Vinyl acetate with low deuterium content

Abstract

The present invention relates to: processes for producing vinyl acetate on the basis of methanol having a deuterium content of less than 90 ppm, comprising a step of reacting acetic acid with ethylene to obtain vinyl acetate; and processes for producing vinyl acetate based on methanol having a deuterium content of less than 90 ppm, comprising the steps of reacting acetic anhydride with acetaldehyde to form ethylidene diacetate, and reacting ethylidene diacetate to obtain vinyl acetate by thermal elimination of acetic acid; and vinyl acetate having a deuterium content of less than 90 ppm based on the total hydrogen content. The invention further relates to vinyl acetate of carbon-14 with natural abundance from non-fossil resources, preferably from biomass, and to the use thereof. The invention also relates to a process for the preparation of an alkoxylated compound comprising ethylene oxide units and / or propylene oxide units, comprising the steps of (a) reacting hydrogen with carbon dioxide to form methanol, (b) converting the methanol from step (a) to ethylene and / or propylene, (c) reacting the ethylene and / or propylene from step (b) with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and (d) reacting the ethylene oxide and / or propylene oxide with at least one starter unit having Zerewitinoff-active hydrogen atoms to form the alkoxylated compound, wherein the carbon dioxide in step (a) is at least partially captured from industrial flue gas or from air or from seawater or other natural water or is obtained from a biological process; and an alkoxylated compound obtainable by the process. The invention further relates to graft polymers based on ethylene oxide-containing main chains grafted with ethylenically polymerizable monomers, preferably vinyl monomers, more preferably vinyl lactams, a) vinyl esters or b) vinyl lactams wherein such graft polymers are based at least in part on hydrogen from non-fossil-based sources, wherein the molar fraction of deuterium in such a graft polymer is lower than the molar fraction of deuterium in the same compound when only derived from fossil-based sources.

Description

[0001] The present invention relates to methods for producing vinyl acetate based on methanol having a deuterium content of less than 90 ppm, the methods comprising the step of reacting acetic acid with ethylene to obtain vinyl acetate.

[0002] The present invention further relates to methods for producing vinyl acetate based on methanol having a deuterium content of less than 90 ppm, the methods comprising the steps of: reacting acetic anhydride with acetaldehyde to form ethylene diacetate, and reacting the ethylene diacetate to obtain vinyl acetate by thermal elimination of acetic acid.

[0003] The present invention further relates to vinyl acetate having a deuterium content based on a total hydrogen content of less than 90 ppm.

[0004] The present invention further relates to a method for producing vinyl acetate with natural abundance of C-14 from non-fossil resources, preferably biomass, the vinyl acetate obtained therefrom, and its uses.

[0005] In the chemical industry, methanol serves as a raw material for the production of olefins, formaldehyde, acetaldehyde, acetic acid, methyl acetate, acetic anhydride, and vinyl acetate. Conventional production methods involve catalytic processes using fossil fuels such as natural gas or coal.

[0006] Synthesis gas, used to produce methanol, can be produced from many sources, including natural gas, coal, biomass, or virtually any hydrocarbon feedstock, by reacting with steam (steam reforming), carbon dioxide (dry reforming), or oxygen (partial oxidation).

[0007] Syngas is produced from solid feedstock via coal gasification. This involves reacting coal in a mixture of partial oxidation with air or pure oxygen and gasification with steam to produce a mixture of carbon monoxide and hydrogen. Through the Boudouard equilibrium, carbon monoxide is in equilibrium with carbon and carbon dioxide.

[0008]

[0009] In addition, the water-gas shift reaction must also be considered.

[0010]

[0011] The exothermic reaction with oxygen provides the necessary energy to achieve the high reaction temperature used for the endothermic gasification reaction of carbon with water vapor.

[0012] In principle, other solid raw materials (wood, straw) can be used as alternatives to coal.

[0013] The most important gaseous derivative used in the production of syngas is natural gas, which is produced by reacting steam with water vapor through steam reforming. Natural gas provides the highest hydrogen to carbon monoxide ratio.

[0014]

[0015] In addition, liquid segregates (such as light naphtha fractions) can be reformed and reacted with steam after desulfurization.

[0016] To produce methanol, the ratio of carbon monoxide to hydrogen in the synthesis gas is adjusted to satisfy the following reaction equation.

[0017]

[0018] Syngas is primarily produced through steam reforming or partial oxidation of natural gas or through coal gasification. While natural gas is used for methanol production in North America and Europe, syngas production in China and South Africa is mainly based on coal. Depending on the carbon monoxide to hydrogen ratio, the product gas is called water gas (CO + H2), syngas (CO + 2 H2), or spaltgas (CO + 3 H2). Spaltgas can be made hydrogen-lean or carbon monoxide-rich (e.g., via a water-gas shift reaction by adding carbon dioxide and removing water), and water gas can be made hydrogen-rich or carbon monoxide-lean to obtain syngas.

[0019] The exothermic reaction of synthesizing methanol from CO2 is less than that of starting with syngas, and it also involves the reverse water-gas shift (RWGS) reaction as a secondary reaction. To facilitate methanol synthesis, CO in the syngas is converted to CO2 via the water-gas shift (WGS) reaction.

[0020] CO2 + 3 H2 CH3OH + H2OΔH298K = -49.5 kJ mol-1

[0021] CO2 + H2 CO + H2O ΔH298K = 41.2 kJ mol-1

[0022] If the CO2 originates from a suitable direct or indirect biological source, the aforementioned water-gas balance provides a basis for the production of CO2-neutral methanol. Based on the reverse water-gas shift (RWGS) reaction, there is an opportunity to directly incorporate bio-sourced CO2 into a suitable syngas-methanol process. The syngas is then converted to methanol using a CuO / ZnO / Al2O3 catalyst, for example, at temperatures ranging from 250°C to 300°C and pressures from 5 to 10 MPa.

[0023] In this sense, CO2 from different biological carbon sources can be included in syngas to form methanol. The biological source of CO2 can come from the fermentation process of biological materials, the combustion process of waste from biomass or bio-based materials, or the extraction process of atmospheric CO2, such as through extraction and regeneration steps (e.g., ammonia CO2 washing).

[0024] Of course, a mixture of CO2 from biological and fossil carbon sources can also be used to produce methanol.

[0025] 12 The natural isotopic abundance of C is approximately 98.9%. 13 The natural isotopic abundance of C is approximately 1.1%. (The compound's...) 13 C / 12 The C isotope ratio is given relative to the international standard Vienna-Pee-Dee-Belemnite (V-PDB). 13 C / 12 C isotope ratio in δ 13 The C value is given, in units of ‰. By definition, the standard has a δ of 0‰. 13 C value. Has a higher value than the standard. 13 Substances with C content have a positive ‰ value, which is lower than that of the standard. 13 Substances with high C content have negative ‰ values.

[0026] Fossil-based methanol derived from fossil-based syngas typically has a δ0.05 ranging from -50‰ to -25‰. 13 The C value depends on the fossil feedstock. Methanol based on carbon dioxide captured from ambient air typically has a δ value ranging from -10‰ to -2.5‰. 13 The C value corresponds to the δ value of carbon dioxide captured from ambient air. 13 C value.

[0027] In a preferred embodiment of the method of the present invention, the carbon dioxide provided in step (b) has a δ value corresponding to > -20‰. 13 C value 13 C content. Specifically, the carbon dioxide provided in step (b) has a δ value corresponding to -10‰ to -2.5‰. 13 C value 13 C content.

[0028] The present invention also relates to methanol having a deuterium content of less than 90 ppm based on a total hydrogen content. Preferably, the deuterium content is 30 to 75 ppm based on the total hydrogen content.

[0029] Methanol with a deuterium content of less than 90 ppm, preferably 30 to 75 ppm, based on a total hydrogen content of less than 90 ppm, preferably 30 to 75 ppm, can be used to prepare ethylene. Typically, the obtained ethylene also has a low deuterium content of less than 90 ppm, preferably 30 to 75 ppm. If carbon dioxide is captured from ambient air, the obtained ethylene... 13 The C content also corresponds to a δ content that is typically > -20‰. 13 The C value, more specifically, corresponds to δ from -10‰ to -2.5‰. 13 C value.

[0030] In physical organic chemistry, the kinetic isotope effect is the change in the rate of a chemical reaction when one of the atoms in a reactant is replaced by one of its isotopes. Formally, it involves the substitution of light (k) atoms for other atoms. L ) and weight(k H The rate constant k of a reaction involving isotopic substitution reactants (isotopes). L / k H The ratio of the two isotopes. This change in reaction rate is a quantum mechanical effect, primarily caused by the heavier isotope having a lower vibrational frequency compared to its lighter counterpart. In most cases, this means that the heavier isotope requires a larger energy input to reach the transition state, and therefore has a slower reaction rate.

[0031] The isotopic rate change is most significant when the relative mass change is largest because the effect is related to the vibrational frequencies of the affected bonds. For example, replacing hydrogen atoms (H) with their isotope deuterium (D) represents a 100% increase in mass, while using... 13 C substitute 12 At C, the mass increases by only 8%. Reactions involving CH bonds typically occur 6-10 times faster than the corresponding CD bonds, while... 12 The C reaction is only slightly more than the corresponding 13 C reacts 4% faster.

[0032] The first-order kinetic isotope effect can be observed when bonds with isotope atoms form or break. The second-order kinetic isotope effect is observed when bonds with isotope atoms in the reactants remain unbroken or unformed. The second-order kinetic isotope effect is often much smaller than the first-order kinetic isotope effect; however, the second-order deuterium isotope effect can be as large as 1.4 per deuterium atom.

[0033] Polyvinyl acetate (PVAC, PVA) is a thermoplastic. It is an amorphous, odorless, and tasteless plastic with high light and weather resistance. It is flammable but not easily burned. The glass transition temperature of homopolymers varies between 18°C ​​and 45°C, depending on the degree of polymerization. Electrical, mechanical, and thermal properties also depend to a large extent on the degree of polymerization. The minimum film-forming temperature of homopolymer dispersions is approximately 15°C to 18°C. Polyvinyl acetate is processed in the form of solutions in organic solvents or as dispersions.

[0034] PVA is used as a base material in paints and varnishes. This plastic is also used as an adhesive, such as as a white glue (wood glue), wallpaper paste, or parquet flooring adhesive. The general-purpose adhesive UHU, well-known in Germany, is a 40% solution of polyvinyl acetate in methyl acetate and acetone. Simple process adhesives often also primarily contain polyvinyl acetate and are also known as vinyl glues. Other applications include paper and coatings, textile impregnation, carpet backing, or modification of plaster and concrete. Additionally, PVA is commonly a component of chewing gum and is used for coating cheese or sausages.

[0035] Vinyl acetate can form copolymers with a variety of monomers such as ethylene, maleic anhydride, maleate esters, vinyl ethers, and allyl ethers. Copolymers, especially ethylene vinyl acetate copolymers (EVACs), are thus produced in large quantities to manufacture thermoplastic elastomers and thermoplastic materials. Depending on the ethylene:vinyl acetate ratio, a wide variety of applications can be addressed. Vinyl acetate contents of up to 7% are almost exclusively used to improve film properties (especially increasing elongation at break). Approximately half of EVAC production is carried out with vinyl acetate contents of less than 7%. EVACs with vinyl acetate contents of 7% to 18% are also frequently used as specialized materials for specific applications. Examples include cold-resistant pull-out nozzles for tanks, films for agriculture and horticulture, shrink wrap films (office supplies, solar panels), shower curtains, floor coverings, roofing films, and cables. EVACs with vinyl acetate contents of up to 28% are primarily used as hot melt adhesives, which in turn are used for fiber bonding in very high-quality tufted carpets and needle-punched nonwovens, perfect bonding in bookmaking, and manual use with hot melt glue guns. A rubber-like thermoplastic elastomer is produced when the vinyl acetate content is between 30% and 90%. It is mainly used in shoe soles, or as a polymer blend with other elastomers.

[0036] In addition, vinyl acetate monomer (VAM) can be used to prepare water-soluble graft polymers on a polyether matrix. These graft copolymers are used in laundry detergent compositions for anti-ashing purposes, such as Sokalan HP22 (DE3711298; BASF SE).

[0037] Vinyl acetate is produced from precursor bases such as ethylene and acetic acid. These bases are typically derived from fossil carbon sources, such as petroleum or natural gas. Because carbon sources lead to an undesirable CO2 balance, there is a need to produce vinyl acetate monomers (VAMs) and polyvinyl acetate, as well as copolymers, without using fossil carbon sources. Vinyl acetate can form polymers such as polyvinyl acetate, which can be hydrolyzed into biodegradable polyvinyl alcohol and biodegradable acetic acid. The production of vinyl acetate monomers (VAMs) from non-fossil renewable hydrogen and carbon sources has not been previously described.

[0038] The object of this invention is to provide an environmentally friendly method for producing methanol. Another object of this invention is to provide methanol with a low deuterium content. The favorable kinetic isotope effect caused by the low deuterium content of methanol can be cumulative, as it also exists in subsequent production steps further downstream in the value chain.

[0039] Another object of the present invention is to provide an environmentally friendly method for producing vinyl acetate.

[0040] This objective is achieved by a method for producing methanol having a deuterium content of less than 90 ppm based on a total hydrogen content, the method comprising the following steps:

[0041] (a) Using electricity generated at least in part from non-fossil renewable resources, hydrogen with a deuterium content of less than 90 ppm is produced by water electrolysis;

[0042] (b) Provide carbon dioxide;

[0043] (c) React hydrogen and carbon dioxide in the presence of a catalyst to form methanol.

[0044] This objective is further achieved by a method for manufacturing vinyl acetate, the method comprising the following steps:

[0045] (a) Using electricity generated at least in part from non-fossil renewable resources, hydrogen with a deuterium content of less than 90 ppm is produced by water electrolysis;

[0046] (b) Provide carbon dioxide;

[0047] (c) Reacting hydrogen and carbon dioxide in the presence of a catalyst to form methanol with a deuterium content of less than 90 ppm based on a total hydrogen content;

[0048] (d) React the methanol from step (c) to form ethylene; and

[0049] (e) React methanol from step (c) with carbon monoxide to form acetic acid; and / or

[0050] (f1) React a portion of the ethylene from step (d) with oxygen and water to obtain acetaldehyde;

[0051] (f2) React the acetaldehyde from step (f1) with oxygen to give acetic acid;

[0052] (g) React acetic acid from step (e) and / or step (f1) with ethylene from step (d) to obtain vinyl acetate.

[0053] This objective is further achieved by a method for manufacturing vinyl acetate, the method comprising the following steps:

[0054] (a) Using electricity generated at least in part from non-fossil renewable resources, hydrogen with a deuterium content of less than 90 ppm is produced by water electrolysis;

[0055] (b) Provide carbon dioxide;

[0056] (c) Reacting hydrogen and carbon dioxide in the presence of a catalyst to form methanol with a deuterium content of less than 90 ppm based on a total hydrogen content;

[0057] (d) React the methanol from step (c) to form ethylene; and

[0058] (e) React the ethylene from step (d) with oxygen and water to form acetaldehyde;

[0059] (f1) React a portion of the acetaldehyde from step (e) with oxygen to form acetic acid; and / or

[0060] (f2) React methanol from step (c) with carbon monoxide to form acetic acid; and

[0061] (g1) React acetic acid from step (f1) and / or step (f2) with methanol from step (c) to form methyl acetate;

[0062] (g2) React the methyl acetate from step (g1) with carbon monoxide to form acetic anhydride; and / or

[0063] (h1) Producing ketene from acetic acid from step (f1) and / or step (f2);

[0064] (h2) React the ketene from step (h1) with the acetic acid from step (f1) and / or step (f2) to obtain acetic anhydride;

[0065] (i) React the acetic anhydride from step (g2) and / or step (h2) with the acetaldehyde from step (e) to form ethylene diacetate;

[0066] (k) React diacetene with acetic acid to obtain vinyl acetate by thermal elimination of acetic acid.

[0067] Fossil-based methanol derived from syngas typically has a δ0.05 ranging from -50‰ to -25‰. 13 The C value depends on the fossil feedstock. Methanol based on carbon dioxide captured from ambient air typically has a δ value ranging from -10‰ to -2.5‰. 13 The C value corresponds to the δ value of carbon dioxide captured from ambient air. 13 C value.

[0068] In a preferred embodiment of the method of the present invention, the carbon dioxide provided in step (b) has a δ value corresponding to > -20‰. 13 C value 13 C content. Specifically, the carbon dioxide provided in step (b) has a δ value corresponding to -10‰ to -2.5‰. 13 C value 13 C content.

[0069] Therefore, if carbon dioxide is captured from ambient air, then methanol... 13 C content corresponds to δ, which is usually > -20‰. 13 The C value, more specifically, corresponds to δ from -10‰ to -2.5‰. 13 C value.

[0070] The present invention also relates to methanol having a deuterium content of less than 90 ppm based on a total hydrogen content. Preferably, the deuterium content is 30 to 75 ppm based on the total hydrogen content.

[0071] The deuterium content of hydrogen and hydrogen-containing compounds in this paper is based on the total hydrogen content (protium). 1 H and deuterium 2 The atomic percentage (ppm) of the total number of H atoms is given.

[0072] Water electrolysis is an environmentally friendly method for producing hydrogen because it uses renewable H2O and produces only pure oxygen as a byproduct. Furthermore, water electrolysis utilizes direct current (DC) from sustainable energy sources such as solar, wind, hydro, and biomass energy.

[0073] It has been observed that the deuterium content of hydrogen produced by water electrolysis is lower than that of hydrogen produced through petrochemical processes (such as hydrogen contained in syngas), typically below 90 ppm, preferably 30 to 75 ppm. The deuterium content in hydrogen produced by electrolysis can be as low as 15 ppm. Deuterium exists primarily in the form of DH rather than D2.

[0074] A suitable method for water electrolysis is alkaline water electrolysis. Producing hydrogen through alkaline water electrolysis is a mature technology, reaching commercial-grade megawatt levels. In alkaline water electrolysis, initially at the cathode side, two water molecules in the alkaline solution (KOH / NaOH) are reduced to one hydrogen molecule (H₂) and two hydroxide ions (OH⁻). - The generated H2 is released from the cathode surface in gaseous form, and hydroxide ions (OH-) are also released. - Under the influence of the electric field between the anode and cathode, the gases migrate through a porous membrane to the anode, where they are discharged as half-oxygen molecules (O2) and one water molecule (H2O). Alkaline electrolysis operates at relatively low temperatures (e.g., 30°C–80°C) using an alkaline aqueous solution (KOH / NaOH) as the electrolyte, with a concentration of approximately 20% to 30%. A membrane in the middle of the electrolytic cell separates the cathode and anode and also separates the generated gases from their respective electrodes, thus preventing mixing. However, alkaline electrolysis has disadvantages, such as a limited current density (below 400 mA / cm²). 2 It has low operating pressure and low energy efficiency.

[0075] In a preferred embodiment of the method of the present invention, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variations of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE) and anion exchange membrane water electrolysis (AEMWE).

[0076] PEM water electrolysis was developed to overcome the drawbacks of alkaline water electrolysis. 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 and high proton conductivity (0.1 ± 0.02 S cm⁻¹). -1 PEM water electrolysis offers several advantages, including compact design, low thickness (20-300 µm), and allows for high-pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most advantageous methods for converting renewable energy into high-purity hydrogen. PEM water electrolysis offers significant advantages such as compact design and high current density (above 2 A cm⁻¹). -2It features high efficiency, fast response, operation at low temperatures (20°C-80°C), and production of ultrapure hydrogen. Existing electrocatalysts 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.

[0077] One of the greatest advantages of PEM water electrolysis is its ability to operate at high current densities. This results in reduced operating costs, especially for systems combined with highly dynamic energy sources such as wind and solar power, where sudden spikes in energy output would otherwise lead to uncaptured energy. The polymer electrolyte allows PEM water electrolyzers to operate with very thin membranes (approximately 100–200 µm) while still allowing for high operating pressures, resulting in low ohmic losses primarily due to proton conduction through the membrane (0.1 S / cm), and compressed hydrogen output.

[0078] The PEM water electrolyzer utilizes a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while simultaneously insulating the electrodes. Under standard conditions, the enthalpy required to form water is 285.9 kJ / mol. A portion of the energy required for the continuous electrolysis reaction is supplied by heat, and the remainder by electricity.

[0079] The half-reaction that occurs on the anode side of a PEM water electrolyzer is commonly referred to as the oxygen evolution reaction (OER). Here, liquid water reactants are supplied to a catalyst, where they are oxidized into oxygen, protons, and electrons.

[0080] The half-reaction that occurs on the cathode side of a PEM water electrolyzer is commonly referred to as the hydrogen evolution reaction (HER). Here, protons that have moved across the membrane are reduced to gaseous hydrogen.

[0081] PEMs can be made from pure polymer membranes or composite membranes, in which other materials are embedded within a polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA or Nafion® (a product of DuPont). While Nafion® is an ionomer with a perfluorinated backbone like Teflon, many other structural motifs exist for the manufacture of proton exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

[0082] A review of hydrogen production via PEM water electrolysis is given in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442-4454.

[0083] A review of hydrogen production via water electrolysis through anion exchange membranes is given in HA Miller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0084] K. Harada et al., *International Journal of Hydrogen Energy*, 45(2020), pp. 31389-31395, reported a 2-3 fold depletion of deuterium in polymer electrolyte membrane water electrolysis. Corresponding to a stoichiometric number λ between 4 and 9 for a given water mass flow rate at the anode, this was observed at current densities of 1.0 to 2.0 Acm⁻¹. -2 In the case of separation coefficient β

[0085] β = ([H] / [D]) 气体 / ([H] / [D]) 液体

[0086] Between 2 and 3, where "gas" refers to the escaping gas and "liquid" refers to the water before electrolysis. The stoichiometric coefficient λ is defined as follows:

[0087] λ = V x ρ / (J / 2F x 60 x M H2O )

[0088] Where V (mL min) -1 ) is the water mass flow rate in the anode, F is the Faraday constant, J is the electrolysis current (A), and ρ is the density of water (g / mL). -1 And M H2O (g mol) -1 λ is the molar weight of water. A stoichiometric coefficient λ of 10 means that, for a given electrolysis current, the amount of fresh water supplied to the anode can be 10 times the amount theoretically consumed by electrolysis.

[0089] H. Sato et al., International Journal of Hydrogen Energy, 46 (2021), pp. 33689-33695, reported that for anion exchange membrane water electrolysis, at λ = 4, the deuterium concentration in the escaping hydrogen was diluted by about 1 / 5 relative to the feed water.

[0090] Therefore, in the case of feed water in polymer electrolyte membrane water electrolysis, the deuterium content in the escaping hydrogen can be easily depleted by 2 to 5 times. Depending on the electrolysis conditions (water flow rate, current density), even higher depletion factors are possible. Since the average deuterium content of water is based on a total hydrogen content of about 150 ppm, the hydrogen provided in step (a) of the method of the present invention can have a deuterium content of 30 to 75 ppm, or even lower, based on a total hydrogen content.

[0091] Electricity is generated at least partially from non-fossil renewable resources. In other words, some electricity can still be generated from fossil fuels, preferably natural gas, because the combustion of natural gas results in much lower carbon dioxide emissions per megajoule of electricity compared to the combustion of coal. However, the portion of electricity generated from fossil fuels should be as low as possible, preferably ≤ 50%, more preferably ≤ 30%, and most preferably ≤ 20%.

[0092] The electricity generated from non-fossil resources used in the water electrolysis according to the present invention can be produced by nuclear energy. The European Commission considers nuclear energy to be renewable provided certain prerequisites are met (i.e., the safe long-term storage of nuclear waste).

[0093] The electricity derived from non-fossil resources used in the water electrolysis according to the present invention is preferably generated by wind, solar, biomass, hydropower, and geothermal energy.

[0094] In a preferred embodiment of the method of the present invention, the electricity used in water electrolysis is generated by water power. Hydropower generation takes many forms. Traditionally, hydropower generation comes from the construction of large hydroelectric dams and reservoirs. Small hydroelectric systems are hydroelectric power generation devices that typically produce up to 50 MW of power. They are often used on small rivers or as low-impact development projects on large rivers. Hydroelectric power stations operating on rivers obtain energy from the river without creating large reservoirs. Water is typically transported along the side of the valley (using channels, pipes, and / or tunnels) until the water level is above the valley floor, at which point it can be allowed to fall through pressurized pipes to drive turbines.

[0095] Wave energy, which captures the energy of ocean waves, and tidal energy, which converts tidal energy, are two forms of hydropower with future potential.

[0096] In another preferred embodiment of the method of the invention, the electricity used in water electrolysis is generated by wind power. Wind power can be used to operate wind turbines. Modern utility-scale wind turbines have rated power ranging from approximately 600 kW to 9 MW. The power that can be generated from wind is a function of the cube of the wind speed, so as the wind speed increases, the power output increases until the maximum output of a particular turbine. Areas with stronger and more constant winds, such as offshore and high-altitude sites, are preferred locations for wind farms.

[0097] In another preferred embodiment of the method of the invention, the electricity used in water electrolysis is generated by solar energy, particularly preferably by a photovoltaic system. A photovoltaic system converts light into direct current (DC) using the photoelectric effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus sunlight from a large area into a small beam. CSP-Stirling currently boasts the highest efficiency among all solar energy technologies.

[0098] In another preferred embodiment of the method of the present invention, the electricity used in water electrolysis is generated from biomass. Biomass is biological material derived from living organisms or most recently living organisms. It most often refers to plants or plant-derived materials, specifically lignocellulosic biomass. As an energy source, biomass can be used directly to generate heat or electricity through combustion, or indirectly after being converted into various forms of biofuels. The conversion of biomass into biofuels can be achieved through different methods, which are broadly classified as thermal, chemical, and biochemical methods. As of 2012, wood was the largest biomass energy source; examples include forest residues (such as dead trees, branches, and stumps), garden trimmings, wood chips, and even municipal solid waste. Industrial biomass can be grown from a wide variety of plant types, including Miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a range of tree species from eucalyptus to oil palm (palm oil).

[0099] Plant energy is produced by crops specifically grown for fuel, which provide high biomass yields per hectare with low energy inputs. Grains can be used as liquid transport fuels, while straw can be burned to generate heat or electricity. Biomass can be converted into other available energy forms, such as methane gas or transport fuels like ethanol and biodiesel. Decaying waste, as well as agricultural and human waste, releases methane gas – also known as landfill gas or biogas. Crops such as corn and sugarcane can be fermented to produce ethanol, a transport fuel. Biodiesel (another transport fuel) can be produced from leftover food products such as vegetable oils and animal fats.

[0100] In step (b) of the method of the present invention, carbon dioxide is provided. In a preferred embodiment, the carbon dioxide provided in step (b) is captured from industrial flue gas or from ambient air. All available capture technologies can be used.

[0101] Capturing CO2 at point sources, such as large-scale carbon-based energy facilities, industries with high CO2 emissions (e.g., cement production, steelmaking), natural gas processing, synthetic fuel plants, and fossil fuel-based hydrogen production plants, is the most cost-effective approach. Extracting CO2 from the air is possible, although the lower concentration of CO2 in the air compared to combustion sources complicates engineering and therefore makes the process more expensive.

[0102] In some preferred embodiments, the carbon dioxide provided in step (b) is captured from industrial flue gas.

[0103] In post-combustion capture, CO2 is removed after the combustion of fossil fuels (this is the approach used in fossil fuel power plants). CO2 is captured from flue gas at power plants or other point sources. Absorption or amine washing of carbon is the primary capture technology. It is by far the only carbon capture technology used industrially.

[0104] CO2 is adsorbed into MOFs (metal-organic frameworks) through selective physical or chemical adsorption based on MOF porosity, leaving a CO2-lean gas stream. CO2 is then stripped from the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA), allowing the MOF to be reused.

[0105] In some other preferred embodiments, the carbon dioxide provided in step (b) is captured from ambient air.

[0106] Direct air capture (DAC) is a process that directly captures carbon dioxide (CO2) from ambient air and produces a concentrated stream of CO2 for isolation, utilization, or production of carbon-neutral fuels. CO2 removal is achieved when ambient air comes into contact with a chemical medium (typically an aqueous, alkaline solvent or an adsorbent). These chemicals are then stripped of CO2 by the application of energy (i.e., heat), yielding a CO2 stream that can be dehydrated and compressed, while simultaneously regenerating the chemical medium for reuse.

[0107] Diluted CO2 can be efficiently separated using an anion exchange polymer resin called Marathon MSA, which absorbs CO2 from the air when dry and releases it when exposed to moisture. Most of the energy used in this process is supplied by the latent heat of phase change of water. Other materials that can be used are metal-organic frameworks (or MOFs). Membrane separation of CO2 relies on semipermeable membranes.

[0108] In step (c), hydrogen and carbon dioxide are reacted in the presence of a catalyst to form methanol.

[0109] A review of suitable catalyst systems is given by Kristian Stangeland, Hailong Li, and Zhixin Yu, Energy, Ecology and Environment, Vol. 5, pp. 272-285 (2020). This process requires multi-component catalyst systems. Interactions between components are essential for the high activity and selectivity of catalysts for CO2 to methanol production. This has been demonstrated by a variety of catalyst systems composed of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., ZnO, ZrO2, In2O3). These complex systems can contain mixtures of metallic, alloy, and metal oxide phases. The most promising catalyst systems for large-scale industrial methods are currently Cu-based and In-based catalysts due to their excellent catalytic performance.

[0110] The process for the synthesis of methanol from CO2 can be carried out, for example, by a method known from DE-A-42 20 865, which produces methanol under the influence of silent electrical discharges.

[0111] Alternatively, methanol synthesis can also be carried out in a thermal reactor under pressure and elevated temperature in the presence of a copper-based catalyst (DE 43 32 789 A1; DE 19739773 A1).

[0112] For example, a typical catalyst is described by N. Kanoun et al. in the following publication: CATALYSIS LETTERS 15, (1992) 231-235, “Catalytic properties of Cu based catalysts containing Zr and / or V for methanol synthesis from a carbon dioxide and hydrogen mixture”. Potential catalysts such as CuO / ZnO and Cu-ZnO-Al2O3 have also been described by RM Navarro et al. in “Methanol Synthesis from CO2: A Review of the Latest Developments in Heterogeneous Catalysis” Materials (2019), 12, 3902 and “Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies” Chemical Engineering Research and Design 92 (2014) 2557-2567.

[0113] Recently, highly selective catalysts In₂O₃ / ZrO₂ for industrial-relevant conditions have been described. Typical industrial-relevant conditions for CO₂ hydrogenation to methanol range from T = 200°C to 300°C, p = 10⁻⁵ MPa, and gas hourly space velocity (GHSV) of 16,000 to 48,000 h⁻¹. -1 (Angew. Chem. Int. Ed. [Germany's Angewandte Chemie International Edition] 2016, 55, 6261-6265).

[0114] Step (c) can be carried out in the presence of a copper-zinc-alumina catalyst. If a copper-zinc-alumina catalyst is used, the preferred temperature is in the range of 150°C to 300°C, more preferably 175°C to 300°C, and the preferred pressure is in the range of 10 to 150 bar (absolute pressure).

