BASF SE. The deuterium content of the products obtained from NFR is calculated as described above using the D content of the hydrogen in Examples I) to VI) (see Table 1) as starting materials for both the ammonia synthesis route and the ethylene synthesis route.

[0245]

Table 2

[0246] Examples based on NFR show a significantly lower D content and can be clearly distinguished from the conventional products based on FR.

Claims

1. An ethanolamine selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof, wherein the molar share of deuterium is 100 ppm or less, preferably in the range of 10 to 98 ppm or less, more preferably in the range of 10 to 95 ppm or less, and most preferably in the range of 10 to 90 ppm or less, based on the total hydrogen content.

2. A method for producing the ethanolamine according to claim 1, selected from monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof, the method comprising: (a) providing hydrogen having a molar share of deuterium of 100 ppm or less, based on the total hydrogen content, by electrolysis based on electricity generated at least in part from non-fossil energy; (b) reacting the hydrogen obtained in step (a) with nitrogen to form ammonia; (c) reacting the hydrogen obtained in step (a) with a carbon oxide, preferably carbon dioxide, to form methanol; (d) converting the methanol obtained in step (c) to ethylene and further to ethylene oxide; (e) converting the ammonia obtained in step (b) and the ethylene oxide obtained in step (d) to ethanolamine in one or more steps. A method comprising the above steps.

3. The method according to claim 2, wherein the electricity is generated at least in part from wind power, solar energy (heat, photovoltaic, concentrating), hydroelectric power (tidal power, wave power, hydroelectric dam, in-river hydroelectric power), geothermal energy, ambient heat captured by a heat pump, bioenergy (biofuel, biomass), the renewable portion of waste, or nuclear power (nuclear 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 carbon dioxide is used in step (c), and the carbon dioxide is preferably captured from industrial flue gas or ambient air.

6. The ethylene oxide in step (d) is: (d1) preferably a methanol-olefin process for obtaining ethylene using a zeolite catalyst, followed by Epoxidation of ethylene, preferably using a silver-based catalyst The method according to any one of claims 2 to 5, obtained by

7. Reacting the ammonia obtained in step (b) and the ethylene oxide obtained in step (d) in one or more steps to obtain a reaction product containing monoethanolamine, diethanolamine and triethanolamine, according to any one of claims 2 to 6 The method described in the section.

8. A polyethyleneimine in which the molar share of deuterium is 110 ppm or less, preferably in the range of 10 to 105 ppm or less, more preferably in the range of 10 to 95 ppm or less, and most preferably in the range of 10 to 92 ppm or less, 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 method according to any one of claims 2 to 7, or from the ethanolamine according to claim 1 (g) Converting monoethanolamine to ethyleneimine (h) Polymerizing the ethyleneimine obtained in step (g) to obtain polyethyleneimine A method comprising.

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

11. An ammonia in which the molar share of deuterium is 100 ppm or less, preferably in the range of 10 to 95 ppm or less, more preferably in the range of 10 to 90 ppm or less, and most preferably in the range of 10 to 80 ppm or less, based on the total hydrogen content.

12. The method for producing ammonia according to steps (a) and (b) according to any one of claims 2 to 4.

13. Use of the molar share of deuterium in hydrogen and hydrogen-based downstream compounds to trace the origin of the preparation of hydrogen and hydrogen-based downstream compounds, wherein the compounds are preferably selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof Ethanolamine, polyethyleneimine or ammonia.

14. A method for tracing the origin of the preparation of hydrogen and the downstream compound based on hydrogen by determining the molar share of deuterium in hydrogen and the downstream compound based on hydrogen, wherein the compound is preferably ethanolamine, polyethyleneimine or ammonia selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof.

15. CO ２ Capture agent, gas separation membrane, wet strength additive in the paper industry, detergent, cosmetic, adhesion promoter for printing ink and adhesive, primer for coating applications, flocculant for precipitating colloidal particles from water, chelating agent for heavy metal ions in sewage, green foaming agent for polyurethane, antibacterial coating, crosslinking agent in the fiber industry, coating for food packaging materials, gene transfection agent for biomedical applications, mucosal adjuvant for various vaccines, immobilized enzyme biocatalyst, adhesion promoter for weakly immobilizing cells in cell culture, gene delivery agent in gene therapy, protein purification agent or use of the polyethyleneimine according to claim 8 as a coating for biomedical implants or therein.

16. A CO scavenger, gas separation membrane, wet strength additive in the paper industry, detergent, cosmetic, adhesion promoter for printing ink and adhesive, primer in coating applications, flocculant for precipitating colloidal particles from water, chelating agent for heavy metal ions in sewage, green foaming agent for polyurethane, antibacterial coating, crosslinking agent in the fiber industry, coating for food packaging materials, gene transfection agent for biomedical applications, mucosal adjuvant for various vaccines, immobilized enzyme biocatalyst, adhesion promoter for weakly immobilizing cells in cell culture, gene delivery agent in gene therapy, protein purifying agent or coating for biomedical implants, comprising or consisting of at least one polyethyleneimine according to claim 8. ２ A CO scavenger, gas separation membrane, wet strength additive in the paper industry, detergent, cosmetic, adhesion promoter for printing ink and adhesive, primer in coating applications, flocculant for precipitating colloidal particles from water, chelating agent for heavy metal ions in sewage, green foaming agent for polyurethane, antibacterial coating, crosslinking agent in the fiber industry, coating for food packaging materials, gene transfection agent for biomedical applications, mucosal adjuvant for various vaccines, immobilized enzyme biocatalyst, adhesion promoter for weakly immobilizing cells in cell culture, gene delivery agent in gene therapy, protein purifying agent or coating for biomedical implants, comprising or consisting of at least one polyethyleneimine according to claim 8.

17. The ethanolamine according to claim 1, preferably monoethanolamine and / or diethanolamine, or the CO of the polyethyleneimine according to claim 8 ２ for use as a liquid or solid CO ２ absorbent in a capture process.

Images