[0115] Ethylene is typically produced from methanol via the methanol-to-olefins (MTO) process. Because this process involves the breaking of CH and CD bonds, respectively, the associated primary isotope effects are significant. In the MTO process, a mixture of ethylene and propylene is produced from methanol in a fluidized bed operation over a highly selective silica-alumina-phosphate zeolite catalyst. The propylene to ethylene ratio can be adjusted by selecting appropriate process conditions and can vary from 0.77 in the ethylene production mode to 1.33 in the propylene production mode.

[0116] The overall kinetic isotope effect is cumulative because it will also be present in all subsequent production steps downstream of the value chain.

[0117] In the environmentally friendly method for producing vinyl acetate of the present invention, vinyl acetate is produced from methanol obtained in step (c) in the following manner:

[0118] (d) React the methanol from step (c) to form ethylene; and

[0119] (e) React methanol from step (c) with carbon monoxide to form acetic acid; and / or

[0120] (f1) React a portion of the ethylene from step (d) with oxygen and water to obtain acetaldehyde;

[0121] (f2) React the acetaldehyde from step (f1) with oxygen to give acetic acid;

[0122] (g) React acetic acid from step (e) and / or step (f1) with ethylene from step (d) to obtain vinyl acetate.

[0123] In step (d), ethylene is produced from methanol in the methanol-to-olefins (MTO) process as described above.

[0124] Acetic acid can be produced by the carbonylation of methanol in step (e). This method involves iodomethane as an intermediate and is carried out in three steps. The carbonylation (step 2) requires a catalyst, a metal carbonyl compound.

[0125] 1. CH3OH + HI → CH3I + H2O

[0126] 2. CH3I + CO → CH3COI

[0127] 3.CH3COI + H2O → CH3COOH + HI

[0128] There are two relevant methods for methanol carbonylation: the rhodium-catalyzed Monsanto process and the iridium-catalyzed Cativa process.

[0129] The Monsanto process operates at pressures of 30–60 atm and temperatures of 150–200°C, exhibiting selectivity greater than 99%. The catalytically active material is the anionic cis-[Rh(CO)₂I₂]. - The first organometallic step involves the oxidative addition of iodomethane to cis-[Rh(CO)₂I₂]. - To form a six-coordinate compound [(CH3)Rh(CO)2I3] - The anion rapidly transforms via methyl migration to the adjacent carbonyl ligand, yielding the five-coordinate acetyl complex [(CH3CO)Rh(CO)I3]. - The five-coordinate complex then reacts with carbon monoxide to form a six-coordinate dicarbonyl complex, which undergoes reductive elimination to release acetyl iodide (CH3C(O)I). The catalytic cycle involves two non-organometallic steps: the conversion of methanol to iodomethane and the hydrolysis of acetyl iodide to acetic acid and hydrogen iodide.

[0130] The Kativa process is another method for producing acetic acid via the carbonylation of methanol. This technology is similar to the Monsanto process. This method is based on iridium-containing catalysts, such as the complex [Ir(CO)₂I₂]. - The catalytic cycle of the Kativa process begins with the reaction of iodomethane with a square planar active catalyst to form an octahedral iridium(III) compound [Ir(CO)2(CH3)I3]. - This oxidative addition reaction involves the insertion of an iridium (I) center into the carbon-iodine bond of iodomethane. Following ligand exchange between the iodide and carbon monoxide, the carbon monoxide migrates and inserts into the iridium-carbon bond, resulting in the formation of a substance with bound acetyl ligands. The active catalyst is regenerated by reducing and eliminating the acetyl iodide. In the production of hydroiodic acid, the acetyl iodide is hydrolyzed to produce acetic acid, which is then used to convert the starting material methanol into iodomethane used in the first step.

[0131] The Wacker process, or Wacker-Hoechst process, refers to the oxidation of ethylene to acetaldehyde in the presence of palladium(II) chloride as a catalyst.

[0132] The net reaction can be described as follows:

[0133] [PdCl4] 2 - + C2H4 + H2O → CH3CHO + Pd + 2 HCl + 2 Cl -

[0134] This transformation is followed by the reaction to regenerate the Pd(II) catalyst:

[0135] Pd + 2 CuCl2 + 2 Cl - → [PdCl4] 2- + 2 CuCl

[0136] 2 CuCl + 1 / 2 O2 + 2 HCl → 2 CuCl2 + H2O

[0137] Two methods have been commercialized for the production of acetaldehyde: the single-stage method and the two-stage method.

[0138] In the single-stage process, ethylene and oxygen are passed in parallel through a reaction tower at approximately 130°C and 400 kPa. The catalysts are an aqueous solution of PdCl2 and CuCl2. Acetaldehyde is purified by extractive distillation followed by fractional distillation. Extractive distillation with water removes lighter fractions (chloromethane, chloroethane, and carbon dioxide) with lower boiling points than acetaldehyde at the top, while water and higher-boiling byproducts (such as acetic acid, crotonaldehyde, or acetaldehyde chloride) are removed at the bottom along with the acetaldehyde.

[0139] In the two-stage process, the reaction and oxidation are carried out separately in a tubular reactor. Unlike the single-stage process, air can be used instead of oxygen. Ethylene and the catalyst are passed through the reactor together at 105°C–110°C and 900–1000 kPa. The catalyst solution containing acetaldehyde is separated by flash evaporation. The catalyst is oxidized in an oxidation reactor using air as the oxidation medium at 1000 kPa. The oxidized catalyst solution is separated and returned to the reactor. The oxygen in the air is completely used up, and the exhaust gas is recycled as an inert gas. The acetaldehyde-water vapor mixture is pre-concentrated to 60%–90% acetaldehyde using the heat of reaction, and the discharged water is returned to the flash column to maintain the catalyst concentration. This is followed by a two-stage distillation of crude acetaldehyde. In the first stage, low-boiling substances such as chloromethane, chloroethane, and carbon dioxide are separated. In the second stage, water and higher-boiling byproducts (such as acetaldehyde chloride and acetic acid) are removed, and acetaldehyde is obtained in pure form at the top of the column.

[0140] In both the single-stage and two-stage methods, the acetaldehyde yield is approximately 95%.

[0141] For further details, please refer to Marc Eckert, Gerald Fleischmann, Reinhard Jira, Hermann M. Bolt, Klaus Golka, Acetaldehyd, Ullmann's Encyclopedia of Industrial Chemistry, 7th Edition, Volume 1, Chapter 4.3, page 197.

[0142] Acetaldehyde can be oxidized to acetic acid using pure oxygen or air in the presence of a redox catalyst. The oxidation can be carried out in a bubble column at a temperature of 50°C–70°C in the presence of cobalt acetate or manganese acetate as a solvent (Hurster process).

[0143] Most vinyl acetate is produced via a gas-phase reaction of ethylene and acetic acid over a noble metal catalyst (typically palladium). This reaction is typically carried out at 150°C–250°C, preferably 175°C–200°C, and pressures of 5–9 bar. The reaction is usually conducted in a fixed-bed tubular reactor using a supported catalyst in the gas phase. The amount of oxygen in the combined feed is in the range of 5–15 mol%. Preferably, the amount of acetic acid in the combined feed is in the range of 10–25 mol%. Preferably, the amount of ethylene in the combined feed is in the range of 65–80 mol%. Suitable catalysts include those known in the vinyl acetate industry. Preferably, the catalyst is a palladium-gold catalyst. Methods for preparing palladium-gold catalysts are known. For example, U.S. Patent No. 6,022,823 teaches how to prepare palladium-gold catalysts with high activity and selectivity. Preferably, the palladium-gold catalyst is supported on inorganic oxides (such as alumina, silica, titanium dioxide, etc.) and mixtures thereof.

[0144] In another environmentally friendly method of the present invention, vinyl acetate is produced from methanol obtained in step (c) in the following manner:

[0145] (d) React the methanol from step (c) to form ethylene; and

[0146] (e) React the ethylene from step (d) with oxygen and water to form acetaldehyde;

[0147] (f1) React a portion of the acetaldehyde from step (e) with oxygen to form acetic acid; and / or

[0148] (f2) React methanol from step (c) with carbon monoxide to form acetic acid; and

[0149] (g1) React acetic acid from step (f1) and / or step (f2) with methanol from step (c) to form methyl acetate;

[0150] (g2) React the methyl acetate from step (g1) with carbon monoxide to form acetic anhydride; and / or

[0151] (h1) Producing ketene from acetic acid from step (f1) and / or step (f2);

[0152] (h2) React the ketene from step (h1) with the acetic acid from step (f1) and / or step (f2) to obtain acetic anhydride;

[0153] (i) React the acetic anhydride from step (g2) and / or step (h2) with the acetaldehyde from step (e) to form ethylene diacetate;

[0154] (k) React diacetene with acetic acid to obtain vinyl acetate by thermal elimination of acetic acid.

[0155] This alternative route for the production of vinyl acetate involves the reaction of acetaldehyde and acetic anhydride, typically in the presence of a ferric chloride catalyst, to yield ethylene diacetate (step (i)):

[0156] CH3CHO + (CH3CO)2O → (CH3CO2)2CHCH3.

[0157] This reaction can be carried out in the liquid phase at 120°C–140°C. Ethylene diacetate can be converted to vinyl acetate by thermal elimination of acetic acid (step (k)).

[0158] (CH3CO2)2CHCH3 → CH3CO2CH=CH2 + CH3CO2H.

[0159] For further details, see G. Roscher, "Vinyl Esters", Ullmann's Encyclopedia of Chemical Technology, 2007, John Wiley & Sons, New York. doi:10.1002 / 14356007.a27_419.

[0160] In step (g1), acetic acid can be reacted with methanol to obtain methyl acetate.

[0161] For further details, see Aslam, M., Torrence, GP and Zey, EG (2000), Esterification, Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 10, p. 471; Le Berre, C., Serp, P., Kalck, P. and Torrence, GP (2014), Acetic Acid, Ullmann's Encyclopedia of Industrial Chemistry, 7th ed., Chapter 10.2.1, p. 25.

[0162] Esters are most commonly prepared by the reaction of carboxylic acids and alcohols in the absence of water. Esters are also formed through a variety of other reactions utilizing acid anhydrides, acyl chlorides, amides, nitriles, unsaturated hydrocarbons, ethers, aldehydes, ketones, alcohols, and esters (via transesterification). In the production of acetates, primary alcohols are esterified most rapidly and completely, with methanol offering the highest yield and the most rapid reaction. Most commercially available methyl acetate is a byproduct of acetic acid production. Another method is the esterification of methanol and acetic acid using sulfuric acid as a catalyst. The resulting ester is removed as a methanol / methyl acetate azeotrope.

[0163] Acetic anhydride can be produced in step (g2) via the carbonylation of methyl acetate:

[0164] CH3CO2CH3 + CO → (CH3CO)2O

[0165] This method, known as the Tennessee Eastman acetic anhydride process, involves the conversion of methyl acetate to iodomethane and an acetate. The carbonylation of the iodomethane yields acetyl iodide, which reacts with an acetate or acetic acid to give the product. Rhodium chloride is used as a catalyst in the presence of lithium iodide. Because acetic anhydride is unstable in water, the conversion is carried out under anhydrous conditions.

[0166] For further details, see Held, H., Rengstl, A. and Mayer, D. (2000), Acetic Anhydride and Mixed Fatty Acid Anhydrides, Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Volume 1, Chapter 1.3.3, page 248 and following pages.

[0167] Acetic anhydride can also be prepared in step (h2) by reacting ketene with acetic acid, for example, at 45°C-55°C and low pressure (0.05-0.2 bar). Ketene can be produced in step (h1) by dehydrating acetic acid at 700°C-750°C.

[0168] For further details, see Held, H., Rengstl, A. and Mayer, D. (2000), Acetic Anhydride and Mixed Fatty Acid Anhydrides, Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Volume 1, Chapter 1.3.1, page 245 and following pages.

[0169] Acetic anhydride can also be obtained directly in step (f1) by liquid-phase oxidation of acetaldehyde. Peracetic acid, formed from oxygen and acetaldehyde, reacts with a second acetaldehyde molecule under suitable conditions to form acetic anhydride and water. In practice, a 1:2 mixture of acetaldehyde and ethyl acetate is oxidized at 40°C by adding 0.05% to 0.1% cobalt acetate and copper acetate; the Co:Cu ratio is 1:2. The resulting acetic anhydride to acetic acid ratio is 56:44, whereas in the absence of ethyl acetate, this ratio is only 20:80.

[0170] For further details, see Held, H., Rengstl, A. and Mayer, D. (2000), Acetic Anhydride and Mixed Fatty Acid Anhydrides, Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Volume 1, Chapter 1.3.2, page 244 and following pages.

[0171] The present invention further relates to vinyl acetate having a deuterium content of less than 90 ppm based on a total hydrogen content, which can be obtained by the method described herein.

[0172] Vinyl acetate preferably has a deuterium content of 30 to 75 ppm based on the total hydrogen content.

[0173] If the carbon dioxide in step (b) is captured from ambient air, then vinyl acetate can have a δ value corresponding to -10‰ to -2.5‰. 13 C value 13 C content.

[0174] Vinyl acetate can be polymerized into polyvinyl acetate. Polyvinyl acetate eventually hydrolyzes into biodegradable polyvinyl alcohol. If CO2 is obtained from the atmosphere in step (b), the biodegradation of polyvinyl alcohol produces H2O and CO2, thus closing the loop of the CO2 neutral life cycle.

[0175] Poly(vinyl esters) is non-toxic, but it degrades slowly in water. See Rinno, H. (2000), Poly(vinyl esters), Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Volume 28, Chapter 8, page 477 and following pages.

[0176] Polyvinyl alcohol (PVA) is considered one of the very few vinyl polymers that are soluble in water and readily biodegrades in the presence of appropriately adapted microorganisms. PVA is non-toxic but is expected to biodegrade within 90 days under aquatic conditions; see Dominic Byrne et al., Biodegradability of polyvinyl alcohol based film used for liquid detergent capsules, Tenside Surf. Det. 58 (2021) 2; E. Chiellini et al., Prog. Polym. Sci. 28 (2003), pp. 963-1014.

[0177] The present invention further relates to a method for preparing vinyl acetate with natural abundance of C-14 from non-fossil resources, preferably biomass, the vinyl acetate obtained thereby, and its uses.

[0178] In the chemical industry, methanol serves as a raw material for the production of olefins, formaldehyde, acetaldehyde, acetic acid, methyl acetate, acetic anhydride, and vinyl acetate. Conventional production methods involve catalytic processes using fossil fuels such as natural gas or coal.

[0179] Synthesis gas, used to produce methanol, can be produced from many sources, including natural gas, coal, biomass, or virtually any hydrocarbon feedstock, by reacting with steam (steam reforming), carbon dioxide (dry reforming), or oxygen (partial oxidation).

[0180] Syngas is produced from solid feedstocks via coal gasification. This process involves reacting coal in a mixture of partial oxidation with air or pure oxygen and gasification with steam to produce a mixture of carbon monoxide and hydrogen.

[0181] Most vinyl acetate is produced via a gas-phase reaction of ethylene and acetic acid over a noble metal catalyst (usually palladium).

[0182] Acetic acid can be produced via the carbonylation of methanol using either the Monsanto or Kativa processes. Alternatively, acetic acid can be produced by reacting ethylene with oxygen and water to give acetaldehyde, and then further reacting acetaldehyde with oxygen to yield acetic acid.

[0183] Ethylene can be obtained from methanol via the methanol-to-olefins (MTO) process.

[0184] Following the European Committee for Standardization's (CEN) call for the development of a European standard (EN 17035) to define bio-based surfactants and enable the quantification of their bio-based carbon content based on radiocarbon analysis, Stephen M. Mudge, Juergen Tropsch, Thierry Beaudouin, Christophe Séné, and Horacio Hormazabal, J Surfact Deterg (2020) 23: 771-780, reported on the determination of the bio-based carbon content of surfactants. The analytical methods described in the references were tested by direct contract analysis and by the cyclic method procedure of the European Commercial Facilities Authority.

[0185] According to the references, there are two main analytical methods that can be used to determine the amount of bio-based carbon present in any sample:

[0186] - Stable 13 Carbon isotopes. The carbon isotopes present within surfactant molecules will reflect the initial carbon source and any transformations they may have undergone since formation. Many crude oils have δ¹⁸O carbon isotopes. 13 C ranges from -23‰ to -28‰. This can be compared to -26‰ to -36‰ for terrestrial plant matter and -20‰ to -26‰ for unicellular algae. Because these ranges overlap, this may not be definitive when separating the two sources.

[0187] - Radiocarbon ( 14 C). With 13 The very small proportion of carbon in the molecule, along with stable isotopes of carbon, will be in a naturally occurring radioactive form. 14 C, also known as radioactive carbon. 14C atoms form in the upper atmosphere due to the interaction of cosmic rays with nitrogen atoms. In compounds... 14 The natural abundance of C is approximately 1 part per trillion (ppt; 10) -12 This radioactive carbon isotope decays with a half-life of 5,730 years, making it functionally undetectable in the sample after six half-lives. Carbon compounds derived from fossil sources such as oil or natural gas will not contain radioactive carbon, as it will decay over the millions of years required to form such reserves. This contrasts with recently grown deposits that do contain measurable amounts. 14 C forms a contrast with plant-based materials. Radiocarbon can be measured using gas proportional counting, liquid scintillation counting, and accelerator mass spectrometry (AMS). The latter method is the most sensitive of the three.

[0188] The object of this invention is to provide an environmentally friendly method for producing vinyl acetate. Another object of this invention is to provide a vinyl acetate that can be used to determine the content of bio-based vinyl acetate or bio-based vinyl alcohol derived therefrom through hydrolysis in polymers and copolymers containing vinyl acetate or vinyl alcohol. Yet another object of this invention is to provide a vinyl acetate used to determine the source of decay products released during the decomposition of polymers or copolymers containing vinyl acetate or vinyl alcohol.

[0189] This objective is achieved by a method for producing vinyl acetate from biomass, the method comprising the step of reacting (I) ethylene with (II) acetic acid to obtain vinyl acetate, wherein...

[0190] (I) Providing ethylene from biomass or ambient air through methods including:

[0191] (a) Producing carbon oxides from biomass or capturing carbon dioxide from ambient air, optionally followed by electrochemically reducing carbon dioxide to carbon monoxide;

[0192] (b) Electrochemically reducing the carbon oxides from step (a) to obtain ethylene; and / or

[0193] (c1) Hydrogen gas and carbon oxides from step (a) are reacted in the presence of a catalyst to give methanol.

[0194] (c2) React the methanol from step (c1) to form ethylene; and / or

[0195] (d1) Production of ethanol from biomass through fermentation, and

[0196] (d2) Dehydrogenating the ethanol from step (d1) to obtain ethylene; and / or

[0197] (e) Direct production of ethylene from biomass through fermentation;

[0198] (II) Providing acetic acid from biomass or carbon dioxide captured from ambient air by methods including the following

[0199] (f) Reacting methanol from step (c1) with carbon monoxide to give acetic acid; and / or

[0200] (g1) React a portion of the ethylene from steps (b), (c2), (d2), or (e) with oxygen and water to give acetaldehyde, and

[0201] (g2) React the acetaldehyde from step (g1) with oxygen to give acetic acid; and / or

[0202] (h) oxidize the ethanol from step (d1) by fermentation to obtain acetic acid; and / or

[0203] (i) Acetic acid is produced from biomass through biomass pyrolysis.

[0204] According to the present invention, ethylene can be produced by one or more of steps (b), (c1) / (c2), (d1) / (d2), and (e). Acetic acid can be produced by one or more of steps (f), (g1) / (g2), (h), and (i).

[0205] In some embodiments, ethylene is produced by one or more of steps (b), (c1) / (c2), (d1) / (d2), and (e), and acetic acid is produced by step (f). In one specific embodiment, the method includes steps (c1), (c2), and (f). In another specific embodiment, the method includes steps (c1), (c2), (g1), and (g2).

[0206] In some other embodiments, ethylene is produced by one or more of steps (b), (c1) / (c2), (d1) / (d2), and (e), and acetic acid is produced by step (g1) / (g2).

[0207] In some other embodiments, ethylene is produced by one or more of steps (b), (c1) / (c2), (d1) / (d2), and (e), and acetic acid is produced by step (h).

[0208] In some other embodiments, ethylene is produced by one or more of steps (b), (c1) / (c2), (d1) / (d2) and (e), and acetic acid is produced by step (i).

[0209] There are three naturally occurring carbon isotopes on Earth: carbon-12 ( 12 C), which accounts for 99% of all carbon on Earth; carbon-13 ( 13 C), which accounts for 1%; and carbon-14 ( 14 C), which exists in trace amounts, accounting for about 1 or 1.5 atoms / 10 in the atmosphere. 12 It contains one carbon atom. Both carbon-12 and carbon-13 are stable, while carbon-14 is unstable and has a half-life of 5700 ± 30 years. Carbon-14 decays into nitrogen-14 via β decay. 14 The primary natural source of carbon-14 on Earth is the effect of cosmic rays on nitrogen in the atmosphere, and therefore it is a cosmogenic nuclide.

[0210] The natural abundance of carbon-14 (14C) is approximately 1 ppt (per trillion parts per trillion) based on total carbon content. -12 ;10 -10 (Atoms - %), typically 0.5 to 2.0 ppt.

[0211] In step (a), the carbon oxides are produced from biomass. Suitable biomass is lignocellulosic biomass, such as lignocellulosic waste biomass.

[0212] CO2 or CO can be converted into methanol using hydrogen for further processing into ethylene. Alternatively, CO2 or CO can be converted into ethylene via electrochemical conversion, i.e., electrochemical conversion into C2 products. CO2 / CO electrolysis can be implemented using membrane electrode assembly (MEA) technology. Biomass can be used as a renewable carbon feedstock for electrochemical methods.

[0213] Ethylene production via biomass gasification and electrochemical CO reduction is described by Klüh et al. (2023), Assessment of electrified ethylene production via biomass gasification and electrochemical CO reduction, Front. Energy Res. 11:1129076. doi: 10.3389 / fenrg.2023.1129076, and other references.

[0214] Electrochemical reduction of CO2 (CO2R) can produce a wide range of products, such as ethylene, ethanol, acetic acid, propanol, methanol, or formic acid. Compared to direct CO2 conversion, a two-step process using CO as an intermediate to produce C2 products from CO2 is considered advantageous. CO reduction to C2 products (COR) can be combined with biomass gasification or biomass combustion.

[0215] In some embodiments, carbon oxides are produced from biomass via biomass gasification in step (a). In some other embodiments, carbon oxides are produced from biomass via biomass combustion in step (a).

[0216] In recent years, combinations of biomass-based and electrification-based processes, known as power / biomass-to-X (PBtX), have been extensively studied. Two main pathways (both based on the electrochemical reduction of CO) utilize lignocellulosic waste biomass as feedstock, but differ in the thermochemical treatment employed: gasification or combustion. In the gasification pathway, the biomass is dried and gasified in an oxygen- and steam-blown fluidized bed gasifier. A CO-rich stream is then fed to an electrochemical CO reduction unit. Hydrogen is recovered from the membrane-separated purge stream via pressure swing adsorption (PSA). The remaining gas is used to heat a reformer. In the combustion-based pathway, the biomass is combusted in a fluidized bed combined heat and power (CHP) unit that generates heat and electricity for process operation. CO2 is separated from the flue gas by washing with monoethanolamine (MEA). See Klüh et al. (2023), Front. Energy Res. 11:1129076.

[0217] In the CO2 electrolysis unit, CO2 is further converted into CO. Then, CO is further processed in the electrochemical CO reduction unit.

[0218] During electrochemical reduction, CO is converted into ethylene, acetic acid, ethanol, oxygen, and hydrogen in the electrochemical cell. Ethanol and acetic acid are separated from the electrolyte via distillation. Oxygen is readily separated from the liquid phase at the anode. Unreacted CO, H2, and ethylene from the cathode are separated via PSA. Unconverted CO, along with trace amounts of H2 and ethylene, is recycled back into the electrochemical cell.

[0219] Biomass gasification can be carried out as described by Klüh et al. (2023), Front. Energy Res. 11:1129076. The gasification pathway consists of biomass drying and gasification, followed by COR and product separation. The biomass is dried and can then be further processed in the gasification process. The biomass dryer can be, for example, a belt dryer operating at a temperature level of 120°C. The water content is reduced, for example, from 35 wt.% to 15 wt.%. The dried biomass is then gasified in an oxygen-blown fluidized bed gasifier. The gasifier may include two reactors. In the decomposition reactor (yield reactor (RYield)), the biomass is decomposed into its elements, while the subsequent reactor seeks chemical equilibrium.

[0220] The combustion-based approach consists of the following steps: biomass combustion and CO2 capture, CO2 conversion via electrolysis, electrochemical conversion of CO, and subsequent product separation. CO2 is separated from the flue gas of the biomass CHP power plant. Post-combustion capture, using MEA absorption for CO2 separation, is an established technology for capturing CO2 from power plant flue gas.

[0221] In some embodiments, carbon dioxide contained in the product gas obtained from the gasification or combustion of biomass is electrochemically reduced to carbon monoxide.

[0222] CO2 can be electrochemically converted to CO according to equation (1). At the cathode, carbon dioxide is reduced to carbon monoxide, while oxygen is formed at the anode. CO is separated from the product stream, and unreacted CO2 (which also contains some CO) can be recycled back into the electrolytic cell.

[0223] 2 CO2 → 2 CO + O2 (1)

[0224] Electrochemical reduction of the carbon dioxide contained in the gas stream provided in step (a) is performed to obtain a gas stream containing carbon monoxide, optionally carbon dioxide and optionally hydrogen.

[0225] Numerous methods have been proposed for the electrochemical production of CO from CO2. Most of these methods are in the very early stages of development. High-temperature electrolysis in solid oxide batteries is a CO2 electrolysis technology that is nearing commercialization and has demonstrated long-term durability of over a year.

[0226] A review of two alternative electrochemical techniques for CO production (low-temperature and molten carbonate electrolysis) is given in Reiner Küngas (2020), J. Electrochem. Soc. [Journal of Electrochemistry] 167 044508 and other references.

[0227] Regardless of the technology chosen, an electrolytic cell always has at least three components: two electrodes in contact with the electrolyte. The electrolyte is a liquid or solid material that can conduct ions (e.g., protons, hydroxide ions, oxygen ions, carbonate ions, or bicarbonate ions) but is impermeable to electrons. The ionic conductivity of the electrolyte is strongly temperature-dependent, and the choice of electrolyte material thus determines the operating temperature of the cell. When an external voltage is applied between the two electrodes, an electrochemical reaction begins. The electrode where the reduction of reactants (e.g., CO2 to CO) occurs is called the cathode. The electrode where the reduction of reactants (e.g., OH-) occurs is called the cathode. - To O2 and H2O or O 2- The electrode that oxidizes (to O2) is called the anode.

[0228] In solid oxide electrolyzers (SOECs), the electrolyte is a solid ceramic material. At temperatures above approximately 600°C, the electrolyte material begins to conduct oxygen ions but remains impermeable to gaseous oxygen and electrons. As the ionic conductivity of the electrolyte material increases exponentially with temperature, the operating temperature of SOECs is typically chosen between 700°C and 900°C. Commonly used materials include stabilized zirconium oxides such as yttrium-stabilized zirconium oxide (YSZ, a solid solution of Y₂O₃ and ZrO₂) and scandium-stabilized zirconium oxide (ScSZ), as well as doped cerium oxides such as gadolinium-doped cerium oxide (abbreviated as GDC or CGO) or samarium-doped cerium oxide (SDC or CSO).

[0229] CO2 is fed into the cathode side of the battery via gas channels that help distribute the gas throughout the battery. In the porous cathode (also known as the fuel electrode), carbon dioxide is reduced to carbon monoxide following the reaction:

[0230] CO2 + 2e - -> CO + O 2-

[0231] Electrons used in the reaction are provided by an external power source. Oxygen ions (O3) formed in the reaction... 2- These ions combine with the electrolyte and pass through the electrode to the anode (also known as the oxygen electrode), where they are oxidized into molecular oxygen according to the following reaction.

[0232] O 2- -> ½ O2 + 2 e -

[0233] The oxygen produced is drawn out of the battery through a gas channel. It is important to note that as long as pure CO2 (or a mixture of CO and CO2) is fed into the fuel electrode, the products formed will not contain H2 or H2O.

[0234] Composites of metallic Ni and CGO or YSZ are the most commonly used materials for SOEC fuel electrodes. Typical oxygen electrode materials for SOEC include lanthanide and transition metal-doped perovskites, such as Sr-doped LaMnO3 (LSM), Sr-doped La(Fe,Co)O3 (LSCF), and Sr-doped SmCoO3 (SSC).

[0235] In molten carbonate electrolysis (MCEC), the electrolyte is a carbonate melt. Promising results have been shown with a combination of molten Li₂O / Li₂CO₃ electrolyte, titanium cathode, and graphite anode. In this material system, carbonate ions are reduced to CO and oxygen ions (CO₃²⁻) at the cathode. 2- + 2 e - -> CO + 2 O2- Oxygen ions are oxidized to gaseous oxygen (O2) at the anode. 2- -> ½ O2 + 2 e - ).

[0236] In practice, Li₂CO₃ is electrochemically converted to Li₂O at the cathode, thereby increasing the Li₂O / Li₂CO₃ ratio in the melt. As the oxide content in the electrolyte increases, new CO₂ can chemically bind to the mixture. Thus, the Li₂O / Li₂CO₃ ratio in the electrolyte is a function of both the applied current density and the concentration of CO₂ above the melt. A key advantage of MCEC is that the CO₂ feed is immiscible with the CO and O₂ products, allowing for the extraction of pure gas from the cell. Furthermore, the method is only slightly affected by the SO₂ content in the feed gas and may potentially utilize diluted and moistened CO₂ streams, suggesting that industrial flue gas can be used as a feed.

[0237] In low-temperature electrolyzers, CO2 reduction takes place in an aqueous solution. The electrolyte can be a solid ion-selective membrane (e.g., Nafion, Sustainion), an aqueous solution (e.g., KHCO3), or a combination thereof. Most low-temperature electrolyzers today operate under alkaline or pH-neutral conditions.

[0238] Most electrode development work for electrochemical CO2 reduction has been carried out using a cell configuration in which both electrodes of the electrolyzer are immersed in an electrolyte solution (the anolyte and the catholyte, respectively). This electrode configuration is called an H-cell. At the anode of this type of cell, oxygen evolution occurs according to either of the following two reactions:

[0239] 2 OH - -> ½ O2 + H2O + 2 e -

[0240] H2O -> ½ O2 + 2 H + + 2 e -

[0241] At the cathode, CO2 is electrochemically reduced to CO:

[0242] CO2 + H2O + 2 e - -> CO + 2 OH -

[0243] Typically, CO production is accompanied by hydrogen evolution, which occurs in an alkaline medium via the following reaction.

[0244] 2 H2O + 2 e - -> 2 OH - + H2

[0245] Delivering gaseous CO2 to the cathode and using gas diffusion electrodes provides a means to overcome mass transfer limitations in low-temperature electrolysis systems. In some designs, gas diffusion electrodes are used in both electrodes. IrO2 is almost exclusively used as a catalyst material on the anode side of aqueous electrolyzers. Cathode materials for CO production typically include Ag and Au, with the catalyst support showing significant influence on activity, selectivity, and stability.

[0246] The electricity required to electrochemically reduce CO2 to CO must be generated at least partially from non-fossil renewable resources. In other words, some of the electricity can still be generated from fossil fuels, preferably natural gas, because the combustion of natural gas results in much lower CO2 emissions per megajoule of electricity compared to the combustion of coal. However, the portion of electricity generated from fossil fuels should be as low as possible, preferably ≤ 50%, more preferably ≤ 30%, and most preferably ≤ 20%.

[0247] The electricity generated from non-fossil resources and used in the carbon dioxide produced according to the present invention can be produced by nuclear energy. The European Commission considers nuclear energy to be renewable provided certain prerequisites are met (i.e., the safe long-term storage of nuclear waste).

[0248] The electricity derived from non-fossil resources used in the carbon dioxide of the present invention is preferably generated by wind, solar, biomass, hydropower, and geothermal energy.

[0249] In some other preferred embodiments, the carbon dioxide provided in step (b) is captured from ambient air.

[0250] Direct air capture (DAC) is a process that directly captures carbon dioxide (CO2) from ambient air and produces a concentrated stream of CO2 for isolation, utilization, or production of carbon-neutral fuels. CO2 removal is achieved when ambient air comes into contact with a chemical medium (typically an aqueous, alkaline solvent or an adsorbent). These chemicals are then stripped of CO2 by the application of energy (i.e., heat), yielding a CO2 stream that can be dehydrated and compressed, while simultaneously regenerating the chemical medium for reuse.

[0251] Diluted CO2 can be efficiently separated using an anion exchange polymer resin called Marathon MSA, which absorbs CO2 from the air when dry and releases it when exposed to moisture. Most of the energy used in this process is supplied by the latent heat of phase change of water. Other materials that can be used are metal-organic frameworks (or MOFs). Membrane separation of CO2 relies on semipermeable membranes.

[0252] Carbon dioxide captured from ambient air can also be electrochemically reduced by the methods described above prior to its use in step (b) or step (c1).

[0253] In step (b), carbon monoxide is converted into C2 products in an electrochemical reactor. According to equations (2) to (5), in addition to ethylene, ethanol, acetic acid, oxygen, and hydrogen can also be formed as products:

[0254] 2 CO + 2 H2O → C2H4 + 2 O2(2)

[0255] 2 CO + 3 H2O → CH3CH2OH + 2 O2(3)

[0256] 2 CO + 2 H2O → CH3COOH + O2(4)

[0257] 2 H₂O → 2 H₂ + O₂ (5)

[0258] This method is described by Klüh et al. (2023), Front. Energy Res. 11:1129076 and other references.

[0259] In some embodiments, a gas mixture containing carbon monoxide, hydrogen, and carbon dioxide is reacted in step (c1) in the presence of a catalyst to obtain methanol.

[0260] Currently, the world's large-scale methanol synthesis technology is mainly based on the application of Cu / ZnO / Al2O3 (CZA) catalysts in multi-tube reactors (often called isothermal reactors, e.g., the Lurgi process, the Linde process) using boiling water as the cooling fluid, or in adiabatic reactors with intercooled syngas quenching (often called quench reactors, e.g., the ICI and Casale processes, the Haldor Topsoe process). Less common but also industrially used are adiabatic reactors with intercooling (e.g., the Kellogg process, the Toyo process). Typically, temperatures between 200°C and 300°C and pressures between 50 and 100 bar are applied. See Bozzano, G.; Manenti, F. Efficient methanol synthesis: Perspectives, technologies and optimization strategies. Prog. Energy Combust. Sci. 2016, 56, 71–105; and Ott, J.; Gronemann, V.; Pontzen, F.; Fiedler, E.; Grossmann, G.; Kersebohm, DB; Weiss, G.; Witte, C. Methanol. Ullmann's Encyclopedia of Industrial Chemistry; Wiley: New York, NY, USA, 2012.

[0261] In some other embodiments, hydrogen and carbon dioxide are reacted in step (c1) in the presence of a catalyst to form methanol.

[0262] A review of suitable catalyst systems is given in auth-Kristian-Stangeland, Hailong Li and Zhixin Yu, Energy, Ecology and Environment, Vol. 5, pp. 272-285 (2020). This process requires a multi-component catalyst system. Interactions between components are essential for the high activity and selectivity of the CO2 to methanol catalyst. This has been demonstrated by a variety of catalyst systems composed of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., ZnO, ZrO2, In2O3). These complex systems can contain mixtures of metallic, alloy, and metal oxide phases. The most promising catalyst systems for large-scale industrial methods are currently Cu-based and In-based catalysts due to their excellent catalytic performance.

[0263] The process for the synthesis of methanol from CO2 can be carried out, for example, by a method known from DE-A-42 20 865, which produces methanol under the influence of silent discharge.

[0264] Alternatively, methanol synthesis can also be carried out in a thermal reactor under pressure and elevated temperature in the presence of a copper-based catalyst, as described in DE 43 32 789 A1 and DE 19739773 A1.

[0265] For example, a typical catalyst is described by N. Kanoun et al. in the following publication: CATALYSIS LETTERS 15, (1992) 231-235, “Catalytic properties of Cu based catalysts containing Zr and / or V for methanol synthesis from a carbon dioxide and hydrogen mixture”. Potential catalysts such as CuO / ZnO and Cu-ZnO-Al2O3 have also been described by RM Navarro et al. in “Methanol Synthesis from CO2: A Review of the Latest Developments in Heterogeneous Catalysis” Materials (2019), 12, 3902 and “Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies” Chemical Engineering Research and Design 92 (2014) 2557-2567.

[0266] Recently, a highly selective catalyst, In₂O₃ / ZrO₂, for industrially relevant conditions has been described. Typical industrially relevant conditions for CO₂ hydrogenation to methanol range from T = 200°C to 300°C, p = 10⁻⁵ MPa, and gas hourly space velocity (GHSV) of 16,000 to 48,000 h⁻¹. -1 (Angew. Chem. Int. Ed. [Germany's Angewandte Chemie International Edition] 2016, 55, 6261-6265).

[0267] The reaction of hydrogen and carbon dioxide in step (c1) can be carried out in the presence of a copper-zinc-alumina catalyst. If a copper-zinc-alumina catalyst is used, the preferred temperature is in the range of 150°C to 300°C, more preferably 175°C to 300°C, and the preferred pressure is in the range of 10 to 150 bar (absolute pressure).

[0268] In step (c2), the methanol from step (c1) is reacted to produce ethylene.

[0269] C2-C4 olefins can be produced from methanol via the methanol-to-olefins (MTO) process. A preferred method for producing C2-C4 olefins from methanol and optionally ethanol includes the following steps:

[0270] A) A feed stream A containing methanol and optionally ethanol is fed into a dimethyl ether fixed-bed reactor and the methanol is catalytically converted to dimethyl ether, wherein a product stream A1 containing dimethyl ether, methanol, water vapor and optionally ethanol and ethylene is obtained.

[0271] B) Mix the stream A1 with at least one hydrocarbon recycling stream R containing C2-C6 hydrocarbons and catalytically convert it in an olefin fixed-bed reactor to produce C2-C4 olefins, C5-C6 hydrocarbons and C7 hydrocarbons. + Crude hydrocarbon stream B;

[0272] C) Cool the crude product stream B to obtain a crude hydrocarbon product stream C;

[0273] D) Separate the crude hydrocarbon stream C into a valuable product stream containing propylene, optionally a valuable product stream containing ethylene, a product stream containing butene, at least one recycling stream containing C5-C6 hydrocarbons, and at least one C6 hydrocarbon-containing stream. + Hydrocarbon byproduct streams;

[0274] E) Recycle a portion of the C2-C4 olefin and at least a portion of the C5-C6 hydrocarbon as one or more hydrocarbon recycling streams R into step B);

[0275] F) Recover valuable product streams containing propylene, valuable product streams containing ethylene, and optionally valuable product streams containing butene.

[0276] G) Excretion of C6-containing substances + Hydrocarbon byproduct stream.

[0277] In an alternative method, ethanol is produced from biomass by fermentation in step (d1), and the ethanol is dehydrogenated in step (d2) to obtain ethylene.

[0278] A sustainable alternative to petroleum-based methods that utilize forest or agricultural industrial waste to produce ethylene-based ethanol through bioethanol dehydration. Gasification of lignocellulosic biomass is a thermochemical pathway for bioethanol production. Using a chemical catalyst, syngas is used to produce ethanol and a mixture of alcohols. Another option for ethanol production is the fermentation of syngas.

[0279] The bioconversion of wood waste to bio-ethylene is described in Mendieta, CM, Cardozo, RE, Felissia, FE, Clauser, NM, Vallejos, ME and Area, MC (2021). "Bioconversion of wood waste to bio-ethylene: A review," BioResources, 16(2), 4411-4437, and other references.

[0280] The ethylene production method consists of the following steps: pretreatment, enzymatic hydrolysis, fermentation, distillation recovery, and dehydration. The conditions and type of pretreatment depend solely on the chemical composition of the feedstock, which significantly influences the enzymatic hydrolysis and subsequent processes.

[0281] Prior to bioethanol production, the pretreatment of lignocellulosic biomass is crucial. Among other characteristics, effective pretreatment should utilize inexpensive and easily recyclable reagents, applied to various substrates with low energy consumption and low investment and maintenance costs. These reactions must favor sugar formation, prevent their loss due to degradation, and limit the formation of inhibitory products. Pretreatment processes extract lignin and hemicellulose to increase the porosity of the material, thereby improving the accessibility of cellulose to enzymatic attack. Pretreatment processes should also limit the degradation of other carbohydrates and avoid the formation of inhibitory products during the saccharification stage.

[0282] Cellulose obtained through pretreatment can be converted to ethanol in two steps. Initially, cellulose is depolymerized into glucose via hydrolysis, and these sugars are then fermented into ethanol. Common pretreatment strategies are separate hydrolysis and fermentation (SHF) and simultaneous hydrolysis and fermentation (SSF). In the SHF process, cellulose hydrolysis and glucose fermentation are performed separately, allowing each stage to occur under its optimal conditions. On the other hand, the SSF process requires only one reactor for both hydrolysis and fermentation. Considering the low production of inhibitory products and the use of only one fermenter throughout the process (which reduces investment costs), the SSF process is the most feasible and cost-effective alternative for producing bioethanol.

[0283] In the petrochemical industry, the dehydration of ethanol to ethylene is a conventional process. However, for ethylene processes, the ethanol purity must be higher than 95 wt%. Unlike ethanol, bioethanol originates from fermentation broth containing microorganisms, nutrients, and reaction byproducts. The obtained bioethanol must be purified by removing contaminants and additional water. Several methods, combining distillation, adsorption, and extraction, such as membrane pervaporation separation, extractive distillation, or heterogeneous azeotropic distillation, have been described in detail in the literature. For ethylene production, particularly when using SHF, ultra-high concentration (VHG) fermentation has emerged as an interesting option for exploration and optimization because it can improve fermentation performance while simultaneously purifying ethanol. Considering this is a stage with significant energy consumption, it is one of the steps that needs to be optimized to contribute to the economic feasibility of bioethylene production.

[0284] Ethylene is formed through the highly endothermic intramolecular dehydration of ethanol (which eliminates one oxygen atom and two hydrogen atoms). Ethylene formation occurs at temperatures between 350°C and 500°C. At lower temperatures, intermolecular dehydration also produces diethyl ether, which can be sequentially dehydrated to form ethylene. A catalyst is necessary for the dehydration reaction. Alumina, or alumina combined with metal oxides (as promoters), silica, clay, several metal oxides, phosphorus oxides, phosphates, molybdates, sulfuric acid, and zeolites, has been studied as a catalyst. Industrially, phosphoric acid and alumina are already used on a small scale, and they have been used to increase ethylene selectivity. Alumina is the most commonly used catalyst for the dehydration of bioethanol because it can withstand temperatures above 450°C, but it deactivates rapidly at temperatures below 300°C. Zeolites are used for the reaction because they do not require high temperatures, but catalyst deactivation can occur at low temperatures due to coking.

[0285] The effluent contains a significant amount of water from the dehydration reaction, as well as ethanol feedstock and heat transfer fluid. Water can be separated in the quench tower, and residual ethanol and water-soluble oxygenated compounds can be reheated and distilled. Residual ethanol and diethyl ether (low water solubility) can be recovered and recycled back to the feedstock, while C2H4O can be combusted in the furnace. The gas from the top of the quench tower primarily contains ethylene (90% to 99.5%), hydrocarbons, H2, CO, CO2, and oxygenated compounds. Ethylene can be washed with cold water in a second tower to remove oxygenated compounds, and caustic washing can remove CO2 and acids.

[0286] In alternative step (e), ethylene is produced directly from biomass via fermentation. Suitable fermentation methods are described in I. Pirkov, E. Albers, J. Norbeck, C. Larsson, Ethylene production by metabolic engineering of the yeast Saccharomyces cerevisiae, Metabolic Engineering, Vol. 10, No. 5, 2008, pp. 276-280; and Johansson, N., Quehl, P., Norbeck, J. et al., Identification of factors for improved ethylene production via the ethyleneforming enzyme in chemostat cultures of Saccharomyces cerevisiae, Microb Cell Fact, 12, 89 (2013).

[0287] Acetic acid can be produced by the carbonylation of methanol in step (f). This method involves iodomethane as an intermediate and is carried out in three steps. The carbonylation (step 2) requires a catalyst, a metal carbonyl compound.

[0288] 4. CH3OH + HI → CH3I + H2O

[0289] 5. CH3I + CO → CH3COI

[0290] 6.CH3COI + H2O → CH3COOH + HI

[0291] There are two relevant methods for methanol carbonylation: the rhodium-catalyzed Monsanto process and the iridium-catalyzed Kativa process.

[0292] The Monsanto process operates at pressures of 30–60 atm and temperatures of 150–200°C, exhibiting selectivity greater than 99%. The catalytically active material is the anionic cis-[Rh(CO)₂I₂]. - The first organometallic step involves the oxidative addition of iodomethane to cis-[Rh(CO)₂I₂]. - To form a six-coordinate compound [(CH3)Rh(CO)2I3]- The anion rapidly transforms via methyl migration to the adjacent carbonyl ligand, yielding the five-coordinate acetyl complex [(CH3CO)Rh(CO)I3]. - The five-coordinate complex then reacts with carbon monoxide to form a six-coordinate dicarbonyl complex, which undergoes reductive elimination to release acetyl iodide (CH3C(O)I). The catalytic cycle involves two non-organometallic steps: the conversion of methanol to iodomethane and the hydrolysis of acetyl iodide to acetic acid and hydrogen iodide.

[0293] The Kativa process is another method for producing acetic acid via the carbonylation of methanol. This technology is similar to the Monsanto process. This method is based on iridium-containing catalysts, such as the complex [Ir(CO)₂I₂]. - The catalytic cycle of the Kativa process begins with the reaction of iodomethane with a square planar active catalyst to form an octahedral iridium(III) compound [Ir(CO)2(CH3)I3]. - This oxidative addition reaction involves the insertion of an iridium (I) center into the carbon-iodine bond of iodomethane. Following ligand exchange between the iodide and carbon monoxide, the carbon monoxide migrates and inserts into the iridium-carbon bond, resulting in the formation of a substance with bound acetyl ligands. The active catalyst is regenerated by reducing and eliminating the acetyl iodide. In the production of hydroiodic acid, the acetyl iodide is hydrolyzed to produce acetic acid, which is then used to convert the starting material methanol into iodomethane used in the first step.

[0294] Alternatively, acetic acid can be produced by the following methods:

[0295] (g1) React a portion of the ethylene from steps (b), (c1) / (c2), (d2), or (e) with oxygen and water to give acetaldehyde;

[0296] (g2) React the acetaldehyde from step (g1) with oxygen to obtain acetic acid.

[0297] The Wacker process, or Wacker-Hurst process, refers to the oxidation of ethylene to acetaldehyde in the presence of palladium(II) chloride as a catalyst.

[0298] The net reaction can be described as follows:

[0299] [PdCl4] 2 - + C2H4 + H2O → CH3CHO + Pd + 2 HCl + 2 Cl -

[0300] This transformation is followed by the reaction to regenerate the Pd(II) catalyst:

[0301] Pd + 2 CuCl2 + 2 Cl -→ [PdCl4] 2- + 2 CuCl

[0302] 2 CuCl + 1 / 2 O2 + 2 HCl → 2 CuCl2 + H2O

[0303] Two methods have been commercialized for the production of acetaldehyde: the single-stage method and the two-stage method.

[0304] In the single-stage process, ethylene and oxygen are passed in parallel through a reaction tower at approximately 130°C and 400 kPa. The catalysts are an aqueous solution of PdCl2 and CuCl2. Acetaldehyde is purified by extractive distillation followed by fractional distillation. Extractive distillation with water removes lighter fractions (chloromethane, chloroethane, and carbon dioxide) with lower boiling points than acetaldehyde at the top, while water and higher-boiling byproducts (such as acetic acid, crotonaldehyde, or acetaldehyde chloride) are removed at the bottom along with the acetaldehyde.

[0305] In the two-stage process, the reaction and oxidation are carried out separately in a tubular reactor. Unlike the single-stage process, air can be used instead of oxygen. Ethylene and the catalyst are passed through the reactor together at 105°C–110°C and 900–1000 kPa. The catalyst solution containing acetaldehyde is separated by flash evaporation. The catalyst is oxidized in an oxidation reactor using air as the oxidation medium at 1000 kPa. The oxidized catalyst solution is separated and returned to the reactor. The oxygen in the air is completely used up, and the exhaust gas is recycled as an inert gas. The acetaldehyde-water vapor mixture is pre-concentrated to 60%–90% acetaldehyde using the heat of reaction, and the discharged water is returned to the flash column to maintain the catalyst concentration. This is followed by a two-stage distillation of crude acetaldehyde. In the first stage, low-boiling substances such as chloromethane, chloroethane, and carbon dioxide are separated. In the second stage, water and higher-boiling byproducts (such as acetaldehyde chloride and acetic acid) are removed, and acetaldehyde is obtained in pure form at the top of the column.

[0306] In both the single-stage and two-stage methods, the acetaldehyde yield is approximately 95%.

[0307] For further details, please refer to Marc Eckert, Gerald Fleischmann, Reinhard Jira, Hermann M. Bolt, Klaus Golka, Acetaldehyd, Ullmann's Encyclopedia of Industrial Chemistry, 7th Edition, Volume 1, Chapter 4.3, page 197.

[0308] In step (e2), acetaldehyde can be oxidized with pure oxygen or air in the presence of a redox catalyst to obtain acetic acid. The oxidation can be carried out in a bubble column at a temperature of 50°C–70°C in the presence of cobalt acetate or manganese acetate as a solvent (Hurster process).

[0309] Acetic acid can also be produced in step (h) by oxidative fermentation of ethanol from step (d1).

[0310] In another alternative step (i), acetic acid can be produced from biomass through biomass pyrolysis.

[0311] Suitable methods for producing acetic acid via biomass pyrolysis are described, for example, in US 2012 / 0172622 A1. Methods for producing acetic acid include pyrolyzing biomass, typically lignocellulosic materials (such as wood, corn stalks, and / or switchgrass), to provide pyrolysis reactor effluent. Biomass subjected to pyrolysis in an oxygen-deficient environment (e.g., using rapid thermal processing (RTP)) can be any plant material or a mixture of plant materials. These methods also include separating at least a portion of the pyrolysis reactor effluent in a first separation stage (e.g., a quench tower including quench liquid recirculation) to provide a first-stage overhead distillate and a first-stage bottom product. These methods further include recovering acetic acid from the first-stage overhead product or the first-stage bottom product. Recovery can involve various processing steps, some or all of which may enrich the recovered intermediate or final product (e.g., purified acetic acid product) with acetic acid and deplete the recovered product from other compounds produced by pyrolysis (e.g., water and other oxygen-containing compounds).

[0312] According to the present invention, vinyl acetate is produced by reacting (I) ethylene with (II) acetic acid, both of which are produced from biomass or CO2 captured from the atmosphere.

[0313] Most vinyl acetate is produced via a gas-phase reaction of ethylene and acetic acid over a noble metal catalyst (typically palladium). This reaction is typically carried out at 150°C–250°C, preferably 175°C–200°C, and pressures of 5–9 bar. The reaction is usually conducted in a fixed-bed tubular reactor using a supported catalyst in the gas phase. The amount of oxygen in the combined feed is in the range of 5–15 mol%. Preferably, the amount of acetic acid in the combined feed is in the range of 10–25 mol%. Preferably, the amount of ethylene in the combined feed is in the range of 65–80 mol%. Suitable catalysts include those known in the vinyl acetate industry. Preferably, the catalyst is a palladium-gold catalyst. Methods for preparing palladium-gold catalysts are known. For example, U.S. Patent No. 6,022,823 teaches how to prepare palladium-gold catalysts with high activity and selectivity. Preferably, the palladium-gold catalyst is supported on inorganic oxides (such as alumina, silica, titanium dioxide, etc.) and mixtures thereof.

[0314] The present invention further relates to vinyl acetate having a natural abundance of C-14, which can be obtained by the methods described herein.

[0315] If the carbon dioxide in step (b) is captured from ambient air, then vinyl acetate can have a δ value corresponding to -10‰ to -2.5‰. 13 C value 13 C content.

[0316] Vinyl acetate can be polymerized into polyvinyl acetate. Polyvinyl acetate eventually hydrolyzes into biodegradable polyvinyl alcohol. If the carbon oxides in step (a) are produced from biomass or CO2 is obtained from the atmosphere, the biodegradation of polyvinyl alcohol produces H2O and CO2, thus closing the loop of the CO2 neutral life cycle.

[0317] Poly(vinyl esters) is non-toxic, but it degrades slowly in water. See Rinno, H. (2000), Poly(vinyl esters), Ullmann's Encyclopedia of Industrial Chemistry, 7th edition, Volume 28, Chapter 8, page 477 and following pages.

[0318] Polyvinyl alcohol (PVA) is considered one of the very few vinyl polymers that are soluble in water and readily biodegrades in the presence of appropriately adapted microorganisms. PVA is non-toxic but is expected to biodegrade within 90 days under aquatic conditions; see Dominic Byrne et al., Biodegradability of polyvinyl alcohol based film used for liquid detergent capsules, Tenside Surf. Det. 58 (2021) 2; E. Chiellini et al., Prog. Polym. Sci. 28 (2003), pp. 963-1014.

[0319] For the copolymerization of bio-based vinyl acetate, several monomers are relevant, with the most preferred monomers selected from other vinyl esters, such as vinyl propionate and vinyl laurate, vinyl neopentanoate, and vinyl esters of branched alkyl carbonates. Equally important and preferred are maleate esters, fumarate esters, allyl ethers, vinyl ethers such as vinyl ethyl ether, vinyl chloride, and cyclic vinyl amides such as vinylpyrrolidone. Ethylene and styrene are also known to be copolymerized. If a third monomer from among the aforementioned monomers is present, acrylates and methacrylates such as methyl methacrylate can also be effectively copolymerized.

[0320] It is also known that vinyl acetate can be effectively grafted onto polyethers such as polyethylene glycol and other polyalkylene glycols such as randomized copolymers of polyethylene oxide-block-polypropylene oxide or even alkylene oxides. In this manner, block copolymers of polyvinyl acetate with the aforementioned polyethers are available. These block copolymers of polyvinyl acetate can be used as amphiphilic surfactants in laundry detergents and as emulsifiers in formulations containing agriculturally active substances.

[0321] Vinyl acetate grafting also occurs efficiently on polysaccharides and other suitable polyhydroxy polymers (e.g., polyvinyl alcohol), leading to the formation of biodegradable block copolymers. Binary and terpolymers having combined vinyl acetate / vinyl alcohol monomer units can be obtained through partial hydrolysis of vinyl acetate copolymers.

[0322] The present invention also relates to polymers or copolymers of vinyl acetate and polymer dispersions containing vinyl acetate, wherein vinyl acetate has a natural abundance of carbon-14.

[0323] Polymer dispersions containing vinyl acetate, and specifically polymer emulsions, are well known and used in many applications, such as those described in the following literature:

[0324] EP1924633 discloses a method and dispersion consisting of vinyl acetate and 0.05%-5.0% by weight of methacrylic acid, obtained by free radical-initiated emulsion polymerization. A water-soluble polymer is used as a protective colloid and sodium dodecyl sulfate is used as an emulsifier. Target applications are film coating and sustained release of active ingredients in pharmacological and cosmetic applications.

[0325] DE102004031970 describes a method for the solution polymerization of vinyl monomers such as vinyl acetate and olefinically unsaturated polyethers such as allyl polyethers in methanol. Protection is also claimed for esters of polyethers of methacrylic acid corresponding to terminal OH and OR groups, wherein R may be an alkyl group having C1-C40. Target applications include the production of plasticized vinyl acetate solid resins.

[0326] JP2005089540 describes an emulsion process for producing vinyl acetate polymer resins in the presence of polymerizable polyethylene glycol derivatives. The use of cellulose-based protective colloids is reported.

[0327] JP06093007 discloses a polyvinyl acetate-based emulsion, which is produced by emulsion polymerization of 50%-100% by weight of vinyl acetate and 0%-50% by weight of one or more comonomers (e.g., acrylates) using a water-soluble modified starch as a protective colloid. It is intended for the production of films with good low-temperature properties and high hardness.

[0328] US4708999 describes the solution polymerization of vinyl acetate and C1 to C12 alkyl polyethylene glycol methacrylate (polyethylene glycol with 25% ethylene oxide) in methanol. The product is then subjected to methanol decomposition.

[0329] JP59155411 discloses copolymers of alkylene oxide-containing unsaturated monomers with vinyl acetate in solution polymerization in alcohols. The copolymerization of vinyl acetate includes alkylene oxide-containing unsaturated monomers (such as methacrylic acid). The number of alkylene oxides advantageously ranges from 1 to 50. Modified vinyl acetate resins are water-soluble even in the absence of alkali metals, and are particularly suitable for pastes, adhesives, or aqueous solutions in paper processing and other applications.

[0330] US3322703 relates to copolymers composed of vinyl acetate and alkoxy polyalkylene glycol half-esters of unsaturated dicarboxylic acids or / and vinyl acetate and alkoxy polyalkylene glycol esters of unsaturated monocarboxylic acids, and methods for their preparation. Solution polymerization of vinyl acetate and methoxy polyethylene glycol maleate in methanol is given as an example. The intended use is not claimed, but rather described in the form of application of coated articles that can be wetted and form an adhesive film, such as for postage stamps.

[0331] EP199358 describes a terpolymer consisting of vinyl alcohol, vinyl acetate, and alkyl polyoxyethylene methacrylate. Fabric protection includes at least 50% vinyl alcohol in the terpolymer. The terpolymer is used as a barrier layer in the thermoplastic process for packaging articles.

[0332] PCT / EP2023 / 081697 describes aqueous polymer dispersions suitable as light-shielding agents in liquid formulations. These dispersions are obtained by free radical emulsion polymerization in an aqueous environment of the following: i) at least one vinyl ester; ii) at least one (meth)acrylate, optionally a small amount of additional (meth)acrylic acid, wherein the (meth)acrylic acid in the methacrylate is bonded via an ether functional group to a polyepoxide-derived block polymer having 2 to 40 epoxides; and iii) optionally additional polymerizable monomers, the polymerization optionally occurring in the presence of a carboxyl-containing compound and a non-carboxylated compound; and c) at least one emulsifier selected from nonionic and anionic surfactants. Such aqueous polymer dispersions are preferably used in cleaning compositions such as detergents, specifically as light-shielding agents.

[0333] The present invention also relates to the use of vinyl acetate with natural abundance of C-14 for determining the content of bio-based vinyl acetate or vinyl alcohol derived therefrom in polymers and copolymers containing vinyl acetate or vinyl alcohol.

[0334] The present invention further relates to the use of vinyl acetate with natural abundance of C-14 for determining the source of decay products released during the decomposition of polymers or copolymers containing vinyl acetate or vinyl alcohol.

[0335] Polymers and copolymers whose bio-based vinyl acetate or vinyl alcohol content can be determined, or whose sources of decay products released from them during decomposition can be determined, include:

[0336] - Polyvinyl acetate, polyvinyl alcohol, poly(vinyl acetate-co-vinyl alcohol);

[0337] - Poly(vinyl acetate-co-vinylalkyl ether), poly(vinyl acetate-co-allylalkyl ether), poly(vinyl acetate-co-maleic acid derivative), poly(vinyl acetate-co-methacrylic acid derivative), poly(vinyl acetate-co-vinylpyrrolidone) and their partially hydrolyzed derivatives (in the form of terpolymers);

[0338] - A terpolymer of vinyl acetate, vinyl alcohol, and at least one other comonomer selected from the following: vinyl laurate, vinyl versate, vinyl alkyl ether, vinyl silyl ether, vinyl pyrrolidone, vinyl caprolactone, maleic acid and maleic anhydride and their derivatives (e.g., methyl esters), fumaric acid and fumaric acid derivatives, allyl alkyl ether, allyl alcohol ester, acrylic acid and methacrylic acid and their derivatives (e.g., amides and esters), ketone derivatives (such as cyclic enone acetal monomers), and ethylene (the terpolymer can be obtained by partial hydrolysis of the corresponding vinyl acetate copolymer);

[0339] - Graft copolymers derived from vinyl acetate polymers, such as poly(vinyl acetate)-g-polyepoxide, or poly(vinyl acetate)-g-polyglucan / polysaccharide derivatives, and their derivatives obtained by hydrolysis or partial hydrolysis.

[0340] The carbon-14 content in (co)polymers or decay products can be determined using gas proportional counting, liquid scintillation counting, and accelerator mass spectrometry (AMS).

[0341] Alkoxylated compounds from ethylene oxide and propylene oxide

[0342] Alkoxylated compounds such as polyalkylene glycols and compounds containing alkylene glycol groups are used in a variety of industrial applications and exhibit high performance when used in, for example, the following: home care products, cosmetic products, pharmaceutical products, the food industry, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agricultural chemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages, and poly(urethane) applications.

[0343] A review of polyalkylene glycols is given in Chem. Rev. 2016, 116, 2170-2243. It describes polyalkylene glycols as aliphatic polyethers produced by ring-opening polymerization (ROP) of epoxide monomers, particularly ethylene oxide (EO), propylene oxide (PO), and to a lesser extent, butylene oxide (BO). The characteristic properties of polyether-based materials are due to their unique backbone, particularly their high flexibility resulting from a low glass transition below -60°C, and their hydrophilicity due to the COC bonds.

[0344] In this application, the terms "polyalkylene glycol", "polyethylene glycol", "polypropylene glycol", and "polybutylene glycol" are used for the corresponding polymers or polymer blocks of any molecular weight.

[0345] The present invention further relates to a method for preparing alkoxylated compounds, the alkoxylated compounds comprising

[0346] i) 20 wt% to < 100 wt% ethylene oxide units and / or propylene oxide units,

[0347] ii) at least one alkylene oxide unit, different from ethylene oxide and propylene oxide units, ranging from 0 wt% to 30 wt%.

[0348] iii) > 0 wt% to 80 wt% of at least one starting unit having a Zerewitinoff active hydrogen atom,

[0349] The sum of the units mentioned under i), ii) and iii) is 100 wt%

[0350] The method includes the following steps:

[0351] (a This allows hydrogen to react with carbon dioxide to form methanol.

[0352] (b ) will come from step (a) The methanol is converted into ethylene and / or propylene.

[0353] (c ) make from step (b) The ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and

[0354] (d In one or more steps, make step (c) The ethylene oxide and / or propylene oxide obtained in the process, and optionally at least one alkyl oxide different from ethylene oxide and propylene oxide, react with the at least one starting unit having a Zelevithinov active hydrogen atom to form the alkoxylated compound.

[0355] Among them, step (a) The carbon dioxide in the substance is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

[0356] The terms ethylene and propene are the IUPAC names of compounds with the formulas CH2=CH2 and CH3CH=CH2, which are also known as ethylene and propylene.

[0357] The IUPAC name for the term ethylene oxide used in this application is oxirane (C2H4O).

[0358] In the context of this application, propylene oxide is 1,2-propylene oxide. The IUPAC name for the term propylene oxide as used herein is 2-methylethylene oxide (C3H6O). An alternative name is 1,2-propylene oxide.

[0359] Ethylene oxide unit is the reactive form of ethylene oxide in alkoxylated compounds, propylene oxide unit is the reactive form of propylene oxide in alkoxylated compounds, and alkyl oxide unit is the reactive form of alkyl oxide in alkoxylated compounds.

[0360] As used in this application, the term "alkoxylated compound" encompasses an alkoxylated compound consisting of at least one ethylene oxide unit and / or propylene oxide unit and at least one starting unit having a Zelevithinov active hydrogen atom.

[0361] According to REACH (Article 3(5)) (EC 1907 / 2006 of the European Parliament and of the Council of 18 December 2006), polymers are defined as substances that meet the following criteria:

[0362] (a) The substance is composed of polymer molecules comprising more than 50% of its weight (see definition below); and,

[0363] (b) The amount of polymer molecules of the same molecular weight must be less than 50% of the weight of the substance.

[0364] In the context of this definition:

[0365] • A “polymer molecule” is a molecule containing a sequence of at least three monomer units that are covalently bonded to at least one other monomer unit or other reactant.

[0366] • “Monomer unit” refers to the reaction form of monomeric substances in a polymer (in order to identify one or more monomer units in the chemical structure of a polymer, the mechanism of polymer formation can be considered, for example).

[0367] • A “sequence” is a continuous chain of monomeric units within a molecule that are covalently bonded to each other and are not interrupted by units other than monomeric units. This continuous chain of monomeric units may follow any network within the polymer structure.

[0368] • "Other reactants" refers to molecules that can be linked to one or more sequences of a monomer unit but cannot be considered monomers under the relevant reaction conditions used in the polymer formation method.

[0369] As used herein, the term "polymer" includes both homopolymers and copolymers. A "polymer" can be linear or branched.

[0370] The biodegradability of the alkoxylated compounds according to the present invention is determined based on currently effective OECD guidelines.

[0371] The OECD distinguishes six biodegradation forms in its guidelines, as follows (OECD, 1981b, 1991, 1992a, 1992b, 2001, 2002, 2004a, 2008) (see https: / / www.ecetoc.org / technical-report-123 / measured-partitioning-property-data / biodegradation / definitions-according-to-oecd / ).

[0372] (i) Final biodegradation (mineralization): The level of degradation achieved when the test compound is fully utilized by microorganisms, resulting in the production of carbon dioxide, water, mineral salts and new microbial cell components (biomass).

[0373] (ii) Primary biodegradation (biotransformation): Changes in the chemical structure of a substance caused by biological processes, resulting in the loss of the substance's specific properties.

[0374] (iii) Easily biodegradable: Any classification of chemicals that have passed certain specific screening tests for ultimate biodegradability; these tests are so rigorous that it is assumed that such compounds will be rapidly and completely biodegraded in aquatic environments under aerobic conditions.

[0375] (iv) Inherently biodegradable: A classification of chemicals that have clear evidence of biodegradability (primary or final) in any test for biodegradability.

[0376] (v) Half-life (t0.5): The time taken for 50% conversion of the test substance when the conversion can be described by first-order kinetics; it is independent of the initial concentration.

[0377] (vi) Disappearance Time 50 (DT50): The time it takes for the initial concentration of the test substance to decrease by 50%.

[0378] The alkoxylated compounds according to the invention are typically tested according to OECD 301B regarding their biodegradability.

[0379] Test No. 301: Ready to biodegrade (https: / / www.oecd-ilibrary.org / environment / test-no-301-ready-biodegradability_9789264070349-en)

[0380] This testing guide describes six methods that allow screening for chemicals that are readily biodegradable in aerobic aqueous media. These methods are: DOC reduction (301A), CO2 escape (modified Sturm test) (301B), MITI (I) (Ministry of International Trade and Industry, Japan) (301C), closed bottle (301D), modified OECD screening (301E), and manometry (301F).

[0381] A solution or suspension of the clearly identified / described test substance is inoculated into a mineral medium and incubated under aerobic conditions in the dark or in diffuse light. A parallel run with the inoculum but without the test substance allows for the determination of the inoculum's endogenous activity. A parallel run of a reference compound (aniline, sodium acetate, or sodium benzoate) is performed to check the procedure's operation. Typically, the test lasts 28 days. At least two flasks or containers containing both the test substance and the inoculum should be used, as well as at least two flasks or containers containing only the inoculum; a single container is sufficient for the reference compound. Typically, parameters such as DOC, CO2 production, and oxygen uptake are determined after degradation. For respiration assays, the pass level for biodegradability is 70% removal of DOC and 60% of ThOD or ThCO2 production. These pass values ​​must be achieved within a 10-day window of the 28-day test period.

[0382] The ethylene glycol and propylene glycol moieties (i.e., alkylene oxide units) in alkoxylated compounds have a significant impact on the carbon footprint of the alkoxylated compound product. Therefore, the objective is achieved by compounds based on ethylene glycol and / or propylene glycol (referred to as alkoxylated compounds in this invention because one or more additional alkylene glycols may be present in addition to ethylene glycol and propylene glycol), wherein the ethylene oxide and / or propylene oxide used in the synthesis of the alkoxylated compound are prepared by the specific methods of this invention.

[0383] The methods for preparing alkoxylated compounds, especially precursors ethylene oxide and propylene oxide, are energy-intensive, and the steps of the methods for preparing alkoxylated compounds (a ) to (d Many of these steps can be performed using a variety of alternative methods. The inventors have discovered a method for preparing alkoxylated compounds, wherein each step is optimized or at least prepared to obtain alkoxylated compounds with a low carbon footprint.

[0384] The inventors further discovered that when used in step (a) to prepare methanol The hydrogen used in the process is obtained by using electricity generated at least in part from non-fossil resources, and at least in part by water splitting, preferably electrolysis, to obtain alkoxylated compounds with particularly low PCF.

[0385] Preferably, step (a) The hydrogen in the process is obtained at least in part by water splitting, preferably by electrolysis, which preferably uses energy generated at least in part from non-fossil resources.

[0386] More preferably, in the method for preparing alkoxylated compounds, in step (a) In and in another step (b) ), (c ) and (d In one or both of the steps (a), energy in the form of heat and / or electricity is used, and the energy used is at least partially generated from non-fossil resources. Most preferably, in all steps (a) ) to (d In this process, energy in the form of heat and / or electricity is used, and in step (a) ) to (d The energy used in ) is at least partially generated from non-fossil resources.

[0387] More preferably, in the method for preparing ethylene oxide or propylene oxide, in step (a) In and in another step (b) ) and (c In one or both of the steps (a), energy in the form of heat and / or electricity is used, and the energy used is at least partially generated from non-fossil resources. Most preferably, in all steps (a) ) to (c In this process, energy in the form of heat and / or electricity is used, and in step (a) ) to (c The energy used in ) is at least partially generated from non-fossil resources.

[0388] Most preferably, in all steps (a) ) to (d In this process, energy in the form of heat and / or electricity is used, and in step (a) ) to (d The energy used in ) is at least partially generated from non-fossil resources.

[0389] The term "at least partially derived from non-fossil resources" means that some energy can still be produced from fossil fuels, preferably natural gas, because the combustion of natural gas results in much lower carbon dioxide emissions per megajoule of energy compared to the combustion of coal. However, the portion of energy produced from fossil fuels should be as low as possible, in step (a) In the preferred step (a) In and other steps (b) ), (c ) and (d In one or two of the steps (a), more preferably all of the steps (a) ) to (d The energy in the fossil fuel is preferably ≤ 50%, more preferably ≤ 30%, most preferably ≤ 20%, and even more preferably ≤ 10% derived from fossil resources.

[0390] More preferably, step (a) In the preferred step (a) In and other steps (b) ), (c ) and (d In one or two of the steps (a), more preferably all of the steps (a) ) to (d At least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90%, and most preferably 100% of the total required energy input used in the process shall be generated from non-fossil resources.

[0391] Most preferably, in the method for preparing alkoxylated compounds, step (a) In the preferred step (a) In and other steps (b) ), (c ) and (d In one or two of the steps (a), more preferably all of the steps (a) ) to (d The energy in it is produced solely from non-fossil resources.

[0392] Most preferably, in the method for preparing ethylene oxide or propylene oxide, step (a) In the preferred step (a) In and other steps (b) ) and (c In one or two of the steps (a), more preferably all of the steps (a) ) to (c The energy in it is produced solely from non-fossil resources.

[0393] In another preferred embodiment, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90%, and most preferably 100% of the total energy input required in the method of the invention is generated from non-fossil resources.

[0394] Typically, step (a) (b) ), (c ) and (d The energy used in the process is in the form of heat and / or electricity.

[0395] Energy generated from non-fossil resources is preferably selected from the group consisting of: solar energy (thermal, photovoltaic, and concentrated solar power), wind power, hydropower (tidal, wave, hydroelectric dams, river hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), and renewable portions of waste. 、 Nuclear energy and its mixtures.

[0396] The types of energy resources mentioned above are generally known to those skilled in the art, and these types have been described in detail above.

[0397] Step (a) )

[0398] Step (a) involves reacting hydrogen with carbon dioxide to form methanol. In the method of the present invention, step (a) is mandatory. The carbon dioxide in the product is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass. The method of the present invention provides alkoxylated compounds and ethylene oxide or propylene oxide, respectively, having low cradle-to-grave (i.e., including downstream products of scope 3 (see above for details)) product carbon footprints (PCF), and the alkoxylated compounds generally also possess good biodegradability.

[0399] The term "at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass" means that a portion of the carbon dioxide may still be obtained from other sources. For example, carbon dioxide is technically obtained by burning coke with excess air or as a byproduct of lime combustion and subsequent purification, and also by using natural gas sources (mineral water) for extraction. However, the portion of carbon dioxide obtained from sources other than industrial flue gas, from the air, or from seawater or other natural water, or from biological processes, such as fermentation processes from waste or biomass, should be as low as possible in the method of the invention, preferably ≤ 50%, preferably ≤ 30%, most preferably ≤ 20%, and further most preferably ≤ 10%. In a most preferred embodiment, carbon dioxide is obtained only from industrial flue gas, from the air, or from seawater or other natural water, or from biological processes, such as fermentation processes from waste or biomass.

[0400] All available capture techniques can be used.

[0401] More preferably, in step (a) of the method of the present invention At least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90%, and most preferably 100% of the total required carbon dioxide used in the process is captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

[0402] Step (a) This typically corresponds to step (c) of the method for manufacturing vinyl acetate mentioned above. Therefore, the process conditions and descriptions mentioned for step (c) also apply to step (a). ), as long as they apply to step (a) ).

[0403] By performing step (a) Methanol (CH3OH) is formed by reacting carbon dioxide, which is at least partially captured or obtained from industrial flue gas, air, seawater, or other natural water, or from a fermentation process of waste or biomass, with hydrogen.

[0404] Preparation (generation) of hydrogen:

[0405] Step (a) Hydrogen in the form of fuel can generally be obtained by any method known in the art. Hydrogen can be produced using a variety of different methods. Thermochemical methods use heat and chemical reactions to release hydrogen from organic materials (such as fossil fuels and biomass) or from materials like water. Water (H2O) can also be broken down into hydrogen (H2) and oxygen (O2) using electrolysis or solar energy. Microorganisms such as bacteria and algae can produce hydrogen through biological methods. These methods are known in the art (see, for example, https: / / en.wikipedia.org / wiki / Hydrogen_production and https: / / www.energy.gov / eere / fuelcells / hydrogen-production-processes).

[0406] As of 2020, most hydrogen (approximately 95%) was produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

[0407] Preferably, step (a) The hydrogen in the gas is obtained using energy generated at least in part from non-fossil resources.

[0408] More preferably, step (a) The hydrogen in the process is obtained at least partially through water splitting, preferably by electrolysis. Most preferably, water splitting, and more preferably electrolysis, uses energy generated at least partially from non-fossil resources.

[0409] The above details the term "at least in part from non-fossil resources".

[0410] The term "at least partially by water splitting" means that a portion of the hydrogen can still be produced by other methods, typically by steam reforming of natural gas and / or other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification, preferably by steam reforming of natural gas and / or other light hydrocarbons. However, in step (a) The amount of hydrogen produced in the process, other than through water splitting, should be as low as possible.

[0411] Preferably, in step (a) of the method of the present invention In this process, ≤ 50%, preferably ≤ 30%, most preferably ≤ 20%, and further most preferably ≤ 10% of the hydrogen is produced by methods other than water splitting. In one embodiment, step (a) The hydrogen in the solution is produced solely through water decomposition, preferably through electrolysis.

[0412] Step (a) in the method of the present invention The hydrogen used in this process (which is obtained, not by water splitting, but preferably by electrolysis using energy generated at least partially from non-fossil resources) can generally be obtained by any suitable energy source using any method known in the art, i.e., the hydrogen can have any of the colors mentioned above. In one embodiment, the hydrogen obtained, not by water splitting, but preferably by electrolysis using energy generated at least partially from non-fossil resources, is blue hydrogen obtained through steam methane reforming (SMR) with carbon capture and storage (CCS) (i.e., a method for producing hydrogen from natural gas while simultaneously capturing and storing the resulting carbon dioxide emissions).

[0413] Step (a) in the method of the present invention The hydrogen used in the process (which is obtained by water splitting, preferably by electrolysis but using energy generated from fossil resources) can generally be obtained by using any energy source known in the art that is generated from fossil resources. Preferred fossil resources are natural gas because the combustion of natural gas results in much lower carbon dioxide emissions per megajoule compared to the combustion of, for example, coal. However, in the method of the invention, the portion of energy generated from fossil fuels should be as low as possible. Most preferably, in step (a) In the case where hydrogen is obtained through water decomposition, preferably through electrolysis, the energy is entirely generated from non-fossil resources.

[0414] Water splitting is an environmentally friendly method for producing hydrogen because it uses renewable H2O and produces only pure oxygen as a byproduct. Water splitting can generally be carried out by known methods such as electrolysis; photocatalytic water splitting, also known as photoelectrochemical (PEC) water splitting; chemically assisted electrolysis, such as carbon / hydrocarbon assisted water electrolysis (CAWE); radiation splitting; ultrasound; thermal splitting, especially via solar energy, for example involving the use of solar concentrators to directly collect solar energy to heat water; pyrolysis of biomass; nuclear-assisted thermal splitting, such as in high-temperature gas-cooled reactors (HTGRs); thermochemical cycles that combine only a heat source with a chemical reaction to split water into its hydrogen and oxygen components, such as the sulfur-iodine cycle (SI cycle); ferrosilicon process; photobiological water splitting and mixtures thereof.

[0415] Generally, any water source can be used in water splitting.

[0416] Preferably, water splitting is carried out by electrolysis and / or photocatalytic water splitting, more preferably by electrolysis.

[0417] In photocatalysis (photoelectrochemistry (PEC)), hydrogen is produced from water using sunlight and one or more photocatalysts (specialized semiconductors commonly referred to as photoelectrochemical materials, which use light energy to directly dissociate water molecules into hydrogen and oxygen).

[0418] The photocatalysts (semiconductor materials) used in photocatalysis (PEC) methods are similar to those used in photovoltaic solar power generation, but for photocatalysis (PEC) applications, the photocatalysts (semiconductors) are typically immersed in a water-based electrolyte, where sunlight provides energy for the water splitting process.

[0419] PEC reactors can be constructed, for example, in the form of a panel (similar to a photovoltaic panel) as an electrode system or a slurry-based particle system.

[0420] The preferred method of water electrolysis typically utilizes direct current (DC) power, which is at least partially derived from non-fossil energy sources.

[0421] The above details suitable water electrolysis methods.

[0422] Most preferably, step (a) Hydrogen gas in the solution is obtained by water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0423] Step (b) )

[0424] In step (b) In step (a), the material will be... Methanol is converted into ethylene and / or propylene.

[0425] Preferably, step (b) Ethylene and / or propylene in the product are obtained by the methanol-to-olefins (MTO) process.

[0426] The methanol-to-olefins (MTO) process is one of the methods for producing olefins (especially ethylene and propylene) from methanol.

[0427] The MTO method is generally known to those skilled in the art.

[0428] Step (b) This typically corresponds to step (d) of the method for manufacturing vinyl acetate mentioned above. Therefore, the process conditions and descriptions mentioned for step (c) also apply to step (b). ), as long as they apply to step (b) ).

[0429] Step (b) Ethylene and / or propylene in the product are preferably obtained by methanol-to-olefins process, preferably using a zeolite catalyst.

[0430] Step (c) )

[0431] In step (c) In step (b), make the... Ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide.

[0432] Ethylene oxide:

[0433] Typically, ethylene oxide can be prepared by any method known in the art. Preferably, step (c) Ethylene oxide in ) is obtained by the oxidation of ethylene (direct oxidation method).

[0434] The direct oxidation method is preferably carried out in the gas phase (e.g., a gas phase containing oxygen or air) in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0435] The direct oxidation of ethylene is typically carried out at temperatures between 230°C and 270°C. The pressure is preferably in the range of 10 to 30 bar.

[0436] In a preferred embodiment, step (c) The direct oxidation of ethylene is carried out via gas-phase selective ethylene oxidation, which is typically conducted in a fixed-bed tubular reactor with a supported Ag / Al2O3 catalyst at 230°C–270°C and 10–30 bar.

[0437] For step (c) In the direct oxidation of ethylene, the preferred catalyst is a silver-based catalyst, such as...

[0438] - Preferably, a supported Re / Cs / Ag / Al2O3 catalyst operating with excess C2H4 / O2; or

[0439] - Preferably, it is a supported Ag / Al2O3 catalyst promoted by an alkali metal (Na, Cs) operating with excess O2 / C2H4.

[0440] It has been found that oxides of Mo and S also promote supported Re / Cs / Ag / Al2O3 systems for ethylene oxide (EO) formation. Therefore, supported Re / Cs / Ag / Al2O3 systems can additionally incorporate oxides of Mo and / or S as promoters.

[0441] Alternatively, C2H4Cl2 can be added to deposit Cl onto the catalyst, which acts as a promoter.

[0442] Examples of the description can be found, for instance, in “Ethylene Oxide” by Mia Monconduit and Karen Jobes of IHS Markit, Chemical Economics Handbook, December 22, 2020, pp. 14–16.

[0443] Surprisingly, in the method according to the invention, a measurable increase in epoxide selectivity was found compared to conventional methods using fossil-based raw materials (correspondingly fewer byproducts such as acetaldehyde and CO2 were formed and the catalyst ran for a longer time), especially in the case of ethylene oxide.

[0444] In particular, for propylene oxide (see below) (HPPO process), a significant improvement in catalyst run-time reliability was found. Higher operational reliability has the advantage of improving planning efficiency in industrial production practices, especially for methods with relatively high catalyst regeneration-recycling frequencies (such as HPPO).

[0445] Propylene oxide:

[0446] Typically, propylene oxide can be prepared by any method known in the art. Suitable methods for preparing propylene oxide have been mentioned above. Preferably, step (c) Propylene oxide in the product is obtained by oxidizing propylene with hydrogen peroxide as an oxidant, typically in the presence of a catalyst, preferably a zeolite catalyst, and more preferably in the presence of titanium silicate zeolite-1 (TS-1) (HPPO method).

[0447] The HPPO process is typically carried out at temperatures below 90°C and pressures below 35 bar. This method can be performed in single-reactor or multi-reactor systems, such as in tubular reactors, or in fixed-bed or trickle-bed systems.

[0448] The HPPO method and other industrially relevant methods are described, for example, in M. Di Serio et al., Ind. Eng. Chem. Res. [Industrial and Engineering Chemistry Research] 2013, 52, 1168-1178.

[0449] Hydrogen peroxide, used as an oxidant in the HPPO process preferably used to prepare propylene oxide according to the invention, can be obtained by any known method. Typically, hydrogen peroxide is obtained via the anthraquinone process (Jia Lin and Adam Chan's NexantECA research publication, Propylene Oxide, TECH 2022-3, December 2022).

[0450] The anthraquinone process is based on the catalytic hydrogenation of anthraquinone to anthrahydroquinone over a catalyst (e.g., a palladium catalyst). Subsequently, the anthraquinone is reformed by re-oxidation with oxygen (e.g., pure oxygen or atmospheric oxygen) under the elimination of hydrogen peroxide.

[0451] Typically, the process steps in the anthraquinone process are carried out under mild reaction conditions (usually pressures below 1 MPa (i.e., 10 bar) and temperatures below 100°C) and preferably continuously.

[0452] Since anthraquinones to anthraquinones should not flocculate during this process, solubility can be adjusted via alkyl substituents and solvent compositions. For this purpose, alkylated derivatives such as 2-ethyl-, 2-tert-butyl-, or 2-pentylanthraquinones are used. To retain anthraquinones in solution, nonpolar substances such as C9- / C10-alkylbenzene mixtures are typically part of the working solution. Polar substances such as tri-(2-ethylhexyl)-phosphate, diisobutylmethanol, tetrabutylurea, or urea or methylcyclohexyl acetate fulfill this role for hydroquinones.

[0453] The preparation of hydrogen peroxide is described, for example, in Anjali A. Ingle et al., Environmental Science and Pollution Research (2022) 29:86468-86484 (anthraquinone process); Shu Hu et al., ACS Appl. Energy Mater. 2019, 2, 11, 7972-7979 (electrochemical synthesis of hydrogen peroxide from oxygen and water); and Sandrine Romand's NexantECA research publication, Hydrogen Peroxide, TECH 2019-8, mid-September 2019.

[0454] In a preferred embodiment of the present invention, the propylene oxide in step c) is obtained by oxidizing propylene, preferably in the HPPO process, using hydrogen peroxide as an oxidant.

[0455] Preferably, the present invention therefore relates to a method for preparing propylene oxide, the method comprising the following steps:

[0456] (a This allows hydrogen to react with carbon dioxide to form methanol.

[0457] (b ) will come from step (a) The methanol is converted into propylene.

[0458] (c ) make from step (b) Propylene reacts with an oxidizing agent to form propylene oxide.

[0459] Among them, step (a) The carbon dioxide in the gas is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

[0460] The propylene oxide in step c) is therefore obtained by oxidizing propylene, preferably in the HPPO process, using hydrogen peroxide as an oxidant.

[0461] Hydrogen peroxide is preferably obtained via the anthraquinone process.

[0462] As mentioned above, the steps of the method of the present invention (a) The hydrogen in the process is preferably obtained at least partially by water splitting, and more preferably by electrolysis. The byproduct of water splitting, and more preferably electrolysis, is pure oxygen, which is usually released into the environment without further use.

[0463] In one embodiment of the present invention, step (c) The oxygen in the solution is obtained at least in part by water splitting, preferably by electrolysis, which preferably uses energy generated at least in part from non-fossil resources.

[0464] The steps mentioned above (c) The oxygen in this process is the same oxygen that can be used in the preparation of ethylene oxide (preferably by direct oxidation) and in the preparation of the oxidant used in the preparation of propylene oxide. The oxidant is preferably hydrogen peroxide, more preferably hydrogen peroxide prepared by the anthraquinone process.

[0465] In step (a) In the production of methanol, one carbon source used to produce ethylene oxide and propylene oxide is captured carbon dioxide. Therefore, the byproduct profile of methanol used in the method according to the invention for preparing ethylene oxide and propylene oxide differs from that of methanol obtained by conventional methods (i.e., using synthesis gas, often derived from a combination of varying amounts of H2, CO, and CO2 from gasified coal or natural gas). For example, conventionally obtained methanol typically contains more methyl formate, acetone, and higher alcohols (≥ C3) than methanol obtained by the method according to the invention. The byproduct profile of ethylene and propylene produced by cracking fossil-based hydrocarbon feedstocks (such as naphtha or natural gas used in conventionally obtained ethylene oxide and propylene oxide) is even more different from that of ethylene oxide and propylene oxide obtained by CO2 MTO via the methanol-to-olefins route according to the invention, for example, due to the presence of highly undesirable sulfur components, especially in naphtha.

[0466] Different byproduct profiles of methanol (ethylene and propylene, respectively) are also reflected in downstream products, such as in ethylene oxide and propylene oxide, and in alkoxylated compounds obtained according to the present invention.

[0467] Step (d) )

[0468] In step (d) In one or more steps, step (c) is made to... The ethylene oxide and / or propylene oxide obtained in the process, and optionally at least one alkyl oxide different from ethylene oxide and propylene oxide, react with the at least one starting unit having a Zelevitinov active hydrogen atom to form an alkoxylated compound.

[0469] The alkoxylated compound prepared in the method of the present invention comprises

[0470] i) 20 wt% to < 100 wt%, preferably 30 wt% to < 99.3 wt% of ethylene oxide units and / or propylene oxide units,

[0471] ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of at least one epoxide unit different from ethylene oxide and propylene oxide units.

[0472] iii) > 0 wt% to 80 wt%, preferably 0.2 wt% to 70 wt% of at least one starting unit having a Zelevitinov active hydrogen atom,

[0473] The sum of the units mentioned under i), ii) and iii) is 100 wt%.

[0474] i) Ethylene oxide units and / or propylene oxide units:

[0475] The alkoxylated compounds according to the present invention comprise ethylene oxide (EO), propylene oxide (PO), or both.

[0476] EO and PO can be present in various weight ratios. Typically, alkoxylated compounds have EO:PO weight ratios of 100:0 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.

[0477] ii) At least one alkylene oxide unit that is different from ethylene oxide and propylene oxide units:

[0478] The alkoxylated compounds according to the present invention may contain at least one alkylene oxide unit different from ethylene oxide and propylene oxide units.

[0479] Examples of epoxide units other than ethylene oxide and propylene oxide units are based on 1,2-epoxide butane, 2,3-epoxide butane, styrene oxide, 1,3-epoxide propane, or tetrahydrofuran, preferably 1,2-epoxide butane or 2,3-epoxide butane, more preferably 1,2-epoxide butane (BuO).

[0480] Preferably, there are no alkyl oxide units different from ethylene oxide and propylene oxide units, that is, the alkoxylated compound prepared in the method of the present invention contains 0 wt-% of alkyl oxide units different from ethylene oxide and propylene oxide units.

[0481] The alkylene oxide unit can be in the form of only one type of alkylene oxide unit (i.e., only ethylene oxide unit or only propylene oxide unit), for example, in the case of alkylene oxide units polymerized in the form of homopolymers, or in the form of two or more different alkylene oxide units (e.g., ethylene oxide units and propylene oxide units in the ratios mentioned above, or ethylene oxide units and / or propylene oxide units and 1,2-butylene oxide units). For example, in the case of alkylene oxide units polymerized in the form of random copolymers or block copolymers.

[0482] In some embodiments, the polymer is EO-terminated. In other embodiments, the polymer is PO-terminated. This termination can be referred to as a small block, such as a small block of EO acting as the terminator. If the polymer is terminated, it can be referred to in the art as a block copolymer. In some embodiments, the polymer is a block PAG. Such a block PAG can comprise blocks of all EO or PO, blocks of random EO / PO monomers having at least two blocks with different EO / PO ratios, or a combination of all EO or PO blocks and random EO / PO blocks.

[0483] Preferred ethylene oxide units and / or propylene oxide units according to the present invention are characterized by the following formula:

[0484] ia) (Ia)

[0485] ib) (Ib)

[0486] ic) (Ic),

[0487] in

[0488] n, m, n' and m' are each independently 1 to 500, preferably 1 to 100, more preferably 2 to 50;

[0489] And groups

[0490] and In formula (Ic), they are in the form of two or more, preferably two or three, blocks and / or arranged randomly.

[0491] The total average molecular weight of the ethylene oxide units is in the range of 88 to 22,000 Da, preferably 88 to 4,400 Da, and more preferably 88 to 2,200 Da, and the total average molecular weight of the propylene oxide units is in the range of 116 to 29,000 Da, preferably 116 to 5,800 Da, and more preferably 116 to 2,900 Da. The average molecular weight of the ethylene oxide units and / or propylene oxide units can be calculated based on their monomer structure.

[0492] iii) At least one starting unit having a Zelevitinov active hydrogen atom

[0493] Zelevitinov active hydrogen is reactive, as determined by the Zelevitinov method as described in Analyst 1963, 88, 782-790. The quantitative determination of active hydrogen in a chemical substance by adding methyl magnesium iodide in pentyl ether to the substrate solution and quantitatively measuring the volume of escaping gaseous methane is commonly referred to as the Zelevitinov determination.

[0494] Preferably, the starting unit having a Zelevithinov active hydrogen atom is selected from the group consisting of: water, at least one of: monofunctional alcohols, difunctional alcohols or polyfunctional alcohols, monofunctional amines, difunctional amines or polyfunctional amines, and monofunctional, difunctional or polyfunctional thio compounds. More preferably, the starting unit is water, a monofunctional alcohol, a difunctional alcohol or polyfunctional alcohol and / or a monofunctional amine, a difunctional amine or polyfunctional amine.

[0495] The starting unit preferably contains 1 to 100, more preferably 2 to 50, most preferably 2 or 8, and even more preferably 2 or 3 Zelevitinov active hydrogen atoms.

[0496] When polyalkylene imide is used as the starting unit, the preferred polyalkylene imide starting unit has an amine value of 3 to 30 mmol / g, preferably 5 to 25 mmol / g, and more preferably 10 to 22 mmol / g.

[0497] The amine value refers to the proportion of amines present in an element. The amine value is determined according to DIN 53176 (version 2000-12).

[0498] Examples of suitable monofunctional, difunctional, or polyfunctional alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetrahydric alcohols, or higher alcohols, which may also be referred to in the art as polyhydric alcohols. In some embodiments, the alcohol is a monohydric alcohol. Examples of suitable monohydric alcohols include C1- to C1-C ... 20 Alcohols, such as n-butanol, isobutanol, 2-ethylhexanol, 2-propylheptanol, butanediol, butyl diethylene glycol, butyl triethylene glycol, butyl propylene glycol, butyl dipropylene glycol, butyl tripropylene glycol, methyl diethylene glycol, methyl triethylene glycol, methyl dipropylene glycol, methanol, ethanol, hexanol, isononol, decanol, 2-butyloctanol, oleyl alcohol, octadecanol (C 18 Alcohols (e.g., stearyl alcohol), isononadecanol, C 12 alcohols, C 13 alcohols, C 14 alcohols, C 15 alcohols, C 16 alcohols, C 17 Alcohols, 2-ethylhexanol, 2-propylheptanol, 2-butyloctanol, 2-pentylnonanol, 2-hexyldecanol, and the alcohols like C 13 -C 15 alcohols, C 12 -C 18 alcohols, C 16 -C 18 alcohol, or C 12 -C 14A mixture of alcohols. In other embodiments, the alcohol is a diol. Examples of suitable diols include ethylene glycol, 1,2-propanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. In yet another embodiment, the alcohol is a polyol. Examples of suitable polyols include glycerol, trimethylolpropane, and pentaerythritol.

[0499] Various types of amines can be used to form alkoxylated compounds. Examples of suitable amines include monoamines, diamines, triamines, or higher amines, which may also be referred to in the art as polyamines. Specific examples of suitable amines include alkanolamines, ethylenediamines, diethylenetriamines, and polyethyleneimines.

[0500] In the context of this invention, the term "polyethylimide" refers not only to polyethylimide homopolymers but also to polyalkylimides containing NH-CH2-CH2-NH structural units and other alkylene diamine structural units such as NH-CH2-CH2-CH2-NH, NH-CH2-CH(CH3)-NH, NH-(CH2)4-NH, NH-(CH2)6-NH, or (NH-(CH2)8-NH structural units, but with the NH-CH2-CH2-NH structural units being the majority in molar proportion. Preferred polyethylimides contain the majority of NH-CH2-CH2-NH structural units in molar proportion, for example, 60 mol-% or more, more preferably at least 70 mol-% relative to all alkylene imide structural units. In particular embodiments, polyethylimide refers to those polyalkylene imides having one or zero alkylene imide structural units per molecule that are different from NH-CH2-CH2-NH.

[0501] In the context of this invention, "polyethyleneimine" can be linear or branched. The degree of branching can be determined by a person skilled in the art using 13C NMR based on the specific application.

[0502] Polyalkylimides (including polyethylimides) can be characterized by their degree of branching (DB). For a definition of branching degree, refer to H. Frey et al., Acata Polym. [Acta Polymerica Sinica] 1997, 48, 30. The branching degree DB is defined therein as...

[0503] DB (%) = (T+Z) / (T+Z+L) x 100, where

[0504] T is the average number of terminally bound monomer units (primary amino groups).

[0505] Z is the average number of branched monomer units (tertiary amines).

[0506] L is the average number of linearly linked monomer units (secondary amines). T, Z, and L can be determined in D2O by 13C-NMR.

[0507] The degree of branching (DB) of the polyalkylene imine, especially the polyethylene imine, according to the present invention is preferably in the range of 55% to 95%, more preferably in the range of 57% to 90%, and even more preferably in the range of 60% to 80%.

[0508] The polyalkylene imide, preferably polyethylene imide, used in the reaction mixture may preferably have a weight-average molecular weight (MW) of 300 to 20,000, for example 300 to 15,000, suitably 300 to 10,000, more suitably 300 to 5,000, preferably 500 to 1,500, and more preferably 500 to 1,000 g / mol. The weight-average molecular weight (Mw) can be determined by gel permeation chromatography (GPC), wherein hexafluoroisopropanol and 0.05 w% ammonium acetate are used as eluents and a narrowly distributed polyethylene glycol standard is used as the stationary phase.

[0509] preparation:

[0510] There are no specific requirements for the method used to obtain the alkoxylated compounds of the present invention, and the preparation of the alkoxylated compounds of the present invention is generally known to those skilled in the art.

[0511] Alkoxylation can generally be carried out in three ways: (i) anionic (base-initiated) polymerization, (ii) acid-initiated polymerization, and (iii) through coordination polymerization.

[0512] Anionic polymerization of epoxides represents a "classic" technique for synthesizing corresponding polymers / compounds comprising ethylene oxide and / or propylene oxide units. Anionic polymerization is typically carried out by catalytic addition of ethylene oxide and / or propylene oxide, and optionally at least one alkyl oxide other than ethylene oxide and propylene oxide, to at least one starting unit having a Zelevitinov active hydrogen atom.

[0513] As catalysts, highly nucleophilic metal compounds, preferably alkali metals (especially sodium, potassium, or cesium) compounds, can be used. Examples include alkali metal hydroxides, alkali metal salts, alkali metal hydrides, or alkali metal amides. In practice, potassium hydroxide is of the greatest significance (see, for example, US 6156720 A).

[0514] Other suitable classes of catalysts are polymetallic cyanide compounds, preferably bimetallic cyanide compounds, and especially zinc hexacyanometalates. These catalysts are also often referred to as DMC catalysts. Polyether alcohols prepared using polymetallic cyanide compounds are characterized by very low contents of unsaturated components. Another advantage of using polymetallic cyanide compounds as catalysts is the significantly increased space-time yield upon the addition of alkyl epoxides. Alkoxylation in the presence of DMC catalysts is described, for example, in DD 203 735, DD 203 734, WO 97 / 29146, WO 98 / 03571, WO 00 / 14143, WO 99 / 44739 and US 2008 / 0161509 A1.

[0515] Solvents used for the anionic polymerization of epoxides are typically polar and aprotic; therefore, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO), and hexamethylphosphoramide (HMPA) are commonly used. Furthermore, polymerization in bulk monomers is possible and is the preferred method.

[0516] Alkoxides containing sodium, potassium, or cesium counterions in THF or other polar aprotic solvents represent commonly used initiator systems.

[0517] Adding a complexing agent (such as a crown ether suitable for the corresponding cation) can strongly accelerate the anionic polymerization of epoxides.

[0518] The temperature during alkoxylation is typically between 80°C and 200°C, preferably between 90°C and 180°C.

[0519] The alkoxylated compounds of the present invention can be prepared by batch, semi-batch, or continuous methods.

[0520] In semi-intermittent alkoxylation, for example, a catalyst and at least one starting material are initially loaded, and an epoxide (ethylene oxide or propylene oxide) is added simultaneously during the reaction process. This particular synthetic strategy is due to the high reactivity of the alkoxide and the high heat involved in the alkoxylation reaction.

[0521] The polymerization rate of EO is significantly faster than that of PO, which plays an important role in the commonly used anionic copolymerization of EO and PO. Generally, the reactivity of alkyl oxides decreases with increasing length and size of the alkyl substituent at the epoxide moiety.

[0522] The alkoxylated polyethylimide of the present invention can be obtained by alkoxylation of polyethylimide using methods known in the art. The alkoxylation of polyethylimide using ethylene oxide, propylene oxide, and butane is described, for example, in Houben-Weyl, Methoden der organischen Chemie, 4th edition, Vol. 14 / 2, p. 440 and subsequent pages (1963) and Vol. E 20, p. 1367 and subsequent pages (1987). The alkoxylated polyethylimide of the present invention can be obtained, for example, as described in US5445765 and DE-A 2227546.

[0523] In cases where at least one starting unit is a monofunctional, difunctional, or polyfunctional alcohol, the resulting alcohol alkoxide component (alkoxylated alcohol) can be converted to an alkyl ether sulfate by sulfation with sulfuric acid or a sulfuric acid derivative in a manner known per se to give an acid alkyl ether sulfate (see, for example, US 2008 / 0207939 A1). Sulfation reactions of alcohols have been described, for example, in US 3,462,525, US 3,420,875, and US 3,524,864. Details regarding the conduct of this reaction are given in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A25 (1994), pp. 779-783, and in the references given therein.

[0524] If sulfuric acid itself is used for esterification, it is convenient to typically use an acid with a concentration of 75% to 100% by weight, preferably 85% to 98% by weight (referred to as "concentrated sulfuric acid" or "monohydrate"). If it is desirable to control the reaction, such as through thermal development, the esterification can be performed in a solvent or diluent.

[0525] Typically, the alcohol reactant is introduced first, and the sulfating agent is added gradually with continuous mixing. If complete esterification of the alcohol alkoxide component is desired, the sulfating agent and the alcohol alkoxide component are usually used in a molar ratio of 1:1 to 1:1.5, preferably 1:1 to 1:1.2. If a mixture of alcohol alkoxides is used, a smaller amount of sulfating agent may be advantageous. Esterification is typically carried out at temperatures ranging from 25°C to 85°C, preferably from 45°C to 75°C. If appropriate, it may be advantageous to carry out esterification at its boiling point in a low-boiling, water-immiscible solvent and diluent, where the water formed during esterification is azeotropically distilled off.

[0526] Instead of the sulfuric acid of the above concentration, for the sulfation of the alcohol alkoxide components of the present invention, sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (“fuming sulfuric acid”), chlorosulfonic acid, thioyl chloride, or other aminosulfonic acids can also be used. The reaction conditions must then be appropriately modified as known to those skilled in the art.

[0527] If sulfur trioxide is used as the sulfation reagent, the reaction can also advantageously be carried out in a falling film reactor in countercurrent or cocurrent flow, and, if appropriate, continuously. After esterification, these batches are neutralized by adding alkali, and, if appropriate, post-processed after removing excess alkali metal sulfates and any solvents present.

[0528] If chlorosulfonic acid is used as the sulfation reagent, the corresponding alcohol alkoxide component is loaded into a stirred apparatus under inert conditions. The appropriate amount of chlorosulfonic acid is added dropwise under vigorous stirring. The molar ratio between the alcohol component and chlorosulfonic acid is typically 0.5:1 to 1:0.5, preferably 0.75:1 to 1:0.75. Very particularly preferably, the molar ratio of the alcohol alkoxide component to chlorosulfonic acid is 1:1. After removing HCl gas, the reaction batch is adjusted to a slightly alkaline pH using a sodium hydroxide solution.

[0529] Step (d) The alkoxylated compounds obtained in this process are characterized by a lower cradle-to-grave product carbon footprint compared to the same alkoxylated compounds obtained by conventional methods (i.e., without CO2 to olefins via the methanol-to-olefins route, without carbon capture, etc.) (see explanation above). Therefore, the present invention addresses the aforementioned challenges and provides alkoxylated compounds with a low cradle-to-grave (i.e., including downstream products in scope 3 (see explanation above)) carbon footprint and good overall biodegradability.

[0530] As discussed above, the different byproduct profiles of methanol, ethylene, and propylene, as well as ethylene oxide and propylene oxide, are also reflected in the downstream products, namely the alkoxylated compounds obtained according to the present invention.

[0531] The inventors of this application have unexpectedly discovered that, compared with conventionally prepared ethylene oxide and / or propylene oxide, the use of ethylene oxide and / or propylene oxide according to the invention produces lower levels of polymeric byproducts during the alkoxylation process.

[0532] In the preparation of polyurethane (from polyether polyols), it is desirable to reduce these polymeric byproducts because very high molecular weight byproduct fractions are known to be effective surfactants that cause polyurethane foam collapse or have negative effects on other applications (e.g., causing turbidity or precipitation in blends).

[0533] Preferably, the alkoxylated compounds according to the present invention meet the biodegradability requirements set forth in OECD 301B (as mentioned above).

[0534] Both the alkoxylated compounds and the methods of this invention achieve low cradle-to-grave product carbon footprints and generally good biodegradability.

[0535] The alkoxylated compounds of the present invention comprise

[0536] i) 20 wt% to < 100 wt%, preferably 30 wt% to 99.3 wt% of ethylene oxide units and / or propylene oxide units,

[0537] ii) 0 wt% to 30 wt%, preferably 0.5 wt% to 20 wt%, of at least one epoxide unit different from ethylene oxide and propylene oxide units.

[0538] iii) > 0 wt% to 80 wt% and 0.2 wt% to 70 wt% of at least one starting unit having a Zelevitinov active hydrogen atom.

[0539] The sum of the units mentioned under i), ii) and iii) is 100 wt%

[0540] The ethylene oxide unit and / or propylene oxide unit, alkyl oxide units different from ethylene oxide and propylene oxide units, and starting unit units having Zelevitdinov active hydrogen atoms are defined above.

[0541] In one embodiment, the alkoxylated compound of the present invention comprises an EO:PO weight ratio of 100:1 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.

[0542] Ethylene oxide units and / or propylene oxide units, alkyl oxide units other than ethylene oxide and propylene oxide units, and starting units having Zelevithinov active hydrogen atoms are defined above.

[0543] The alkoxylated compounds of the present invention typically have a number-average molecular weight of 100 to 50,000 Da, preferably 200 to 30,000 Da, and more preferably 300 to 20,000 Da, as determined by GPC in THF using PEG standards.

[0544] The alkoxylated compounds of this invention have a wide range of applications in various industries. Some of these applications are:

[0545] - Lubricants: Alkoxylated compounds can be used as lubricants in various industries such as automotive, aerospace, and industrial machinery. They offer excellent lubrication properties, high thermal stability, and oxidation resistance.

[0546] - Personal care products: Alkoxylated compounds can be used in the formulation of personal care products such as lotions, creams, and shampoos. They provide skin and hair with properties such as moisturizing and conditioning.

[0547] - Household care products: Alkoxylated products can be used as surfactants in laundry detergents, hard surface cleaners, and rinsing aids. They provide excellent wetting, cleaning, and emulsifying properties.

[0548] - Pharmaceutical Industry: Alkoxylated compounds can be used as excipients in the pharmaceutical industry to improve drug solubility, stability, and bioavailability. They are also used in formulations of ointments, creams, and gels.

[0549] - Textile Industry: Alkoxylated compounds can be used as softeners and antistatic agents in the textile industry. They can improve the texture and feel of fabrics and reduce static electricity.

[0550] -Food Industry: Alkoxylated compounds can be used as emulsifiers, thickeners, and stabilizers in the food industry. They can be used in the production of ice cream, dairy products, and baked goods.

[0551] - Oil and Gas Industry: Alkoxylated compounds can be used as hydraulic fluids, oil shut-off agents, and heat transfer fluids in the oil and gas industry. They offer, for example, excellent lubrication properties and high thermal stability.

[0552] -Agricultural / Agrochemicals: Alkoxylated compounds can be used as adjuvants in the agricultural industry, for example, to improve the effectiveness of herbicides and pest control agents.

[0553] - Chemical Industry: Alkoxylated compounds can be used as reaction media, surfactants, and dispersants in the chemical industry. They can be used in the production of polymers, resins, and coatings.

[0554] - Building materials: Alkoxylated compounds can be used in the construction industry as additives in cement, concrete and mortar to improve, for example, their workability, strength and durability.

[0555] - Polyurethane production: Alkoxylated compounds can be used as starting materials for the production of products such as polyurethane foams, adhesives, and coatings. They can act as chain extenders and crosslinking agents in the polymerization process.

[0556] - Metalworking fluids: Alkoxylated compounds can be used as coolants and lubricants in metalworking processes such as cutting, grinding, and drilling. They offer, for example, excellent thermal stability, low volatility, and high lubricity.

[0557] - Electronics: Alkoxylated compounds can be used as heat transfer fluids in electronic cooling systems. They offer advantages such as high thermal conductivity, low viscosity, and compatibility with a wide range of materials.

[0558] - Fuels and Energy: Alkoxylated compounds can be used as additives in fuels and lubricants (such as fuel performance packs) to improve their performance and reduce emissions. They can also be used as heat transfer fluids in solar and geothermal energy systems.

[0559] - Water treatment: Alkoxylated compounds can be used as flocculants and coagulants in water treatment processes. They can help remove suspended particles and impurities from water.

[0560] - Adhesives and sealants: Alkoxylated compounds can be used as base materials and thickeners in the formulation of adhesives and sealants. They can provide improved adhesion, flexibility, and moisture resistance.

[0561] Therefore, the present invention further relates to the use of the alkoxylated compounds of the present invention in any of the applications mentioned above.

[0562] Therefore, preferably, the present invention further relates to the use of alkoxylated compounds obtained according to the invention or by the method according to the invention in: home care products, cosmetic products, pharmaceutical products, the food industry, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agricultural chemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(carbamate) Applications of esters; and home care products, cosmetic products, pharmaceutical products, products in the food industry, building materials, lubricants such as engine oil, bearing oil, gear oil, compressor oil, grease, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agricultural chemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications.

[0563] The starting unit having a Zelevitninov active hydrogen atom is preferably selected from the group consisting of at least one of the following: monofunctional alcohols, difunctional alcohols or polyfunctional alcohols, monofunctional amines, difunctional amines or polyfunctional amines, and monofunctional, difunctional or polyfunctional thio compounds.

[0564] The present invention further relates to the method according to the invention, based on step (a) ) to (d Alkoxylated compounds can be obtained by the method of ).

[0565] Alkoxylated compounds preferably meet the biodegradability requirements set forth in OECD 301B.

[0566] Due to precise analysis of the different method steps used to obtain alkoxylated compounds, especially step (a) (b) ) and (c Obtaining alkoxylated compounds with low cradle-to-grave product carbon footprints is crucial; therefore, the present invention further relates to a method for preparing ethylene oxide or propylene oxide, the method comprising the following steps:

[0567] (a This allows hydrogen to react with carbon dioxide to form methanol.

[0568] (b ) will come from step (a) The methanol is converted into ethylene and / or propylene.

[0569] (c ) make from step (b) The ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide.

[0570] Among them, step (a) The carbon dioxide in the substance is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

[0571] Step (a) in the method of the present invention for preparing ethylene oxide or propylene oxide (b) ) and (c ) and step (a) of the method of the present invention for preparing alkoxylated compounds. (b) ) and (c The steps above and below are the same, and the method steps (a) are the same. (b) ) and (c The definition of ) applies to both methods.

[0572] Therefore, the present invention also relates to the following:

[0573] 1. A method for preparing an alkoxylated compound, the alkoxylated compound comprising...

[0574] i) 20 wt% to < 100 wt% ethylene oxide units and / or propylene oxide units,

[0575] ii) at least one alkylene oxide unit, different from ethylene oxide and propylene oxide units, ranging from 0 wt% to 30 wt%.

[0576] iii) > 0 wt% to 80 wt% of at least one starting unit having a Zelevitinov active hydrogen atom,

[0577] The sum of the units mentioned under i), ii) and iii) is 100 wt%

[0578] The method includes the following steps:

[0579] (a This allows hydrogen to react with carbon dioxide to form methanol.

[0580] (b ) will come from step (a) The methanol is converted into ethylene and / or propylene.

[0581] (c ) make from step (b) The ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and

[0582] (d In one or more steps, make step (c) The ethylene oxide and / or propylene oxide obtained in the process, and optionally at least one alkyl oxide different from ethylene oxide and propylene oxide, react with the at least one starting unit having a Zelevithinov active hydrogen atom to form the alkoxylated compound.

[0583] Among them, step (a) The carbon dioxide in the substance is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

[0584] 2. The method according to Embodiment 1, wherein step (a) The hydrogen gas in the process is obtained at least in part by water splitting, preferably by electrolysis, which preferably uses energy generated at least in part from non-fossil resources.

[0585] 3. The method according to embodiment 1 or 2, wherein in all steps (a) ) to (d In this process, energy in the form of heat and / or electricity is used, and in step (a) ) to (d The energy used in this process is generated at least in part from non-fossil resources.

[0586] 4. The method according to Example 2 or 3, wherein the energy generated from non-fossil resources is selected from the group consisting of: solar energy (thermal, photovoltaic and concentrated), wind energy, hydropower (tidal energy, wave energy, hydroelectric dams, river hydrodynamics), geothermal energy, heat captured by heat pumps, bioenergy (biofuels, biomass), renewable portions of waste, nuclear energy and mixtures thereof.

[0587] 5. The method according to any one of Examples 2 to 4, wherein the hydrogen is obtained by water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0588] 6. The method according to any one of Examples 1 to 5, wherein step (b) The ethylene and / or propylene in the product are obtained by methanol-to-olefins process, preferably using a zeolite catalyst.

[0589] 7. The method according to any one of Examples 1 to 6, wherein step (c) The ethylene oxide in the figure is obtained by epoxidation of ethylene with oxygen, preferably in the presence of a silver-based catalyst.

[0590] 8. The method according to any one of Examples 1 to 7, wherein step (c) The propylene oxide in the present invention is obtained by oxidizing propylene with hydrogen peroxide as an oxidant, preferably in the presence of a zeolite catalyst, more preferably in the presence of titanium silicate zeolite-1 (TS-1).

[0591] 9. The method according to any one of Examples 1 to 8, wherein step (c) The oxygen in the solution is obtained at least in part by water splitting, preferably by electrolysis, which preferably uses energy generated at least in part from non-fossil resources.

[0592] 10. The method according to any one of Examples 1 to 9, wherein the starting units having Zelevitinov active hydrogen atoms are selected from the group consisting of at least one of the following: monofunctional alcohols, difunctional alcohols or polyfunctional alcohols, monofunctional amines, difunctional amines or polyfunctional amines, and monofunctional, difunctional or polyfunctional thio compounds.

[0593] 11. An alkoxylated compound, which can be obtained by the method according to any one of Examples 1 to 10.

[0594] 12. An alkoxylated compound that is available according to Example 11 or by any one of the methods specified in Nos. 1 to 10, wherein such alkoxylated compound satisfies the biodegradability requirements set forth in OECD 301B.

[0595] 13. A method for preparing ethylene oxide or propylene oxide, the method comprising the following steps:

[0596] (a This allows hydrogen to react with carbon dioxide to form methanol.

[0597] (b ) will come from step (a) The methanol is converted into ethylene and / or propylene.

[0598] (c ) make from step (b) The ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide.

[0599] Among them, step (a) The carbon dioxide in the substance is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

[0600] 14. Uses of the alkoxylated compounds according to Example 11 or 12 or obtained by the method according to any one of numbers 1 to 10 in the following: home care products, cosmetic products, pharmaceutical products, food industry, building materials, lubricants such as engine oil, bearing oil, gear oil, compressor oil, grease, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agricultural chemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications.

[0601] The present invention is further illustrated by the following examples 1 to 3.

[0602] Graft polymers based on non-fossil resources, production methods, uses, and compositions comprising them.

[0603] The present invention further relates to graft polymers having a low molar fraction of deuterium, a method for manufacturing such graft polymers based on non-fossil energy, wherein the molar fraction of deuterium in hydrogen and therefore in such hydrogen-based graft polymers is used to trace the source of hydrogen and thus the source of such hydrogen-based graft polymers, particularly the energy source, wherein the graft polymer is preferably based on a graft polymer containing an ethylene oxide backbone grafted with olefinically polymerizable monomers, preferably vinyl monomers, and more preferably grafted with:

[0604] a) Vinyl esters and optionally additional monomers, preferably selected from vinyl lactams, more preferably vinylpyrrolidones, and free radical polymerizable olefinic unsaturated amine monomers such as vinylamines, more preferably vinylimidazoles, and even more preferably, such monomers are at least one vinyl ester, at least one lactam, and optionally at least one vinylamine, and even more preferably, such monomers are vinyl acetate, vinylpyrrolidone, and vinylimidazoles, or

[0605] b) Vinyl lactams, more preferably vinylpyrrolidones, and free radical polymerizable olefinic unsaturated amine monomers such as vinylamines, more preferably vinylimidazoles; further encompassing a method for tracking the source, particularly the energy source, of hydrogen and thus such hydrogen-based graft polymers by determining the molar fraction of deuterium in the hydrogen-based graft polymer neutralized by hydrogen, wherein the graft polymers are preferably those as previously detailed; applications and uses of such graft polymers as previously detailed; and – further – products, formulations, and compositions comprising any one or mixtures of such graft polymers; and – even further – the use of such graft polymers as liquid or solid CO2 absorbents in CO2 capture methods.

[0606] The grafted polymers of the present invention are known in themselves and are now widely used or have just been recently disclosed - as further detailed below - and are therefore known to those skilled in the art.

[0607] In modern methods, large quantities of hydrogen are thus produced from natural gas through steam reforming.

[0608] However, petrochemical steam reforming processes have negative impacts on their carbon footprint, including the consumption of significant amounts of fossil-based natural resources and energy.

[0609] Today, it is crucial to be able to reliably track the source of hydrogen and downstream compounds obtained through clean energy. This is particularly important for ensuring the following:

[0610] • The production of hydrogen and downstream compounds meets sustainability standards.

[0611] • Renewable properties will not be counted twice.

[0612] Therefore, companies are increasingly focusing on sourcing green energy. Consequently, it is essential to develop tracking systems for the energy sources used in hydrogen production and downstream compounds.

[0613] US 2011 / 136097 relates to a method for determining the origin of a food product, and more specifically, for determining the geographical and / or biological origin of a food product containing alcohol or sugar by using, for example, a specific isotopic ratio of sugar from different plants, which is influenced by climatic conditions and the region of origin as an isotopic “fingerprint” of a particular plant.

[0614] However, the deuterium content utilized in this invention is not a natural "fingerprint," but rather stems from the discovery that the deuterium content of hydrogen obtained through water electrolysis is lower than the naturally occurring deuterium content in hydrogen. Furthermore, instead of specifying a geographical source region, the method of hydrogen production is determined.

[0615] US 6,495,609 relates to a method for recovering carbon dioxide from ethylene oxide production and using the recovered carbon dioxide as a carbon source for methanol synthesis. However, the hydrogen used in the method of US 6,495,609 is present in syngas (such as natural gas) or refinery tail gas.

[0616] GB 2 464 691 A relates to the production of methanol from agricultural by-product cellulose / lignin materials. In the first stage of the synthesis plant, the cellulose / lignin by-products remaining after harvesting agricultural products are converted into carbon dioxide through thermal oxidation. In another stage of the synthesis plant, hydrogen is produced by electrolysis, and then reacted with carbon dioxide to produce methanol.

[0617] WO 2016 / 149507 A1 relates to the oxidative coupling of methane for obtaining a wide variety of different products. For example, claim 217 discloses a method for producing oxalate compounds.

[0618] US 7,119,231 B2 relates to a method for preparing alkanolamines by reacting ammonia with an epoxide in a reaction space in the presence of a catalyst to obtain a monoalkanolamine, a dialkanolamine, or a trialkanolamine, or a mixture of two or three of these compounds. There is no indication regarding the deuterium content of the hydrogen-containing compounds used in US 7,119,231 B2 or regarding the use of non-fossil energy sources.

[0619] FR 2 851 564 A1 relates to a method for preparing ethylene oxide and ethanolamine. As in FR 2 851564 A1, there is no indication of the presence of deuterium in the hydrogen-containing compound or the use of non-fossil energy sources.

[0620] US 2008 / 0283411 A1 relates to a method for converting carbon and hydrogen sources into hydrocarbons. It mentions that the method and apparatus are useful for producing alternatives to fossil fuels, storing renewable energy sources, sequestering carbon dioxide from the atmosphere, offsetting global warming, and storing carbon dioxide in liquid fuels.

[0621] WO 2015 / 102985 A1 relates to a method for preparing ethanolamine, which includes reacting an aqueous ammonia solution with ethylene oxide. However, WO 2015 / 102985 A1 makes no indication of the preparation of hydrogen by electrolysis, the use of renewable energy, or the presence of deuterium in the hydrogen-containing compounds disclosed in WO 2015 / 102985 A1.

[0622] Therefore, the object of the present invention is to provide environmentally friendly grafted polymers having a low molar fraction of deuterium, wherein the grafted polymers are preferably based on ethylene oxide backbones grafted with ethylene monomers, preferably grafted with: a) vinyl esters and optionally additional monomers, such additional monomers preferably being at least one selected from vinyl lactams and vinylamines, such more preferably vinylpyrrolidone and / or vinylimidazole, or b) vinyl lactams and vinylamines, such more preferably vinylpyrrolidone and vinylimidazole; this object further covers an environmentally friendly method for manufacturing them, which uses as little fossil-based energy as possible, ideally none at all, and thus this method therefore increases CO2 emissions as little as possible and ideally none; another object is the use of the molar fraction of deuterium in hydrogen and therefore in such hydrogen-based grafted polymers for tracing the source of hydrogen and thus the source of such hydrogen-based grafted polymers, especially the energy source.

[0623] Methods for determining the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds are known to those skilled in the art and include mass spectrometry and NMR techniques.

[0624] Specifically, this objective is achieved by the grafted polymers of the present invention based on ethylene oxide backbones grafted with ethylene monomers, preferably grafted with: a) vinyl esters and optionally additional monomers, such additional monomers preferably being at least one selected from vinyl lactams and vinylamines, such more preferably vinylpyrrolidone and / or vinylimidazole, or b) vinyl lactams and vinylamines, such more preferably vinylpyrrolidone and vinylimidazole, when using methods for producing non-fossil-based ethylene oxide and then using known means to produce compounds of the present invention, wherein the molar fraction of deuterium is lower than that in products made solely using ethylene oxide (EO) from fossil-based sources. Compared to products using only fossil-based EO, products using non-fossil-based EO preferably have a deuterium content that is at least 10%, more preferably at least 20%, even more preferably at least 30%, even more preferably at least 50%, such as more than 60%, 70%, 80% or even 90%, based on the total hydrogen content of the units derived from the EO that has reacted with the compounds of the present invention.

[0625] In another embodiment of the invention, this objective is achieved by a method for manufacturing grafted polymers based on an ethylene oxide backbone, wherein the ethylene oxide backbone is grafted with ethylene monomers, preferably with: a) vinyl esters and optionally additional monomers, such additional monomers preferably being at least one selected from vinyl lactams and vinylamines, more preferably vinylpyrrolidone and / or vinylimidazole, or b) vinyl lactams and vinylamines, more preferably vinylpyrrolidone and vinylimidazole, wherein the method comprises the following steps:

[0626] (a) Providing hydrogen gas with a molar fraction of deuterium based on a total hydrogen content of ≤ 100 ppm, preferably in the range of 10 to ≤ 95 ppm, more preferably in the range of 10 to ≤ 90 ppm, and most preferably in the range of 10 to ≤ 80 ppm, through electrolysis based on electricity generated at least partially from non-fossil energy sources.

[0627] (b) The hydrogen from step (a) is reacted with carbon oxides, preferably carbon dioxide, to form methanol.

[0628] (c) The methanol from step (c) is converted into ethylene and further into ethylene oxide.

[0629] (d) In one or more steps, the ethylene oxide from step (d) is converted into a polymer or mixture of polymers using a known method such as alkoxylation, the polymer comprising ethylene oxide and optionally other monomers selected from alkyl oxidases other than ethylene oxide.

[0630] (e) Using standard means, the polymer from step (d) is further reacted with at least one vinyl monomer, preferably with: a) at least one vinyl ester and optionally at least one additional monomer, preferably at least one monomer selected from vinyl lactams and free-radical polymerizable olefinically unsaturated amine monomers, more preferably vinylpyrrolidone and / or vinylimidazole, or b) at least one vinyl lactam, preferably vinylpyrrolidone and optionally at least one vinylamine, preferably vinylimidazole.

[0631] To obtain grafted polymers containing deuterium with a lower total hydrogen content compared to grafted polymers obtained solely from fossil-based sources with the same chemistry.

[0632] Today, it is even more important to be able to reliably track the source of hydrogen and downstream compounds obtained through clean energy.

[0633] This is especially to ensure that:

[0634] • Hydrogen and the grafted polymers produced from the use of such hydrogen have been produced in accordance with sustainability standards.

[0635] • Renewable properties will not be counted twice.

[0636] As companies place increasing emphasis on sourcing green energy, it is essential to develop tracking systems for the energy sources used in hydrogen production and downstream compounds.

[0637] This invention provides the possibility of tracking the grafted polymers of this invention back to non-fossil-based resources.

[0638] Therefore, the method for tracing the molar fraction of deuterium in the grafted polymer of the present invention through the use of hydrogen and thus based on such hydrogen to return the grafted polymer to its source, especially its energy source and to non-fossil-based resources, is also part of the present invention.

[0639] Methods for determining the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds are known to those skilled in the art. Suitable methods are described in the examples of this application.

[0640] Due to further advances in science and technology, and consequently, the development of increasingly sophisticated measurement techniques, the resolution of measurement methods used to determine deuterium content relative to total hydrogen content is expected to become increasingly precise, making even more accurate determinations possible in the future, and thus enabling the differentiation between minute differences. However, the invention disclosed herein will not be altered by such scientific advancements, but merely the increased likelihood of detecting the invention.

[0641] Another environmental benefit of the environmentally friendly grafted polymers according to the invention is their use in carbon capture methods, because the grafted polymers according to the invention use as little fossil-based energy as possible, ideally none, for production, at least relative to the content derived from EO, and indeed, therefore, increase CO2 emissions only as little as possible, ideally none.

[0642] Of course, if environmentally friendly methods are also employed for other components such as other epoxides and / or monomers (i.e., vinyl esters, vinyl lactams, vinylamines), then the present invention will be even more environmentally friendly. Therefore, the present invention also covers such even more environmentally friendly products in which the other epoxides and / or monomers used are derived from or made from renewable or even better non-fossil-based sources. To date, such sources are known for at least some of those other components.

[0643] Another embodiment of the present invention is the use of the grafted polymer according to the invention as a liquid or solid CO2 absorbent in a CO2 capture method.

[0644] Another embodiment of the invention is the use of the grafted polymer according to the invention in compositions, products or formulations, wherein such compositions, products or formulations are those that are chemically identical grafted polymers as are currently known for use in conventionally produced grafted polymers for use in such compositions, products or formulations – except for differences in deuterium content.

[0645] The molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds is given in this application in ppm based on the total hydrogen content, which is the mol-ppm content of deuterium based on the total hydrogen content (in hydrogen or in the compounds discussed, respectively).

[0646] The deuterium content of hydrogen and hydrogen-based downstream compounds is expressed in this application based on the total molar hydrogen content (total tritium). 1 H and deuterium 2 The atomic fraction (ppm) of H atoms is given. The terms “deuterium content” and “molar fraction of deuterium” are used synonymously throughout the application.

[0647] In physical organic chemistry, the kinetic isotope effect is the change in the rate of a chemical reaction when one of the atoms in a reactant is replaced by one of its isotopes. Formally, it involves the substitution of light (k) atoms for other atoms. L ) and weight(k H The rate constant k of a reaction involving isotopic substitution reactants (isotopes). L / k HThe ratio of the two isotopes. This change in reaction rate is a quantum mechanical effect, primarily caused by the heavier isotope having a lower vibrational frequency compared to its lighter counterpart. In most cases, this means that the heavier isotope requires a larger energy input to reach the transition state, and therefore has a slower reaction rate.

[0648] The isotopic rate change is most significant when the relative mass change is largest because the effect is related to the vibrational frequencies of the affected bonds. For example, replacing hydrogen atoms (H) with their isotope deuterium (D) represents a 100% increase in mass, while using... 13 C substitute 12 At C, the mass increases by only 8%. Reactions involving CH bonds typically occur 6-10 times faster than the corresponding CD bonds, while... 12 The C reaction is only slightly more than the corresponding 13 C reacts 4% faster.

[0649] The first-order kinetic isotope effect can be observed when bonds with isotope atoms form or break. The second-order kinetic isotope effect is observed when bonds with isotope atoms in the reactants remain unbroken or unformed. The second-order kinetic isotope effect is often much smaller than the first-order kinetic isotope effect; however, the second-order deuterium isotope effect can be as large as 1.4 per deuterium atom.

[0650] A method for manufacturing the grafted polymer of the present invention is described in detail, the method comprising the various method steps mentioned above:

[0651] Step (a)

[0652] Step (a) involves providing a molar fraction of deuterium as hydrogen gas with a total hydrogen content of less than 100 ppm, preferably less than 90 ppm, by electrolysis based on electricity generated at least in part from non-fossil energy.

[0653] Electricity is generated at least in part from non-fossil resources.

[0654] The term "at least partially" means that a portion of the electricity can still be generated from fossil fuels, preferably natural gas, because the combustion of natural gas results in much lower carbon dioxide emissions per megajoule of electricity compared to the combustion of coal. However, the portion of the electricity generated from fossil fuels should be as low as possible, preferably ≤ 50%, more preferably ≤ 30%, most preferably ≤ 20%, and further most preferably ≤ 10%. In one embodiment, the electricity is generated solely from non-fossil resources.

[0655] Local legislation has established various methods for certifying and tracking the “energy mix.” For example, certificates under the “Non-Fossil Certificate Contract” are a common practice for tracking the percentage of non-fossil energy used in industrial processes and related products (https: / / www.ekoenergy.org / ecolabel / criteria / tracking / ).

[0656] Preferably, the electricity is generated at least in part from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydropower (tidal energy, wave energy, hydroelectric dams, river hydrodynamics), geothermal energy, environmental or industrial heat captured by heat pumps, bioenergy (biofuels, biomass), the renewable portion of waste energy or nuclear energy (fission).

[0657] In another embodiment, the electricity is generated at least in part from renewable resources, preferably wind, solar (thermal, photovoltaic and concentrated solar), hydropower (tidal, wave, hydroelectric dam, river hydrodynamic), geothermal, ambient heat captured by a heat pump, bioenergy (biofuel, biomass), or the renewable portion of waste.

[0658] The types of power resources mentioned above are generally known to those skilled in the art.

[0659] In a preferred embodiment of the method of the invention, the electricity generated from the non-fossil resources used in the electrolysis according to the invention can be at least partially generated by nuclear energy. Nuclear energy can be obtained through fission.

[0660] When a neutron enters the nucleus of a larger atom, fission occurs, forcing it to become excited and split into two smaller atoms—also known as fission products. Additional neutrons are also released, which can trigger a chain reaction. As each atom splits, a tremendous amount of energy is released. Uranium and plutonium isotopes are most commonly used in fission reactions in nuclear reactors because they are easy to initiate and control. The energy released through fission in these reactors heats water into steam. The steam is used to power turbines to produce carbon-free electricity.

[0661] The electricity derived from non-fossil resources used in the water electrolysis according to the present invention is preferably generated by wind, solar, biomass, hydropower, and geothermal energy.

[0662] In a preferred embodiment of the method of the present invention, the electricity used in the electrolysis is at least partially generated by wind power. Wind power can be used to operate wind turbines. Modern utility-scale wind turbines have rated power ranging from approximately 600 kW to 9 MW. The power that can be generated from wind is a function of the cube of the wind speed, so as the wind speed increases, the power output increases until the maximum output of a particular turbine. Areas with stronger and more constant winds, such as offshore and high-altitude sites, are preferred locations for wind farms.

[0663] In another preferred embodiment of the method of the invention, the electricity used in electrolysis is at least partially generated by solar energy, particularly preferably by a photovoltaic system. A photovoltaic system converts light into direct current (DC) using the photoelectric effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus sunlight from a large area into a small beam. CSP-Stirling systems currently possess the highest efficiency of all solar energy technologies to date.

[0664] In a preferred embodiment of the method of the present invention, the electricity used in the electrolysis is at least partially generated by hydropower. Hydropower comes in many forms. Traditionally, hydropower is generated by constructing large hydroelectric dams and reservoirs. Small hydroelectric systems are hydroelectric power generation devices that typically produce up to 50 MW of power. They are often used on small rivers or as low-impact development projects on large rivers. Hydropower stations operating on rivers obtain energy from the river without creating large reservoirs. Water is typically transported along the side of the valley (using channels, pipes, and / or tunnels) until the water level is above the valley floor, at which point it can be allowed to fall through pressurized pipes to drive turbines.

[0665] Wave energy, which captures the energy of ocean waves, and tidal energy, which converts tidal energy, are two forms of hydropower with future potential.

[0666] In another preferred embodiment of the method of the invention, the electricity used in the electrolysis is generated at least in part by geothermal energy. Geothermal energy is heat originating from beneath the Earth's surface. It is contained in rocks and fluids beneath the Earth's crust and can be found as far as the Earth's fiery lava and fusiforme. To generate electricity from geothermal energy, wells are dug a mile deep into underground reservoirs to obtain the steam and hot water there, which can then be used to drive turbines connected to generators. There are three types of geothermal power plants: dry steam, flash, and binary. Dry steam is the oldest form of geothermal technology and extracts steam from underground and uses it to directly drive turbines. Flash plants use high-pressure hot water to pass through cold, low-pressure water, while binary plants pass hot water through a secondary liquid with a lower boiling point, which is converted into steam to drive turbines.

[0667] In another preferred embodiment of the method of the invention, the electricity used in electrolysis is at least partially generated by biomass. Biomass is biological material derived from living organisms or recently living organisms. It most often refers to plants or plant-derived materials, specifically lignocellulosic biomass. As an energy source, biomass can be used directly by generating heat (e.g., heat from fermentation processes) or electricity through combustion, or indirectly after being converted into various forms of biofuels and gases. The conversion of biomass into biofuels can be achieved through different methods, which are broadly classified as thermal, chemical, and biochemical methods. As of 2012, wood was the largest biomass energy source; examples include forest residues (such as dead trees, branches, and stumps), garden trimmings, sawdust, and even municipal solid waste. Industrial biomass can be grown from a wide variety of plant types, including Miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a range of tree species from eucalyptus to oil palm (palm oil).

[0668] Plant energy is produced by crops specifically grown for fuel, which provide high biomass yields per hectare with low energy inputs. Grains can be used as liquid transport fuels, while straw can be burned to generate heat or electricity. Biomass can be converted into other available energy forms, such as methane gas or transport fuels like ethanol and biodiesel. Decaying waste, as well as agricultural and human waste, releases methane gas – also known as landfill gas or biogas. Crops such as corn and sugarcane can be fermented to produce ethanol, a transport fuel. Biodiesel (another transport fuel) can be produced from leftover food products such as vegetable oils and animal fats.

[0669] Bioenergy technologies utilize processes similar to those using fossil fuels to convert renewable biomass fuels into heat or electricity. There are three ways to extract energy stored in biomass to produce bioenergy: combustion, bacterial decomposition, and conversion into gaseous or liquid fuels.

[0670] Bioenergy can offset the need for carbon fuels burned in power plants, thereby reducing the carbon intensity of power generation. Unlike some forms of intermittent renewable energy, bioenergy can increase the flexibility of power generation and enhance the reliability of the power grid.

[0671] The electrolysis in step (a) is usually the electrolysis of water.

[0672] Water electrolysis is an environmentally friendly method for producing hydrogen because it uses renewable H2O and produces only pure oxygen as a byproduct. Furthermore, water electrolysis utilizes direct current (DC) from sustainable energy sources such as solar, wind, hydro, and biomass energy.

[0673] According to the present invention, electrolysis, typically water electrolysis, utilizes direct current (DC) from at least a portion of non-fossil energy sources as electricity.

[0674] It has now been observed, as a key observation of this application, that the deuterium content of hydrogen produced by water electrolysis is lower than that of hydrogen produced by petrochemical means (e.g., hydrogen contained in fossil-based syngas), specifically based on a total hydrogen content ≤ 100 ppm, preferably in the range of 10 to ≤ 95 ppm, more preferably in the range of 10 to ≤ 90 ppm, and most preferably in the range of 10 to ≤ 80 ppm. The deuterium content in the hydrogen produced by electrolysis can be as low as 10 ppm. The remaining deuterium exists primarily in the form of DH rather than D2.

[0675] A suitable method for water electrolysis is alkaline water electrolysis. Producing hydrogen through alkaline water electrolysis is a mature technology, reaching commercial-grade megawatt levels. In alkaline water electrolysis, initially at the cathode side, two water molecules in the alkaline solution (KOH / NaOH) are reduced to one hydrogen molecule (H₂) and two hydroxide ions (OH⁻). - The generated H2 is released from the cathode surface in gaseous form, and hydroxide ions (OH-) are also released. - Under the influence of the electric field between the anode and cathode, the gases migrate through a porous membrane to the anode, where they are discharged as half-oxygen molecules (O2) and one water molecule (H2O). Alkaline electrolysis operates at relatively low temperatures (e.g., 30°C–80°C) using an alkaline aqueous solution (KOH / NaOH) as the electrolyte, with a concentration of approximately 20% to 30%. A membrane in the middle of the electrolytic cell separates the cathode and anode and also separates the generated gases from their respective electrodes, thus preventing mixing. However, alkaline electrolysis has disadvantages, such as a limited current density (below 400 mA / cm²). 2 It has low operating pressure and low energy efficiency.

[0676] A review of hydrogen production via alkaline water electrolysis powered by renewable energy is given in J. Brauns and T. Turek, Processes, 8(2) (2020), p. 248.

[0677] In another embodiment of the method of the present invention, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variations of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).

[0678] 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 and high proton conductivity (0.1 ± 0.02 S cm⁻¹). -1 PEM water electrolysis offers several advantages, including compact design, low thickness (20-300 µm), and allows for high-pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most advantageous methods for converting renewable energy into high-purity hydrogen. PEM water electrolysis offers significant advantages such as compact design and high current density (above 2 A cm⁻¹). -2 It features high efficiency, fast response, operation at low temperatures (20°C-90°C), and production of ultrapure hydrogen. Existing electrocatalysts 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.

[0679] One of the greatest advantages of PEM water electrolysis is its ability to operate at high current densities. This results in reduced operating costs, especially for systems combined with highly dynamic energy sources such as wind and solar power, where sudden spikes in energy output would otherwise lead to uncaptured energy. The polymer electrolyte allows PEM water electrolyzers to operate with very thin membranes (approximately 100–200 µm) while still allowing for high operating pressures, resulting in low ohmic losses primarily due to proton conduction through the membrane (0.1 S / cm), and compressed hydrogen output.

[0680] The PEM water electrolyzer utilizes a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while simultaneously insulating the electrodes. Under standard conditions, the enthalpy required to form water is 285.9 kJ / mol. A portion of the energy required for the continuous electrolysis reaction is supplied by heat, and the remainder by electricity.

[0681] The half-reaction that occurs on the anode side of a PEM water electrolyzer is commonly referred to as the oxygen evolution reaction (OER). Here, liquid water reactants are supplied to a catalyst, where they are oxidized into oxygen, protons, and electrons.

[0682] The half-reaction that occurs on the cathode side of a PEM water electrolyzer is commonly referred to as the hydrogen evolution reaction (HER). Here, protons that have moved across the membrane are reduced to gaseous hydrogen.

[0683] PEMs can be made from pure polymer membranes or composite membranes, in which other materials are embedded within a polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA (e.g., Nafion®, a DuPont product). While Nafion® is an ionomer with a perfluorinated backbone like Teflon, many other structural motifs exist for the manufacture of proton exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

[0684] A review of hydrogen production via PEM water electrolysis is given in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442-4454.

[0685] A review of hydrogen production via water electrolysis through anion exchange membranes is given in HA Miller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0686] K. Harada et al., *International Journal of Hydrogen Energy*, 45(2020), pp. 31389-31395, reported a 2-3 fold depletion of deuterium in polymer electrolyte membrane water electrolysis. Corresponding to a stoichiometric number λ between 4 and 9 for a given water mass flow rate at the anode, this was observed at current densities of 1.0 to 2.0 Acm⁻¹. -2 In the case of separation coefficient β

[0687] β = ([H] / [D]) 气体 / ([H] / [D]) 液体

[0688] Between 2 and 3, where "gas" refers to the escaping gas and "liquid" refers to the water before electrolysis. The stoichiometric coefficient λ is defined as follows:

[0689] λ = V x ρ / (J / 2F x 60 x M H2O )

[0690] Where V (mL min) -1 ) is the water mass flow rate in the anode, F is the Faraday constant, J is the electrolysis current (A), and ρ is the density of water (g / mL). -1 And M H2O (g mol) -1λ is the molar weight of water. A stoichiometric coefficient λ of 10 means that, for a given electrolysis current, the amount of fresh water supplied to the anode can be 10 times the amount theoretically consumed by electrolysis.

[0691] H. Sato et al., International Journal of Hydrogen Energy, 46 (2021), pp. 33689-33695, reported that for anion exchange membrane water electrolysis, at λ = 4, the deuterium concentration in the escaping hydrogen was diluted by about 1 / 5 relative to the feed water.

[0692] Therefore, in the case of feed water in polymer electrolyte membrane water electrolysis, the deuterium content in the escaping hydrogen can be easily depleted by 2 to 5 times. Depending on the electrolysis conditions (water flow rate, current density), even higher depletion factors are possible. Since the average deuterium content of water is based on a total hydrogen content of about 150 ppm, the hydrogen provided in step (a) of the method of the present invention can have a deuterium content of 30 to 75 ppm, or even lower, based on a total hydrogen content.

[0693] AEM water electrolysis technology employs low-cost catalytic materials (as in alkaline electrolysis) and solid polymer electrolyte structures (as in PEM electrolysis). AEM electrolysis operates in an alkaline environment (pH approximately 10), enabling the use of suitable non-precious metal electrocatalysts (i.e., platinum group metal-free catalysts = PGM-free catalysts) while accommodating zero-gap structures. The membranes used in this type of electrolysis are polymer membranes containing quaternary ammonium salts. These are relatively inexpensive and exhibit low interaction with atmospheric CO2.

[0694] catalyst:

[0695] As an example of a hydrogen evolution reaction (HER) catalyst, a catalyst based on Ni-Mo alloying material is suitable.

[0696] Highly active transition metal mixed oxides are suitable as examples of oxygen evolution reaction (OER) catalysts. Specific examples are CuxCo3_xO4, NiCo2O4:Fe and Ni-Fe alloys on Ni foam supports, such as PGM-free catalysts (Ni-Fe, Ni-Mo, Ni / (CeO2-La2O3) / C and CuxCo3_xO4).

[0697] Membranes and ionomers:

[0698] The chemical stability of AEM under alkaline conditions has been significantly improved due to the formation of stable functional groups on the polymer backbone. This allows for the long-term use of such membranes at higher temperatures in AEM electrolysis. Suitable membranes and ionomers are known to those skilled in the art and are described, for example, in the reviews mentioned below. One example is the commercial membrane Tokuyama A201.

[0699] Membrane electrode assembly fabrication and battery performance:

[0700] Physical and electrochemical characterization of membrane electrode assemblies prepared by catalyst-coated substrate (CCS) or catalyst-coated membrane (CCM) methods indicates that CCM is preferred because the improvement in ionic conductivity far outweighs any improvement in electronic conductivity.

[0701] Liquid electrolytes: Pure water feed typically results in poor current density, while 1% K₂CO₃ or dilute KOH solution provides good results. Good electrolytic performance was achieved using a 1% K₂CO₃ electrolyte. Therefore, it is preferable that the aqueous electrolyte contains 0.1 to 2 wt% K₂CO₃ or KOH.

[0702] A review of hydrogen production via water electrolysis through anion exchange membranes is given in HA Miller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0703] In addition to alkaline water electrolysis (AEM and PEM), another commercially available electrolysis technology is solid oxide electrolysis (SOE).

[0704] In a SOEC (Solid Oxide Electrolyte Cell), water is fed into the cathode and undergoes a water reduction reaction (WRR), which converts the water into hydrogen and oxygen ions. This hydrogen is then passed to a purification module to separate it from the remaining water. The oxygen ions then migrate from the cathode to the anode and release electrons into an external circuit via the oxygen evolution reaction (OER) to become oxygen gas. Typically, SOFCs operate at temperatures between 800°C and 1,000°C because the high temperatures are required to thermally activate the migration of oxygen ions and promote the electrochemical reactions at both electrodes. This improves the overall efficiency. SOECs are described, for example, in K. Kamlungsua et al., FUEL CELLS 20 [Fuel Cells 20], 2020, Vol. 6, pp. 644-649.

[0705] Preferably, the electrolysis in step (a) is water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

[0706] In another preferred embodiment, the electrolysis in step (a) is solid oxide water electrolysis (SOE).

[0707] It is known in the art that, regarding the feed water in water electrolysis (e.g., polymer electrolyte membrane water electrolysis), the deuterium in the released hydrogen can be depleted. The depletion factor depends on the electrolysis conditions (water flow rate, current density). Since the average deuterium content (molar 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 molar fraction of deuterium (deuterium content) based on the total hydrogen content ≤ 100 ppm, preferably in the range of 10 to ≤ 95 ppm, more preferably in the range of 10 to ≤ 90 ppm, most preferably in the range of 10 to ≤ 80 ppm, or even lower.

[0708] Generally, any water source can be used in the preferred water electrolysis in step (a). However, since the hydrogen produced in step (a) has a deuterium molar fraction (deuterium content) based on a total hydrogen content of less than 100 ppm, preferably in the range of 10 to ≤ 95 ppm, more preferably in the range of 10 to ≤ 90 ppm, and most preferably in the range of 10 to ≤ 80 ppm, it is preferred to use water having a deuterium molar fraction (deuterium content) based on a total hydrogen content of less than 160 ppm.

[0709] Vienna Standard Mean Ocean Water (VSMOW) is an isotopic water standard defined by the International Atomic Energy Agency (IAEA) in 1968. Despite some misleading phrases like "seawater," VSMOW refers to pure water (H2O) and does not include any salts or other substances typically found in seawater. VSMOW serves as a reference standard for comparing the ratios of hydrogen and oxygen isotopes (primarily in water samples). Very pure, distilled VSMOW water is also used for high-precision measurements of water's physical properties and for determining laboratory standards, as it is considered representative of "mean ocean water," essentially representing the Earth's water content.

[0710] The isotopic composition of VSMOW water is specified as the ratio of the molar abundance of the rare isotope under discussion 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, which has eight protons and eight neutrons) is ubiquitous in seawater. 17 It is approximately 2,632 times that of O (which has an extra neutron). The isotopic ratio of water in VSMOW is defined as follows:

[0711] 2 H / 1H = 155.76 ± 0.1 ppm (ratio of 1 part to approximately 6420 parts)

[0712] 3 H / 1 H = 1.85 ± 0.36 times; 10 -11 ppm (1 part / approximately 5.41 times; 10) 16 (The ratio of components is negligible due to the effects of physical properties.)

[0713] 18 O / 16 O = 2005.20 ± 0.43 ppm (1 part / approximately 498.7 parts)

[0714] 17 O / 16 O = 379.9 ± 1.6 ppm (ratio of 1 part to approximately 2632 parts)

[0715] (See: https: / / en-academic.com / dic.nsf / enwiki / 753132)

[0716] More preferably, the water in step (a) has an average deuterium content of 1 ppm (ultralight water) to 156 ppm, and most preferably 2 ppm to 150 ppm, based on a total hydrogen content.

[0717] Methods for depleting deuterium in water are known to those skilled in the art. However, such methods are typically energy-intensive electrolysis methods, as described, for example, in CN103848399A.

[0718] Therefore, when using deuterium-depleted water, it is preferable to use deuterium-depleted water obtained from the following resources:

[0719] - A byproduct of heavy water (D2O) production (heavy water has applications in organic chemistry, drug development, and nuclear reactors); (deuterium content is approximately 10-120 ppm).

[0720] - Mountain water; (deuterium content approximately 120-150 ppm)

[0721] - Surface river and lake water; (deuterium content approximately 130-150 ppm)

[0722] - Any water source with seasonally low deuterium content, such as water collected at low temperatures (water in cold winters contains less deuterium than water in warm summers); such as water obtained during winter, such as water obtained from snow or ice; (deuterium content is approximately 120-150 ppm).

[0723] -Polar water and Antarctic glacial water (deuterium content approximately 90-150 ppm)

[0724] - Low-salinity seawater, such as low-salinity seawater near river mouths, desalinated seawater or brackish water, and wastewater treatment effluent; (deuterium content approximately 130-155 ppm)

[0725] Step (b)

[0726] Step (b) involves reacting the hydrogen from step (a) with carbon oxides, preferably carbon dioxide, to form methanol.

[0727] Suitable carbon oxides are carbon monoxide, carbon dioxide, or a mixture of both, with carbon dioxide being preferred.

[0728] The conditions for the methods used to hydrogenate carbon monoxide or a mixture of carbon monoxide and carbon dioxide are known in themselves, such as low-pressure synthesis, medium-pressure synthesis and high-pressure synthesis.

[0729] i) Low-pressure synthesis

[0730] Low-pressure synthesis is typically carried out at pressures between 50 and 100 bar. Temperatures are typically between 220°C and 300°C. Catalysts based on Cu, Zn, and Al₂O₃ (e.g., CuO / ZnO / Al₂O₃) are commonly used. Low-pressure synthesis is the preferred method for preparing methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0731] ii) Medium-pressure synthesis

[0732] Medium-pressure synthesis is typically carried out at pressures between 100 and 250 bar. Temperatures are typically up to 300°C. Zn / Cr₂O₃-based catalysts or Zn-Cu catalysts are commonly used as catalysts.

[0733] iii) High-Pressure Synthesis: High-pressure synthesis is typically carried out at pressures between 250 and 350 bar. Temperatures are typically between 320°C and 380°C. Zinc-chromium oxide-based catalysts are commonly used. This process is less preferred for the production of methanol from carbon monoxide or a mixture of carbon monoxide and carbon dioxide.

[0734] The current global energy system remains primarily based on the use of fossil fuels, and this will continue in the medium and short term, despite an increase in the use of renewable energy. The extensive use of fossil fuels in industry and transportation generates significant CO2 emissions. Since the purpose of this invention is to provide environmentally friendly grafted polymers and environmentally friendly methods for manufacturing them, it is preferred to produce methanol by reacting hydrogen from step (a) with carbon dioxide from step (c) according to the method of the invention.

[0735] In a preferred embodiment, the carbon dioxide provided in step (c) is captured from industrial flue gas or from ambient air. All available capture technologies can be used.

[0736] A review of commercial CO2 capture technologies is given in Koytsoumoa et al., The Journal of Supercritical Fluids, Vol. 132, February 2018, pp. 3-16.

[0737] Capturing CO2 at point sources, such as large carbon-based energy facilities, industries with high CO2 emissions (e.g., cement production, ammonia synthesis, steelmaking), natural gas processing, synthetic fuel plants, and fossil fuel-based hydrogen production plants, is the most cost-effective approach. Extracting CO2 from the air is possible, although the lower concentration of CO2 in the air compared to combustion sources complicates engineering and therefore makes the process more expensive.

[0738] In some preferred embodiments, the carbon dioxide provided in step (b) is captured from industrial flue gas.

[0739] The main industrial sources of CO2 are power plants that burn fossil fuels, oil refineries, biogas desulfurization (e.g., fermentation), and the production of chemicals. Related chemical production methods include, for example, the production of C1-C4 olefins and C6 aromatics, as well as downstream chemicals such as, in particular, ammonia and other CO2-intensive products from naphtha cracking. Additionally, the production of industrial paper, food, cement, minerals, and iron and steel can be cited as examples.

[0740] In post-combustion capture, CO2 is removed after the combustion of fossil fuels (this is the approach used in fossil fuel power plants). CO2 is captured from flue gas at power plants or other point sources. Absorption or carbon washing with amines is the primary capture technology. It is the only carbon capture technology used industrially to date. Suitable post-carbon capture methods include, for example, absorption (chemisorption, physisorption), adsorption (chemisorption, physisorption), membrane processes, biological processes, and cryogenic processes.

[0741] Preconversion capture refers to the capture of CO2 produced as an undesirable co-product of intermediate reactions in a conversion process. Some examples include ammonia production and coal gasification in power plants. In ammonia production, CO2 produced with hydrogen during steam reforming must be removed before ammonia synthesis can occur – absorption in monoethanolamine (MEA) and / or diethanolamine (DEA) is commonly used for these purposes. Similarly, in integrated gasification combined cycle (IGCC) power plants, CO2 must be separated from hydrogen. This is typically achieved using physical solvents such as selexol and rectisol. Note that when applied to power plants, preconversion capture is also referred to as pre-combustion capture.

[0742] Oxygen-fuel combustion technology involves the combustion of carbonaceous fuels in a stream of pure oxygen instead of air. Because the oxidant (O2) does not contain other components found in air (such as nitrogen), the CO2 concentration in the flue gas will be very high, while the water vapor content can be easily removed.

[0743] CO2 is adsorbed into MOFs (metal-organic frameworks) through selective physical or chemical adsorption based on MOF porosity, leaving a CO2-lean gas stream. CO2 is then stripped from the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA), allowing the MOF to be reused.

[0744] In some other preferred embodiments, the carbon dioxide provided in step (b) is captured from ambient air.

[0745] Direct air capture (DAC) is a process that directly captures carbon dioxide (CO2) from ambient air and produces a concentrated stream of CO2 for isolation, utilization, or production of carbon-neutral fuels. CO2 removal is achieved when ambient air comes into contact with a chemical medium (typically an aqueous, alkaline solvent or an adsorbent). These chemicals are then stripped of CO2 by the application of energy (i.e., heat), yielding a CO2 stream that can be dehydrated and compressed, while simultaneously regenerating the chemical medium for reuse.

[0746] In Chen, Lackner et al., Angew. Chem. Int. Ed. 2020, 59, 6984-7006, “Sorbents for the Direct Capture of CO2 from Ambient Air”, the main types of adsorbents designed to capture CO2 from ambient air are described, which are classified by the following adsorption mechanisms: physisorption, chemisorption, and moisture-dependent adsorption.

[0747] The application of polyethylene imide in carbon dioxide capture and separation is described in Kommalapati et al., Energy Technol. 2017, 5, 822-833.

[0748] Diluted CO2 can be efficiently separated using an anion exchange polymer resin called Marathon MSA, which absorbs CO2 from the air when dry and releases it when exposed to moisture. Most of the energy used in this process is supplied by the latent heat of phase change of water. Other materials that can be used are metal-organic frameworks (or MOFs). Membrane separation of CO2 relies on semipermeable membranes.

[0749] Therefore, in another embodiment, the present invention relates to the use of the grafted polymer according to the invention as a CO2 absorbent in a CO2 capture method.

[0750] Suitable carbon capture methods are mentioned above and are known in the art.

[0751] In step (b), carbon dioxide and hydrogen are reacted to form methanol.

[0752] The conditions for the hydrogenation of carbon dioxide are known in themselves. Different approaches are being developed for the synthesis of methanol from hydrogenated CO2: (1) heterogeneous catalysis, (2) homogeneous catalysis, (3) electrochemistry, and (4) photocatalysis (see R. Guil-López, Materials 2019, 12, 3902; doi:10.3390 / ma12233902). Preferably, the synthesis of methanol from hydrogenated carbon dioxide is carried out in the presence of a heterogeneous catalyst.

[0753] Methanol production typically takes place in synthetic converters (such as fixed-bed catalytic reactors).

[0754] The average temperature inside the reactor is typically in the range of 150°C to 300°C. The average pressure inside the reactor is typically in the range of 50 to 150 bar (absolute pressure).

[0755] A review of suitable heterogeneous catalyst systems is given by Kristian Stangeland, Hailong Li, and Zhixin Yu, Energy, Ecology and Environment, Vol. 5, pp. 272-285 (2020). This process requires multi-component catalyst systems. Interactions between components are essential for the high activity and selectivity of catalysts for CO2 to methanol production. This has been demonstrated by numerous catalyst systems composed of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., Al2O3, ZnO, ZrO2, In2O3). These complex systems can contain mixtures of metallic, alloy, and metal oxide phases. The most promising catalyst systems for large-scale industrial methods are currently Cu-based and In-based catalysts due to their excellent catalytic performance. Suitable catalysts are, for example, copper-zinc-alumina.

[0756] By performing step (b), methanol is formed by reacting carbon oxides, preferably carbon dioxide, with hydrogen from step (a). The deuterium content is even lower than the deuterium content corresponding to the distribution obtained through classical petrochemical processes.

[0757] Step (c)

[0758] In step (c), the methanol from step (b) is converted into ethylene and further into ethylene oxide.

[0759] Preferably, the ethylene oxide in step (c) is obtained by the following method:

[0760] (c1) The methanol-to-olefins process, in which ethylene is obtained, followed by...

[0761] (c2) Epoxidation of ethylene.

[0762] Step (c1)

[0763] Ethylene is typically produced from methanol using the methanol-to-olefins (MTO) process.

[0764] The MTO process is an acid-catalyzed reaction. Preferred catalysts are zeolites, such as zeolites containing silica and alumina (e.g., ZSM-5) and silica-alumina phosphate (SAPO) zeolite catalysts (e.g., SAPO-34).

[0765] The reaction is typically carried out at temperatures between 300°C and 600°C. The pressure is typically 0.1–0.3 MPa.

[0766] This process is preferably carried out in a fluidized catalytic reactor.

[0767] The ratio of propylene to ethylene can be adjusted by selecting appropriate process conditions, and can vary from 0.77 in the ethylene production mode and 1.33 in the propylene production mode.

[0768] Examples of commercial MTO technology licensors include UOP (e.g., UOP Advanced MTO process), Energy Technology Co. Ltd. (DMTO process), and Sinopec (SMTO process).

[0769] A more detailed description can be found, for example, in "Ethylene" by Adam Chan of Nexant, TECH 2018-1, July 2018, pp. 100-109.

[0770] Step (c2)

[0771] In step (c2), the ethylene from step (c1) is converted into ethylene oxide.

[0772] The direct oxidation method is preferably carried out in the gas phase (e.g., a gas phase containing oxygen or air) in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

[0773] Step (c2) is typically carried out at a temperature of 230°C to 270°C. The pressure is preferably in the range of 10 to 30 bar.

[0774] In a preferred embodiment, step (c2) is carried out by gas-phase selective ethylene oxidation (ethylene epoxidation), which is typically carried out in a fixed-bed tubular reactor with a supported Ag / Al2O3 catalyst at 230°C-270°C and 10-30 bar.

[0775] The preferred catalyst for the method in step (c2) is a silver-based catalyst, such as...

[0776] - Preferably, a supported Re / Cs / Ag / Al2O3 catalyst operating with excess C2H4 / O2; or

[0777] - Preferably, it is a supported Ag / Al2O3 catalyst promoted by an alkali metal (Na, Cs) operating with excess O2 / C2H4.

[0778] It has been found that oxides of Mo and S also promote supported Re / Cs / Ag / Al2O3 systems for EO formation. Therefore, supported Re / Cs / Ag / Al2O3 systems can additionally incorporate oxides of Mo and / or S as promoters.

[0779] Alternatively, C2H4Cl2 can be added to deposit Cl onto the catalyst, which acts as a promoter.

[0780] Examples of the description can be found, for instance, in “Ethylene Oxide” by Mia Monconduit and Karen Jobes of IHS Markit, Chemical Economics Handbook, December 22, 2020, pp. 14–16.

[0781] Step (d) of a method for producing polymers containing ethylene oxide

[0782] In step (d), the ethylene oxide from step (c) is converted into a polymer or mixture of polymers using a known method such as alkoxylation reaction. Such polymers contain ethylene oxide and optionally other monomers selected from alkyl oxidases other than ethylene oxide.

[0783] This polymer is also referred to below as the "polymer backbone" and "polymer backbone (A)".

[0784] The resulting polymer comprises ethylene oxide and optionally additional monomers. Thus, the polymer is a homopolymer of ethylene oxide such as polyethylene oxide and polyethylene glycol (distinguished only by the end groups; typically, it is “polyethylene glycol” as the end group, which usually consists of two hydroxyl groups), and a copolymer comprising ethylene oxide and at least one additional monomer that can react with ethylene oxide.

[0785] Such copolymers include copolymers of ethylene oxide with at least one other monomer, and can be obtained by polymerization of ethylene oxide and at least one alkyl oxide selected from the group consisting of C3- to C4-. 10 - epoxides, preferably C3- to C5-epoxides, such as 1,2-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane and / or 2,3-epoxypentane; and optionally at least one polyol selected from the group consisting of C2- to C8-polyols, preferably C2- to C6-polyols.

[0786] This type of copolymer can be any known type of copolymer, such as block copolymers, alternating copolymers, or statistical copolymers. Statistical copolymers are also known as random copolymers.

[0787] As used herein, the term "block copolymer" means that the corresponding polymer contains at least two (i.e., two or more) homopolymer subunits (blocks) linked by covalent bonds. A diblock copolymer has two different blocks (homopolymer subunits), while a triblock copolymer therefore has three different blocks (homopolymer subunits), and so on. The number of individual blocks in such block copolymers is not limited; therefore, an "n-block copolymer" contains n different blocks (homopolymer subunits). Within each individual block (homopolymer subunit), the size / length of this block can vary. The minimum length / size of the block is based on at least two individual monomers. Various types of block copolymer backbones are commercially available, for example, under the trademark series "Pluronic" (BASF AG, Ludwigshafen, Germany). Specific examples are Pluronic PE 6100, Pluronic PE 6800, or Pluronic PE 3100. When more than one alkyl oxide is polymerized to obtain a polymer backbone (A), the alkyl oxide is preferably selected from ethylene oxide, 1,2-propylene oxide, and / or 1,2-butoxyethylene. In a preferred embodiment, ethylene oxide is polymerized with at least one alkyl oxide selected from 1,2-propylene oxide and / or 1,2-butoxyethylene, preferably only 1,2-propylene oxide.

[0788] To obtain the polymer, at least one polyol or at least one polyamine 30 may optionally be polymerized with at least one epoxide.

[0789] When at least one polyol is polymerized to obtain a polymer, the polyol is a C2- to C14-polyol, preferably a C2- to C12-polyol, and more preferably a C2- to C8-polyol. The polyol can act as a “core” molecule from which the polymer chain extends. This means that the polyol is preferably present at the start of the polymerization reaction used to obtain the polymer. A polyol is an organic compound containing multiple hydroxyl groups. Polyols are preferably aliphatic or alicyclic polyols, particularly aliphatic polyols. Polyols are preferably selected from diols containing two hydroxyl groups and polyols containing three to ten hydroxyl groups. Suitable aliphatic diols include such aliphatic diols (i.e., glycols) such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, triethylene glycol, and neopentyl glycol. A suitable alicyclic diol is cyclohexanediol. Suitable polyols containing three to ten hydroxyl groups include aliphatic and alicyclic polyols such as glycerol, trimethylolpropane, pentaerythritol, sorbitol, glucose, fructose, sucrose, and lactose, particularly glycerol. In one embodiment, the polymer backbone is obtained by polymerization of ethylene oxide and at least one alkyl oxide selected from 1,2-epoxypropane and / or 1,2-epoxybutane, preferably only 1,2-epoxypropane, and at least one polyol, particularly diethylene glycol and / or glycerol. When at least one polyamine is polymerized to obtain the polymer, the polyamine is a C2- to C14-polyamine, preferably a C2- to C12-polyamine, more preferably a C2- to C8-polyamine. The polyamine can act as a “core” molecule from which the polymer chain extends. This means that the polyamine is preferably present at the start of the polymerization reaction used to obtain the polymer backbone.

[0790] Polyamines are organic compounds containing multiple amino groups. Polyamines are preferably aliphatic or alicyclic polyamines, particularly aliphatic polyamines. Polyamines are preferably selected from alkylene polyamines, such as ethylenediamine, propylenediamine, diethylenetriamine, and dipropylenetriamine. In a preferred embodiment, the polymer backbone is obtained by polymerizing at least one epoxide selected from the group consisting of C2- to C10-epoxides in the absence of polyamines. In a more preferred embodiment, the polymer backbone is obtained by polymerizing at least one epoxide selected from the group consisting of C2- to C10-epoxides in the absence of polyols and polyamines.

[0791] Technicians are fully aware of how to obtain different types of copolymers. Appropriate discussions can be found, for example, in EP 0362 688 A2.

[0792] The polymer preferably has a number-average molecular weight Mn of 500 to 12,000 g / mol, more preferably up to 9,000 g / mol, more preferably up to 6,000 g / mol, even more preferably up to 3,800 g / mol or up to 3,500 g / mol, particularly up to 3,000 g / mol, such as up to 2,750 g / mol, up to 2,700 g / mol or up to 2,650 g / mol and at least 1,000 g / mol, more preferably at least 1,500 g / mol. A low number-average molecular weight Mn in the polymer backbone (A) increases biodegradability. The molecular weight can be determined as described below in the experimental section.

[0793] The polymer can be based on varying amounts of hydrophilic ethylene glycol units (-C2H4-O) derived from ethylene oxide, which influence the overall properties of the grafted polymer. The total EO content (%EO), describing the total amount of ethylene glycol units in the polymer backbone (A), is defined as: %EO = m(EO) / (m(total backbone)), where m(EO) is the total mass of the ethylene glycol units and m(total backbone) is the total mass of the polymer backbone (A). The polymer backbone can have low, medium, or high total EO content (%EO), which affects biodegradability and the performance of agrochemical compositions. These ranges are defined as follows: Low: 5% to 20% EO; Medium: 21% to 50% EO; High: 51% to 90% EO. In preferred embodiments, the total EO content (%EO) is in the range of 10% to 80%, preferably at least 20%, and preferably at most 70%.

[0794] In another embodiment, the amount of ethylene oxide in polymer backbone A is within 10-100% by weight (relative to the total molar amount of ethylene oxide in polymer backbone (A)).

[0795] More preferably, the monomers in the polymer backbone are derived from ethylene oxide and optionally at least one other monomer selected from 1,2-propylene oxide (PO) and 1,2-butoxyethylene, preferably only PO, wherein the amount of ethylene oxide in polymer backbone A is between 10 and 100, preferably 10-90, more preferably at least 30, even more preferably at least 50, even more preferably at least 70, and most preferably at least 80% by weight (relative to the total amount of ethylene oxide in polymer backbone (A)).

[0796] Therefore, the preferred polymer backbone (A) is selected from i) poly(ethylene oxide) and ii) polyepoxides containing only ethylene oxide (EO) and propylene oxide (PO), preferably EO / PO / EO triblock polymers, PO / EO / PO triblock polymers or random EO / PO copolymers, more preferably EO / PO / EO triblock polymers or PO / EO / PO triblock polymers, and most preferably PO / EO / PO triblock polymers, wherein PO / EO / PO is generally superior (in descending order) to random EO / PO > 100%EO > EO / PO / EO.

[0797] The polymer backbone (A) may optionally be end-capped at one or two end groups, which is accomplished in a separate process step using known techniques via C1-C25-alkyl, preferably C1 to C4-groups, after polymerization to obtain the polymer (i.e., the polymer backbone (A)).

[0798] In a preferred embodiment, the polymer backbone (A) is not capped at the chain ends but carries hydroxyl groups.

[0799] Step (e)

[0800] In step (e), the polymer from step (d) is polymerized using standard means in a free radical polymerization reaction with at least one free radical polymerizable olefinic monomer, preferably an ethylene monomer, more preferably with the following free radical polymerization: a) at least one vinyl ester and optionally at least one additional monomer, preferably at least one monomer selected from vinyl lactams and free radical polymerizable olefinic unsaturated amine monomers, more preferably vinylpyrrolidone and / or vinylimidazole, or b) at least one vinyl lactam, preferably vinylpyrrolidone and optionally at least one vinylamine, preferably vinylimidazole.

[0801] For example E1 of grafted polymers:

[0802] In Example E1, the grafted polymer includes polymer side chains (B) grafted onto the polymer backbone (A), wherein the polymer side chains (B) are obtained by polymerization of a monomer comprising at least one vinyl ester monomer (B1) and optionally at least one minor monomer (B2) in the presence of the polymer backbone (A).

[0803] Preferably, the polymer side chain (B) is obtained by free radical polymerization of a monomer comprising at least one vinyl ester monomer (B1) and optionally at least one minor monomer (B2) in the presence of the polymer backbone (A).

[0804] As the vinyl ester monomer (B1), any vinyl ester known to those skilled in the art can be used, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl valerate, neovinyl valerate, neovinyl decanate, vinyl decanoate, or vinyl benzoate. Preferably, the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate, and vinyl laurate, particularly vinyl acetate and vinyl laurate. In a particularly preferred embodiment, the polymer side chain (B) is obtained by free radical polymerization of vinyl acetate.

[0805] The minor monomer (B2) is preferably selected from olefinic unsaturated nitrogen-containing monomers such as vinyl lactam and vinyl imidazole, especially vinyl lactam; and vinyl ether.

[0806] Suitable vinyl lactams include N-vinyl lactams, such as N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam, with N-vinylpyrrolidone and N-vinylcaprolactam being preferred, and N-vinylpyrrolidone (NVP) being particularly preferred.

[0807] Suitable vinylimidazoles include 1-vinylimidazole and C1-C8 alkyl-substituted derivatives of 1-vinylimidazole (including 2-methyl-1-vinylimidazole), preferably 1-vinylimidazole.

[0808] Suitable vinyl ethers include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether, especially n-butyl vinyl ether, isobutyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether.

[0809] When a minor monomer (B2) is used to obtain the polymer side chain (B), there is no particular limitation on the weight ratio of the vinyl ester monomer (B1) to the minor monomer (B2). However, the amount of vinyl ester monomer (B1) is generally not less than 1 wt.% relative to the total amount of monomers constituting the polymer side chain (B). In this case, the polymer side chain (B) can be obtained by polymerization, particularly free radical polymerization, of 1 to 100 wt.% of monomer (B1) (most preferably vinyl acetate) and 0 to 99 wt.% of at least one minor monomer (B2).

[0810] In one embodiment, the polymer side chain (B) is obtained by polymerization, particularly (free) radical polymerization, in the presence of the polymer backbone (A):

[0811] - Relative to the total amount of monomers constituting the polymer side chain (B), 10 to 100 wt.-%, preferably 25 to 100 wt.-%, more preferably 50 to 100 wt.-%, most preferably 75 to 100 wt.-%, of at least one vinyl ester monomer (B1), and optionally

[0812] - Relative to the total amount of monomers constituting the polymer side chain (B), at least one minor monomer (B2) is present in amounts of 0 to 90 wt.-%, preferably 0 to 75 wt.-%, more preferably 0 to 50 wt.-%, and most preferably 0 to 25 wt.-%.

[0813] In a preferred embodiment, the polymer side chain (B) is obtained by polymerization, particularly (free) radical polymerization, in the presence of the polymer backbone (A):

[0814] - Relative to the total amount of monomers constituting the polymer side chain (B), 65 to 100 wt.-%, preferably 70 to 100 wt.-%, more preferably 75 to 100 wt.-%, most preferably 80 to 100 wt.-%, of at least one vinyl ester monomer (B1), and optionally

[0815] - At least one minor monomer (B2) in 0 to 35 wt.-%, preferably 0 to 30 wt.-%, more preferably 0 to 25 wt.-%, and most preferably 0 to 20 wt.-%, relative to the total amount of monomers constituting the polymer side chain (B).

[0816] In a preferred embodiment, the polymer side chain (B) is obtained by polymerization of at least one vinyl ester monomer (B1), particularly vinyl acetate, in the presence of the polymer backbone (A) and in the absence of other monomers.

[0817] Alternative embodiment E2 for grafted polymers:

[0818] In alternative embodiment E2, instead of using vinyl ester monomers, at least one vinyl lactam and at least one free radical polymerizable olefinic unsaturated amine monomer are used for free radical polymerization in the presence of the polymer backbone.

[0819] The olefinic unsaturated amine monomer is preferably 1-vinylimidazole or its derivatives such as alkyl-substituted derivatives of 1-vinylimidazole such as 2-methyl-1-vinylimidazole, and more preferably only 1-vinylimidazole.

[0820] The vinyl lactam monomer is preferably selected from N-vinyl lactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone.

[0821] Other monomers may be used as optional monomers, such as any one or more of the following: 1-vinyloxazolidinone and other vinyloxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide (and its amines, if hydrolyzed after polymerization), N-vinylacetamide, N-vinyl-N-methylacetamide, acrylamide, methacrylamide, N,N'-dialkyl(methyl)acrylamide, but such other monomers do not cover vinyl ester monomers; preferably, no other monomers are used; such other monomers may be present at most as undesirable impurities in very low amounts.

[0822] The grafted polymer of the present invention, as detailed in Example E2 above, contains, in its preferred, more preferred, and most preferred composition, the following amounts (each in weight % based on the total weight of the grafted polymer) of first and second structural units:

[0823] - The amount of polymer backbone (A) is 70 to 95, preferably 73 to 90, more preferably 73 to 87, even more preferably 75 to 85, and most preferably 77 to 85.

[0824] - The amount of polymer side chain (B) is 5 to 30, preferably 10 to 27, more preferably 13 to 27, even more preferably 15 to 25, and most preferably 15 to 23, and

[0825] - The amount of vinyl lactam (B1) is at least 4 and up to 29, and

[0826] The amount of the amine monomer is at least 1 and at most 15.

[0827] -The amount of amine monomer (B2) relative to vinyl lactam is in all cases no more than 4 times, preferably no more than 3 times, more preferably no more than 2 times, and even more preferably the same amount, and preferably at least 5% based on the amount of vinyl lactam / the amount of vinyl lactam, more preferably at least 10%, even more preferably at least 25%, even more preferably at least 50%, even more preferably at least 75%, and

[0828] - The amount of the additional monomer is 0 to 5, preferably up to 2, more preferably 0, but in all cases up to 50% of the amount of vinyl lactam, and not exceeding the amount of amine monomer.

[0829] Therefore, in a more preferred embodiment, the following amounts are selected – each expressed as a percentage by weight based on the total weight of the grafted polymer:

[0830] - The amount of polymer backbone (A) is 75 to 85, and most preferably 77 to 85, and

[0831] The amount of polymer side chain (B) is 15 to 25, most preferably 15 to 23, and

[0832] The amount of -(B1) is at least 6 and up to 24, more preferably up to 20, even more preferably up to 15, even more preferably up to 12, and most preferably at least 7.5 and up to 10.

[0833] The amount of -(B2) is at least 1 and up to 15, more preferably up to 13, even more preferably up to 12, even more preferably up to 11, and most preferably at least 7.5 and up to 10.

[0834] -More preferably, (B2) is the same amount as (B1), but does not exceed the total upper or lower limit of (B).

[0835] In another embodiment, the following amounts are selected – each expressed as a percentage by weight based on the total weight of the grafted polymer:

[0836] - The amount of polymer backbone (A) is 75 to 85, and most preferably 77 to 85, and

[0837] The amount of polymer side chain (B) is 15 to 25, most preferably 15 to 23, and

[0838] The amount of -(B1) is at least 6 and up to 24, more preferably up to 20, even more preferably up to 15, even more preferably up to 12, and most preferably at least 7.5 and up to 10.

[0839] The amount of -(B2) is at least 1 and up to 15, more preferably up to 13, even more preferably up to 12, even more preferably up to 11, and most preferably at least 7.5 and up to 10.

[0840] - Preferably, the amount of (B2) relative to (B1) is at most 75% of the amount of (B1) / the amount of (B1) in all cases, even more preferably at most 50%, and most preferably at most 25%.

[0841] In a preferred embodiment, the grafted polymer, as disclosed herein and specifically as detailed previously in the embodiments, wherein...

[0842] (A) The polymer backbone (A) is a triblock polymer EO / PO / EO, wherein the molecular weight of Mn in the polymer backbone (A) is between 400 and 3000 in g / mol, and wherein the relative amount of EO in the polymer backbone (A) is between 10-90, preferably 10-60, and more preferably 15-50% by weight, relative to the total molar amount of epoxide in the polymer backbone (A).

[0843] and

[0844] (B) The polymer side chain is composed of the following monomers:

[0845] B1 is 1-vinylimidazole, and

[0846] B2 is an N-vinyl lactam, preferably an N-vinylpyrrolidone.

[0847] It should be understood that—in both Examples E1 and E2—the amounts of polymer backbone and various monomer types, as well as the amounts of other monomers, can be selected from various independently given detailed ranges, i.e., the lower and upper boundaries can also be combined from two different given ranges to produce numerical ranges not explicitly specified numerically herein, and such combinations of ranges for, for example, backbone and various monomer types, or combinations of ranges for other monomers, are explicitly intended to be covered in this invention.

[0848] Furthermore, in one embodiment of the invention, a wide range and a very particularly preferred narrow range can be combined, wherein the selection of the range of one component is independent of the selection of the range of another component, as long as the total sum is “100% - polymer”: for example, the most preferred range of polymer backbone (A) and monomer (B) can be selected and combined with the widest possible range given for a single monomer type, as well as any other possible combination.

[0849] Alternative embodiment E3 for grafted polymers:

[0850] In this alternative embodiment, the grafted polymer disclosed in WO 2023017061 A1 is prepared using the monomers, backbone, reaction conditions, etc., as detailed in that disclosure, but the preparation uses the elements of the present invention, i.e., steps a) to d) of the present invention, but additionally follows the selection of monomers, monomer ratios, backbone-to-monomer ratios, reaction conditions, free radical initiators, and solvents as detailed in WO 2023017061 A1.

[0851] Therefore, the present invention enables the production of polymers and preferred forms thereof as detailed in WO 2023017061 A1, but these polymers and preferred forms thereof have reduced amounts of fossil-based hydrogen content and thus have an overall reduced carbon footprint.

[0852] In a general embodiment of the invention applicable to E1, E2, and E3, the polymer side chain (B) of the grafted polymer according to the invention is completely or at least partially hydrolyzed after the grafted polymer itself is obtained. This means that the complete or at least partial hydrolysis of the polymer side chain (B) of the grafted polymer occurs after the polymerization process of the polymer side chain (B) is completed.

[0853] Hydrolysis can be carried out by any method known to those skilled in the art. For example, hydrolysis can be induced by adding a suitable base, such as sodium hydroxide or potassium hydroxide.

[0854] In this embodiment, it is preferred that the hydrolysis of the polymer side chain (B) is only carried out in a partial manner, for example, to the extent that up to 20 wt.-%, 40 wt.-% or 60 wt.-% of the units derived from the vinyl ester monomer (B1) are hydrolyzed relative to the total weight of the vinyl ester monomer (B1).

[0855] In a more preferred embodiment, the polymer side chain (B) does not hydrolyze after polymerization.

[0856] As mentioned above, it is important to be able to reliably track the source of hydrogen and downstream compounds obtained through clean energy.

[0857] Today, most hydrogen is produced from fossil fuels through steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

[0858] However, to date, it has been impossible to distinguish between hydrogen obtained through steam reforming, partial oxidation, and coal gasification (i.e., from fossil resources) and hydrogen obtained through electrolysis. As discussed above, hydrogen obtained through electrolysis is preferably obtained using non-fossil energy sources. It is anticipated that the electrification (power generation) of fossil resources will be completely replaced by power generation from non-fossil resources in the near future.

[0859] Therefore, the inventors have discovered a method for tracing the source of hydrogen and its downstream products, preferably the grafted polymers of the present invention, via the deuterium molar fraction of the compound. These downstream products (i.e., the grafted polymers as detailed herein) based on hydrogen (obtained by electrolysis) and hydrogen itself can be distinguished by their deuterium molar fraction from compounds that are essentially chemically identical and prepared by fossil fuel-based methods (i.e., manufactured by petrochemical methods).

[0860] Furthermore, by using carbon oxides (such as carbon monoxide, and preferably carbon dioxide) along with hydrogen instead of petrochemical synthesis gas in subsequent synthetic routes of the grafted polymers, it was found that the molar fraction of deuterium in these compounds is uniquely low, resulting in excellent traceability.

[0861] Therefore, the present invention relates to the use of the molar fraction of deuterium in hydrogen and hydrogen-based downstream compounds for tracing the source, particularly the energy source, of hydrogen and hydrogen-based downstream compounds, wherein these compounds are preferably graft polymers as detailed herein.

[0862] The present invention further relates to a method for tracking the source, particularly the energy source, of hydrogen and said hydrogen-based downstream compounds by determining the molar fraction of deuterium in hydrogen and said hydrogen-based downstream compounds, wherein these compounds are graft polymers as detailed herein.

[0863] In the context of this invention, tracking and tracing are synonymous.

[0864] In the context of this invention, the source refers to the method of hydrogen production employed, particularly electrolysis and / or the energy source, i.e., non-fossil energy. As mentioned above, it is anticipated that the electrification (power generation) of fossil fuel sources will be completely replaced by power generation from non-fossil resources in the near future. Hydrogen produced by electrolysis in this case is non-fossil hydrogen. Examples of non-fossil power sources have been mentioned above.

[0865] The method of the present invention for tracing the source, especially the energy source, of hydrogen and the aforementioned downstream compounds can be used as a single tracing method or in combination with other tracing methods.

[0866] The compounds of this invention available through this invention cover any and all such grafted polymers following the outline given herein, especially those as detailed in more particular terms.

[0867] To date, such grafted polymers are partially known from the prior art, and some of them are commercially available.

[0868] The graft polymer of vinyl acetate grafted onto polyethylene glycol (polyethylene glycol with a molecular weight of about 6000 g / mol) is commercially available from companies such as BASF.

[0869] Another such grafted polymer is Kollicoat IR, which is a polymer obtained by grafting polyethylene glycol (polyethylene glycol with a molecular weight of about 6000 g / mol) with vinyl acetate, wherein the vinyl acetate is hydrolyzed after free radical polymerization to obtain "vinyl alcohol grafted" PEG.

[0870] Another polymer is a graft polymer of vinyl caprolactam and vinyl acetate on polyethylene glycol, which is also available from BASF AG.

[0871] Other grafted polymers are known from, for example, the following publications: WO 2021 / 160795, US 5,318,719A, CN 102 030 871, WO 03 / 042262, US 2019 / 0390142, WO 2007 / 138053, Y. Zhang et al. J.Coll. Inter. Sci [Journal of Colloid and Interface Science] 2005, 285, 80, WO 2020 / 005476, WO 2020 / 264077, WO 0018375, WO 2023017061 A1, US 2008 / 255326 - only a few of the many disclosures are mentioned.

[0872] When using the present invention to produce by replacing at least one element of the prior art method / starting material with an element of the present invention (e.g., replacing standard fossil-based EO with EO that can be produced as by the method of the present invention or preferably produced by the method of the present invention), the present invention covers all grafted polymers previously mentioned and referenced.

[0873] The uses of such grafted polymers of the present invention as disclosed and defined herein and with reference to the prior art are the same as those known in the art; such uses of such grafted polymers of the present invention and products / formulations / compositions containing such grafted polymers of the present invention are in particular those disclosed in any of the following disclosures – provided that the monomers used for grafting are suitable for the application (as defined in such disclosures): for example, US2019 / 390142, WO 2020 / 264077, WO 2020 / 005476, WO 2023017061 A1, WO 03 / 042262, and are also commonly found in pharmaceutical applications, in oilfield applications (e.g., natural gas hydrate inhibitors), in detergents for primary washing, anti-ashing, dye transfer inhibition, in agricultural chemical formulations, printing, electronic devices, etc.

[0874] In all those disclosures of the prior art and known uses and applications, the grafted polymer can be partially or completely replaced by the grafted polymer of the present invention that has the same or closely similar chemical structure but is produced using at least one element of the present invention (e.g., replacing standard fossil-based EO with EO that can be produced as by the method of the present invention or preferably produced by the method of the present invention).

[0875] Uses and cleaning compositions

[0876] The grafted polymers of the present invention, as specifically described above and in detail by reference to the various prior art documents cited herein, may also be referred to hereinafter as "compounds of the present invention" and "compounds of the present invention".

[0877] The terms "at least one compound of the invention" and "compound of the invention" cover one, two, three, four or more compounds of the invention as a mixture.

[0878] The compounds of the present invention, obtained directly from the methods of the present invention, can be advantageously used in cleaning compositions.

[0879] They can be used as at least one compound of the present invention, or a mixture of more than one compound of the present invention.

[0880] Therefore, another subject of the present invention is the use of the compounds of the present invention mentioned above in cleaning compositions, specifically cleaning compositions prepared by the methods defined herein.

[0881] The compounds of the present invention can be added to cleaning compositions. The compounds of the present invention are typically present in the formulation at a concentration of about 0.1% to about 50%, preferably about 0.25% to 15%, more preferably about 0.5% to about 10%, and even more preferably about 0.5% to about 5%, and most preferably at an amount of up to 3%, each in weight percent relative to the total weight of such composition / product. Such composition / product optionally further comprises about 1% to about 70% by weight of a surfactant system, wherein – specifically – for liquid manual dishwashing or spray detergent cleaning compositions, such compositions comprise 0.1% to 50%, preferably 1% to 35%, more preferably 3% to 30% by weight of the total composition of a surfactant system, and such surfactant system preferably comprises 60% to 90%, more preferably 70% to 80% by weight of the surfactant system of anionic surfactants.

[0882] Therefore, another subject of the present invention is the use of the compounds of the present invention obtained by the method of the present invention as detailed above in the fabric and household care products, particularly in cleaning compositions, for improved removal of oily and greasy stains, removal of solid dirt such as clay, prevention of ashing of fabric surfaces, and / or as anti-scaling agents, wherein the cleaning compositions are preferably laundry detergent formulations and / or dishwashing detergent formulations, more preferably liquid laundry detergent formulations and / or liquid hand dishwashing detergent formulations.

[0883] Therefore, another subject of the present invention is a cleaning composition, fabric and household care product, industrial and institutional cleaning product, preferably in a laundry detergent, in a cleaning composition and / or in a fabric and household care product, each comprising at least one compound of the present invention obtained by the method of the present invention.

[0884] Another subject of the invention is a fabric and household care product, a cleaning composition, an industrial and institutional cleaning product, preferably a laundry detergent, a cleaning composition and / or a fabric and household care product, each containing at least one compound of the invention obtained by the method of the invention.

[0885] In a preferred embodiment, the subject matter is a cleaning composition and / or fabric and household care product and / or industrial and institutional cleaning product comprising at least one compound of the present invention obtained by the method of the present invention. In particular, the subject matter is a cleaning composition for improved cleaning performance, especially improved primary washing, preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0886] In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.

[0887] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g., powder or label / single-dose) detergent composition for manual or automatic dishwashing, preferably a liquid manual dishwashing composition. Such compositions are known to those skilled in the art.

[0888] In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that can be used to clean various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, and glass. A preferred example is a detergent formulation for washing tableware and knives, i.e., a "manual dishwashing detergent." Another example is a spray cleaner, which is typically sprayed onto a hard surface and then wiped away to remove dirt and grease, etc.

[0889] In one embodiment of the invention, the compound obtained by the method of the invention is a component that additionally contains at least one surfactant, preferably at least one anionic surfactant, of the following: a cleaning composition or a fabric and household care product, preferably a laundry cleaning composition, a laundry care product or a laundry treatment product or a laundry washing product, preferably a liquid laundry detergent formulation or a liquid laundry detergent product.

[0890] In one embodiment, it is also preferred in the present invention that the cleaning composition additionally comprises (in addition to at least one compound of the present invention obtained by the method of the present invention) at least one enzyme, preferably selected from one or more of the following: lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase, pectic acid lyase, keratinase, deoxyribonuclease, xylanase, oxidoreductase, dispersin, mannanase, and peroxidase, as well as combinations of at least two of the foregoing types, preferably at least one enzyme selected from lipase.

[0891] Even more preferably, the cleaning compositions of the present invention, which contain at least one compound obtained by the method of the present invention and optionally further contain at least one surfactant or surfactant system - as previously detailed - are for improved cleaning performance in applications to clothing and handwashing tableware, or even more specifically for improved cleaning performance (such as those previously detailed) (such as those on fabrics and tableware), and may additionally contain at least one enzyme selected from the list of the following: optionally further containing at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectic acid lyases, keratinases, deoxyribonucleases, xylanases, oxidoreductases, dispersases, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme selected from lipases.

[0892] In one embodiment, the compound of the present invention obtained by the method of the present invention can be used in a cleaning composition comprising a surfactant system comprising a C10-C15 alkylbenzene sulfonate (LAS) as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0893] In another embodiment, the compounds of the present invention obtained by the method of the present invention can be used in cleaning compositions or fabric and household care products, preferably laundry cleaning compositions, laundry care products or laundry washing products, preferably liquid laundry detergent formulations or liquid laundry detergent products, which contain a C12-C18 alkyl ethoxylated surfactant having 5-10 ethoxy units as the main surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

[0894] In another embodiment, the compounds of the present invention obtained by the method of the present invention can be used in cleaning compositions or fabric and household care products, preferably laundry cleaning compositions, laundry care products or laundry treatment products or laundry washing products, preferably liquid laundry detergent formulations or liquid laundry detergent products, which contain a C8-C18 straight-chain or branched alkyl ether sulfate having 1-5 ethoxy units as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0895] In one embodiment of the invention, the compound obtained by the method of the invention is a component that additionally contains at least one surfactant, preferably at least one anionic surfactant, of the following: a cleaning composition such as preferably a laundry or dishwashing preparation, more preferably a liquid laundry or manual dishwashing preparation.

[0896] In another embodiment, the present invention also covers a composition comprising at least one compound of the present invention obtained by the method of the present invention, further comprising an antimicrobial agent disclosed below (preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; and even more preferably comprising 0.1% to 2% phenoxyethanol.

[0897] In other embodiments, the present invention also covers a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand tableware composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising, as described above, the amount of the compound of the present invention obtained by the method of the present invention as detailed above, and such composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6% by weight of each composition.

[0898] In another embodiment, the invention also covers a composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably a concentrated liquid detergent formulation, a single-use, single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation or a solid automatic dishwashing formulation, more preferably a laundry detergent formulation, the composition comprising the compound of the invention obtained by the method of the invention and in the amount detailed above, such composition preferably being a detergent composition, such composition further comprising an antimicrobial agent as disclosed below (the antimicrobial agent is preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprising 0.1% to 2% phenoxyethanol.

[0899] In another embodiment, the present invention also covers a method for preserving an aqueous composition against microbial contamination or growth, wherein the composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, is preferably a concentrated liquid detergent formulation, a single-use, single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation or a solid automatic dishwashing formulation, more preferably a laundry detergent formulation, the composition comprising the amount of the compound of the present invention obtained by the method of the present invention and as previously detailed, the composition being preferably a detergent composition, the method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents disclosed below, the antimicrobial agent being preferably 2-phenoxyethanol.

[0900] In another embodiment, the present invention also covers a method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand tableware composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use in laundry, such composition comprising the compound of the present invention obtained by the method of the present invention in the amounts detailed above, such composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether.

[0901] As used herein, the phrase "cleaning composition" as used with respect to the compositions and products of this invention includes compositions and formulations designed for cleaning soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric reinforcing compositions, fabric freshening compositions, pre-washing garments, pre-treatment garments, garment additives, spray products, dry cleaning agents or compositions, laundry rinsing additives, washing additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit-dose formulations, delayed-delivery formulations, detergents contained on or contained in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as pre-wash treatments, post-wash treatments, or can be added during rinsing or washing cycles of a washing operation. Cleaning compositions may be in the form of liquids, powders, single-phase or multi-phase unit doses, sachets, tablets, gels, pastes, strips, or sheets.

[0902] The cleaning compositions of the present invention comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition comprises about 2% to about 60% of the surfactant system by weight of the composition. In still other embodiments, the cleaning composition comprises about 5% to about 30% of the surfactant system by weight of the composition. In embodiments of liquid manual dishwashing or spray detergent cleaning compositions, such compositions preferably comprise 60% to 90%, more preferably 70% to 80% by weight of the surfactant system, more preferably anionic surfactants. The surfactant system may comprise detergency surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those skilled in the art will understand that detergency surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0903] Even more preferably, the compositions or products of the present invention as detailed above – which contain at least one alkoxylated amino acid ester and / or salt thereof obtained by the method of the present invention and in the amount specified in the preceding paragraphs, optionally further containing at least one surfactant or surfactant system in an amount of about 1% to about 70% by weight of the composition or product – preferably those for primary cleaning (i.e. stain removal) and more preferably in laundry applications, and may additionally contain at least one enzyme selected from the group consisting of: lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, deoxyribonuclease, dispersase, pectinase, oxidoreductase, keratinase, lactase and peroxidase, more preferably at least two of the foregoing types.

[0904] As used herein, the phrase "cleaning composition" includes compositions, formulations, and products designed for cleaning soiled materials. Such compositions, formulations, and products include those designed for cleaning any kind of soiled material or soiled surface.

[0905] Compositions for “industrial and institutional cleaning” include such cleaning compositions designed for use in industrial and institutional cleaning, such as those for cleaning any kind of soiled materials or surfaces, such as hard surface cleaners for any kind of surfaces (including tile, carpet, PVC-coated surfaces, wood surfaces, metal surfaces, and painted surfaces).

[0906] "Compositions for fabric and household care" include cleaning compositions, including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric freshening compositions, laundry pre-wash, laundry pretreatment, laundry additives, spray products, dry cleaning agents or compositions, laundry rinsing additives, washing additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, single-dose formulations, delayed-delivery formulations, detergents contained on or contained in porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as pre-wash treatments, post-wash treatments, or can be added during the rinsing or washing cycle of a washing operation, preferably during the washing cycle of a laundry or dishwashing operation.

[0907] The cleaning compositions of the present invention can be in any form, i.e., in the following forms: liquid; solid, such as powder, granules, agglomerates, pastes, tablets, sachets, sticks, gels; emulsion; delivered in a two- or multi-compartment container; single-phase or multi-phase unit dosage; spray or foam detergent; pre-wet wipes (i.e., cleaning compositions combined with nonwoven materials, such as those discussed in US 6,121,165, Mackey, etc.); dry wipes (i.e., cleaning compositions combined with nonwoven materials, such as those discussed in US 5,980,931, Fowler, etc.), which are activated by water by the user or consumer; and other homogeneous, non-homogeneous, or single-phase or multi-phase cleaning product forms.

[0908] The liquid cleaning composition of the present invention preferably has a strength of 50 to 10000 mPa. The viscosity is s; at 20 1 / s and 20°C, the liquid manual dishwashing cleaning composition (also known as the liquid manual "dishwashing composition") preferably has a viscosity of 100 to 10000 mPa. s, more preferably 200 to 5000 mPa s and the optimal value is 500 to 3000 mPa The viscosity is s; at 20 1 / s and 20°C, the liquid laundry cleaning composition preferably has a viscosity of 50 to 3000 mPa. s, more preferably 100 to 1500 mPa s and the optimal value is 200 to 1000 mPa The viscosity of s.

[0909] The cleaning compositions and formulations of the present invention may—and preferably do—contain auxiliary cleaning additives (also referred to herein as “auxiliaries”), which are preferably in addition to surfactant systems as previously defined.

[0910] Suitable cleaning additives include detergent builders, co-builders, structuring agents or thickeners, clay stain removers / anti-redeposition agents, polymer stain removers, dispersants such as polymer dispersants, polymer grease removers, solubilizers, chelating agents, enzymes, enzyme stabilizers, bleaching compounds, bleaching agents, bleaching activators, bleaching catalysts, brighteners, odor control agents, pigments, dyes, opacifiers, colorants, dye transfer inhibitors, chelating agents, foaming agents, foam inhibitors (defoamers), color speckle removers, silver care products, anti-tarnish agents and / or preservatives, alkalinity sources, pH adjusters, pH buffers, water-soluble additives, detergent granules, antimicrobial agents, antioxidants, softeners, carriers, processing aids, fragrance precursors, and fragrances.

[0911] The liquid cleaning composition may additionally contain – and preferably does contain – at least one of a rheology control agent / modifier, emollient, humectant, skin rejuvenating active, and solvent.

[0912] The solid composition may additionally include, and preferably does include, at least one of filler, bleach, bleach activator and catalytic material.

[0913] Suitable examples and levels of use of such cleaning aids are found in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

[0914] Those skilled in the art will understand that detergency surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0915] Therefore, the cleaning compositions of the present invention, such as fabric and household care products and formulations for industrial and institutional cleaning, more specifically such as laundry detergents and hand dishwashing detergents, preferably additionally contain surfactant systems, and more preferably additional adjuvants, such as those described above.

[0916] A surfactant system may consist of a single surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will understand that surfactant systems for detergents encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0917] The cleaning compositions of the present invention typically comprise a surfactant system in an amount sufficient to provide the desired cleaning properties.

[0918] The liquid cleaning composition of the present invention can have any suitable pH value. Preferably, the pH of the composition is adjusted to be between 4 and 14. More preferably, the composition has a pH of 6 to 13, even more preferably 6 to 10, and most preferably 7 to 9. The pH of the composition can be adjusted using pH-changing ingredients known in the art and measured at 25°C in demineralized water at a 10% product concentration. For example, NaOH can be used, and the actual weight percentage of NaOH can be varied and adjusted to a desired pH, such as pH 8.0. In one embodiment of the invention, the pH is adjusted to > 7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0919] In these embodiments, the selection of additional surfactants and other ingredients may depend on the application and desired benefits.

[0920] All such cleaning compositions, their components (including (auxiliary) cleaning additives), their general compositions and more specific compositions are known, for example, in disclosures 800542 and 800500 disclosed by Liechtenstein Protegas and also shown in WO 2022 / 136409 and WO 2022 / 136408, wherein in any of the preceding prior art documents, the general compositions disclosed in the foregoing disclosures, as well as the inventive compounds in each individual specific cleaning composition (i.e., any grafted polymers as specifically described herein or detailed by reference to prior art disclosures), can be partially or completely replaced by the corresponding inventive compounds prepared using the present invention. Various types of formulations for cleaning compositions are also disclosed in those foregoing documents; all such composition types—general compositions and each individual specific cleaning composition—are equally applicable to those cleaning compositions contemplated herein.

[0921] Therefore, this invention also covers any and all such disclosed compositions in the foregoing prior art disclosures, but these compositions further comprise at least one inventive compound as a supplement to or as a substitute for any compound already contained in such prior art compositions that has similar or—preferably—the same chemical properties and structure, or any such compound (which may be replaced by such inventive compound—such substitution being known in principle to those skilled in the art or readily apparent in light of the invention). Typically, the content of the inventive compound present in the formulations is the same as the concentration used in the referenced prior art literature and in the products and formulations therein; such concentrations are typically 0.05 to 20 wt.%, preferably up to 10 wt.%, more preferably 0.1 to 5 wt%, and even more preferably at a concentration of 0.5 to 2 wt%.

[0922] General description of cleaning compositions, formulations and their ingredients

[0923] Cleaning compositions such as fabric and household care products, as well as formulations for industrial and institutional cleaning, more specifically such as laundry detergents and hand dishwashing detergents, are known to those skilled in the art. Any composition known to those skilled in the art (in conjunction with the corresponding use) can be employed within the context of this invention by containing at least one of the inventive compounds, preferably in an amount suitable for exhibiting certain properties in such a composition (especially when such a composition is used in its field of application).

[0924] Cleaning additives

[0925] The cleaning compositions and formulations of the present invention may—and preferably do—contain auxiliary cleaning additives (also referred to herein as “auxiliaries”), which are preferably in addition to surfactant systems as previously defined.

[0926] Suitable cleaning aids and additives include detergent builders, co-builders, structuring agents or thickeners, clay stain removers / anti-redeposition agents, polymer stain removers, dispersants such as polymer dispersants, polymer grease removers, solubilizers, chelating agents, enzymes, enzyme stabilizers, bleaching compounds, bleaching agents, bleaching activators, bleaching catalysts, brighteners, odor control agents, pigments, dyes, opacifiers, colorants, dye transfer inhibitors, chelating agents, foaming agents, foam inhibitors (defoamers), stain removers, silver care products, anti-tarnish agents and / or preservatives, alkalinity sources, pH adjusters, pH buffers, water-soluble aids, detergent granules, antimicrobial agents, antioxidants, softeners, carriers, processing aids, fragrance precursors, and fragrances. All such aids are further detailed and illustrated in the following sections.

[0927] The liquid cleaning composition may additionally contain – and preferably does contain – at least one of a rheology control agent / modifier, emollient, humectant, skin-renewing active substance and solvent.

[0928] The solid composition may additionally include, and preferably does include, at least one of filler, bleach, bleach activator and catalytic material.

[0929] Suitable examples and levels of use of such cleaning aids are found in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

[0930] Those skilled in the art will understand that detergency surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0931] Therefore, the cleaning compositions of the present invention, such as fabric and household care products and formulations for industrial and institutional cleaning, more specifically such as laundry detergents and hand dishwashing detergents, preferably additionally contain a surfactant system, and more preferably additional adjuvants, such as those described above and below in more detail.

[0932] A surfactant system may consist of a single surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will understand that surfactant systems for detergents encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0933] The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. The surfactant system may comprise detergency surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof.

[0934] Laundry Composition

[0935] "Laundry composition" can be any composition, preparation or product intended for use in laundry (including garment care, garment cleaning, etc.); therefore, the term will be used in the following to refer to any composition, preparation or product.

[0936] In laundry compositions, anionic surfactants typically contribute the largest share of surfactants in such formulations. Therefore, preferably, the cleaning compositions of the present invention for use in laundry contain at least one anionic surfactant and optionally additional surfactants selected from any of the surfactant classes described herein, preferably from nonionic surfactants and / or amphoteric surfactants and / or amphoteric surfactants and / or cationic surfactants.

[0937] The cleaning composition may also contain, and preferably does contain, an anionic surfactant, which may also be used in combination with more than one other surfactant.

[0938] Non-limiting examples of anionic surfactants that can be used herein—which can be used in combinations of more than one surfactant—include C9-C20 linear alkylbenzene sulfonates (LAS), C10-C20 main-chain, branched, and random alkyl sulfates (AS); C10-C18 secondary (2,3)alkyl sulfates; C10-C18 alkylalkoxy sulfates (AExS), wherein x is 1 to 30; C10-C18 alkylalkoxycarboxylates containing 1 to 5 ethoxy units; medium-chain branched alkyl sulfates, as discussed in US 6,020,303 and US 6,060,443; medium-chain branched alkylalkoxy sulfates, as discussed in US 6,008,181 and US 6,020,303; and modified alkylbenzene sulfonates (MLAS), such as WO 99 / 05243, WO 99 / 05242, and WO The methyl ester sulfonate (MES) and α-olefin sulfonate (AOS) discussed in 99 / 05244.

[0939] Preferred examples of suitable anionic surfactants are the following alkali metal and ammonium salts: C8-C12-alkyl sulfates, C12-C18-fatty alcohol ether sulfates, C12-C18-fatty alcohol polyether sulfates, ethoxylated C4-C12-alkylphenol (ethoxylation: 3 to 50 mol / mol ethylene oxide), C12-C18-alkyl sulfonic acids, C12-C18 sulfoalkyl fatty acid esters such as C12-C18 sulfomethyl fatty acid esters, C10-C18-alkylaryl sulfonic acids, preferably n-C10-C18-alkylbenzene sulfonic acids, C10-C18 alkylalkoxycarboxylic acid esters, and soaps such as C8-C24-carboxylic acids. Alkali metal salts of the above compounds are preferred, and sodium salts are particularly preferred.

[0940] In one embodiment of the invention, the anionic surfactant is selected from n-C10-C18-alkylbenzene sulfonic acid and fatty alcohol polyether sulfate, particularly, within the context of the invention, ethoxylated C12-C18-alkanol (preferably n-C12-C18-alkanol) sulfate half-esters (ethoxylation: 1 to 50 mol ethylene oxide / mol).

[0941] In one embodiment of the invention, alcohol polyether sulfates derived from branched (i.e., synthetic) C11-C18-alkanols may also be used (ethoxylation: 1 to 50 mol of ethylene oxide / mol).

[0942] Preferably, the alkoxylation group of either type of alkoxylated alkyl sulfate based on C12-C18-fatty alcohol or based on branched (i.e., synthetic) C11-C18-alcohol is an ethoxylation group, and the average degree of ethoxylation of any alkoxylated alkyl sulfate is 1 to 5, preferably 1 to 3.

[0943] Preferably, the laundry detergent formulation of the present invention comprises at least 1 wt.% to 50 wt.%, preferably in the range of greater than or equal to about 2 wt.% to equal to or less than about 30 wt.%, more preferably in the range of greater than or equal to 3 wt.% to equal to or less than 25 wt.%, and most preferably in the range of greater than or equal to 5 wt.% to equal to or less than 25 wt.%, based on a specific total composition (containing other components and water and / or solvents), one or more of the anionic surfactants as described above.

[0944] In a preferred embodiment of the present invention, the anionic surfactant is selected from C10-C15 linear alkylbenzene sulfonates, C10-C18 alkyl ether sulfates having 1-5 ethoxy units, and C10-C18 alkyl sulfates.

[0945] The cleaning composition may also contain a nonionic surfactant, which may also be used in combination with more than one other surfactant.

[0946] Non-limiting examples of nonionic surfactants—which can also be used in combinations of more than one other surfactant—include: C8-C18 alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell; ethylene oxide / propylene oxide block alkoxylates as PLURONIC® from BASF; C14-C22 medium-chain branched alkyl alkoxylates, BAEx, where x is 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkyl polysaccharides, as discussed in US 4,565,647, published January 26, 1986 in Llenado; specifically, alkyl polyglycosides, as discussed in US 4,483,780 and US 4,483,779; and polyhydroxy fatty acid amides, such as US The same as those discussed in 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants, such as those discussed in US 6,482,994 and WO 01 / 42408.

[0947] Preferred examples of nonionic surfactants include, in particular, alkoxylated alcohols and alkoxylated fatty alcohols, diblock and multiblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitol with ethylene oxide or propylene oxide, as well as alkylphenol ethoxylates, alkyl glycosides, and polyhydroxy fatty acid amides (glucosamides). An additional example of amphoteric surfactants is so-called amine oxides.

[0948] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (A).

[0949] [Formula (A)]

[0950] The variables are defined as follows:

[0951] R1 is selected from straight-chain C1-C10-alkyl, preferably ethyl, and particularly preferably methyl.

[0952] R2 is selected from C8-C22-alkyl groups, such as n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, or n-C18H37.

[0953] R3 is selected from C1-C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, or isodel.

[0954] m and n are in the range of 0 to 300, wherein the sum of n and m is at least 1. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0955] Here, the compound having the general formula (A) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0956] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (B).

[0957] [Formula (B)]

[0958] The variables are defined as follows:

[0959] R1 may be the same or different and is selected from straight-chain C1-C4-alkyl groups, preferably the same in each case and is ethyl, with methyl being particularly preferred.

[0960] R4 is selected from C6-C20 alkyl groups, particularly n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, and n-C18H37.

[0961] 'a' is a number in the range of 0 to 6, preferably 1 to 6.

[0962] b is a number in the range of 0 to 20, preferably 4 to 20.

[0963] d is a number in the range of 4 to 25.

[0964] Preferably, at least one of a and b is greater than zero.

[0965] Here, the compound having general formula (B) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0966] Other suitable nonionic surfactants are selected from diblock and multiblock copolymers of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitol esters. Alkylphenol ethoxylates, alkyl polyglycosides, or polyhydroxy fatty acid amides (glucosamides) are also suitable. A review of suitable other nonionic surfactants can be found in EP A 0 851 023 and DE-A 198 19 187.

[0967] Of course, a mixture of two or more different nonionic surfactants can also exist.

[0968] In a preferred embodiment of the invention, the nonionic surfactant is selected from C12 / 14 and C16 / 18 fatty alcohol alkoxylates, C13 / 15 oxoalkanol alkoxylates, C13-alkanol alkoxylates, and 2-propylheptanol alkoxylates, each of which has 3-15 ethoxy units, preferably 5-10 ethoxy units, or has 1-3 propoxy units and 2-15 ethoxy units.

[0969] The cleaning composition may also contain an amphoteric surfactant, which may also be used in combination with more than one other surfactant.

[0970] Non-limiting examples of amphoteric surfactants—which may also be used in combinations of more than one other surfactant—include: water-soluble amine oxides containing an alkyl moiety having about 8 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl moiety having about 1 to about 3 carbon atoms and a hydroxyalkyl moiety; and water-soluble sulfoxides containing an alkyl moiety having about 10 to about 18 carbon atoms and a moiety selected from the group consisting of an alkyl moiety having about 1 to about 3 carbon atoms and a hydroxyalkyl moiety. See WO 01 / 32816, US 4,681,704 and US 4,133,779. Thus, suitable surfactants include so-called amine oxides, such as lauryl dimethylamine oxide (“laurylamine oxide”).

[0971] Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethylamine oxides or alkylamidopropyl dimethylamine oxides, more preferably alkyl dimethylamine oxides, and especially cocoyl dimethylamine oxides. Amine oxides can have straight-chain or intermediate-branched alkyl moieties. Typical straight-chain amine oxides include water-soluble amine oxides containing an R1 = C8-18 alkyl moieties and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the following formula:

[0972] R1-N(R2)(R3)-O

[0973] Wherein R1 is a C8-18 alkyl group, and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. Linear-chain amine oxide surfactants may in particular include linear C10-C18 alkyl dimethylamine oxides and linear C8-C12 alkoxyethyl dihydroxyethylamine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethylamine oxides. As used herein, “intermediate branch” means that the amine oxide has an alkyl moiety having n1 carbon atoms, wherein an alkyl branch is present on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the α-carbon of the nitrogen from the alkyl moiety. This type of branching of amine oxides is also referred to in the art as internal amine oxides. The sum of n1 and n2 is 10 to 24, preferably 12 to 20, and more preferably 10 to 16 carbon atoms. The number of carbon atoms (n1) of the alkyl moiety should be approximately the same as the number of carbon atoms (n2) of the alkyl branch, such that the alkyl moiety and the alkyl branch are symmetrical. As used herein, "symmetrical" means that in at least 50 wt.%, more preferably at least 75 wt.% to 100 wt.% of the intermediate branched amine oxide used herein, (n1-n2) is less than or equal to 5, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties, each independently selected from C1-C3 alkyl groups, C1-C3 hydroxyalkyl groups, or polyoxyethylene groups containing an average of about 1 to about 3 ethylene oxide groups. Preferably, both moieties are selected from C1-C3 alkyl groups, more preferably both are selected from C1 alkyl groups.

[0974] In a preferred embodiment of the present invention, the amphoteric surfactant is selected from C8-C18 alkyl-dimethylamino oxide and C8-C18 alkyl-di(hydroxyethyl)amino oxide.

[0975] Certain amphoteric surfactants can—in addition to their typical function as surfactants—promote corrosion inhibition, such as compounds having one or two carboxyl groups and one or more amine groups, and optionally further containing amide groups and / or hydroxyl groups; such compounds are, for example, N-(2-carboxyethyl)-N-dodecyl-β-alanine salts (also known as N-lauryl-β-iminodipropionate metal salts), dimetallic salts of cocoamphodiacetic acid, and metal salts of cocoamphodiacetic acid (the metal is typically sodium). Therefore, such amphoteric surfactants are preferred when corrosion inhibition is important, such as in cleaning applications typically with high pH (e.g., automatic dishwashing).

[0976] Cleaning compositions may also contain zwitterionic surfactants – which can also be used in combinations of more than one other surfactant.

[0977] Suitable amphoteric surfactants include betaines, such as alkyl betaines, alkylamidobetaines, imidazolinium betaines, sulfobetaine (INCI sulfobetaine), and phosphate betaines. Examples of suitable betaines and sulfobetaines are as follows (according to INCI nomenclature): Almond amidopropyl betaine, Apricotamidopropyl betaine, avocadoamidopropyl betaine, babasamidopropyl betaine, betaine, betaine, octanoic acid amidopropyl betaine, capryloyl / decanoic acid amidopropyl betaine, carnitine, cetyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl betaine, and cocamidopropyl betaine. propyl hydroxysulfonyl betaine, cocobetaine, cocobetaine hydroxysulfonyl betaine, coco / oleamidopropyl betaine, cocobetaine sulfonyl betaine, decyl betaine, oleyl glycine dihydroxyethyl ester, daidzeinyl glycine dihydroxyethyl ester, stearyl glycine dihydroxyethyl ester, tallow glycine dihydroxyethyl ester, polydimethylsiloxanepropyl PG-betaine, erucamide propyl hydroxysulfonyl betaine, hydrogenated tallow betaine, isostearamide propyl betaine, and more. Laurethamide propyl betaine, lauryl betaine, lauryl hydroxysulfonyl betaine, lauryl sulfonyl betaine, milk amamidopropyl betaine, mink oil amamidopropyl betaine, myristoyl amamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysulfonyl betaine, oil-based betaine, olive oil amamidopropyl betaine, palm oil amamidopropyl betaine, palmitoyl carnitine, palmitoyl carnitine Palm kernel oleamidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, castor oil oleamidopropyl betaine, sesame oil oleamidopropyl betaine, soybean oil oleamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, butteramidopropyl betaine, butteramidopropyl hydroxysulfonyl betaine, butter betaine, butter dihydroxyethyl betaine, undecenoylamidopropyl betaine, and wheat germ oleamidopropyl betaine.

[0978] Preferred betaines are, for example, C12-C18-alkyl betaines and sulfobetaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

[0979] Non-limiting examples of cationic surfactants—which can also be used in combinations of more than one other surfactant—include: quaternary ammonium surfactants, which may have up to 26 carbon atoms, including: alkoxylated quaternary ammonium (AQA) surfactants, as discussed in US 6,136,769; dimethylhydroxyethyl quaternary ammonium, as discussed in US 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants, as discussed in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, and WO 98 / 35006; cationic ester surfactants, as discussed in US Patent Nos. 4,228,042, 4,239,660, 4,260,529, and US 6,022,844; and amino surfactants, as discussed in US 6,221,825 and WO The specific aminopropyl dimethylamine (APA) discussed in 00 / 47708.

[0980] The compositions according to the invention may contain at least one builder. In the context of this invention, no distinction will be made between a builder and such components elsewhere referred to as "co-builders". Examples of builders are complexing agents, also referred to hereinafter as complexing agents, ion exchange compounds, and precipitants. Builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates, and polycarboxylates.

[0981] In the context of this invention, the term citrate includes monoalkali metal salts and dialkali metal salts of citrate, and particularly monosodium salts and preferably trisodium salts of citrate, ammonium salts or substituted ammonium salts of citrate, and citrate itself. Citrates can be used as anhydrous compounds or as hydrates, for example as s...

Claims

1. A method for manufacturing vinyl acetate, the method comprising the following steps: (a) Using electricity generated at least in part from non-fossil renewable resources, hydrogen with a deuterium content of less than 90 ppm is produced by water electrolysis; (b) Provide carbon dioxide; (c) Reacting hydrogen and carbon dioxide in the presence of a catalyst to form methanol with a deuterium content of less than 90 ppm based on a total hydrogen content; (d) React the methanol from step (c) to form ethylene; and (e) React methanol from step (c) with carbon monoxide to form acetic acid; and / or (f1) React a portion of the ethylene from step (d) with oxygen and water to obtain acetaldehyde; (f2) React the acetaldehyde from step (f1) with oxygen to give acetic acid; (g) React acetic acid from step (e) and / or step (f1) with ethylene from step (d) to obtain vinyl acetate.

2. The method according to claim 1, wherein, The electricity is generated from wind, solar, biomass, hydropower, or geothermal energy.

3. The method according to claim 1 or 2, wherein, The carbon dioxide provided in step (b) is captured from industrial flue gas or from ambient air.

4. The method according to any one of claims 1 to 3, wherein, The carbon dioxide provided in step (b) has a δ value corresponding to -10‰ to -2.5‰. 13 C value 13 C content.

5. A method for manufacturing vinyl acetate, the method comprising the following steps: (a) Using electricity generated at least in part from non-fossil renewable resources, hydrogen with a deuterium content of less than 90 ppm is produced by water electrolysis; (b) Provide carbon dioxide; (c) Reacting hydrogen and carbon dioxide in the presence of a catalyst to form methanol with a deuterium content of less than 90 ppm based on a total hydrogen content; (d) React the methanol from step (c) to form ethylene; and (e) React the ethylene from step (d) with oxygen and water to form acetaldehyde; (f1) React a portion of the acetaldehyde from step (e) with oxygen to form acetic acid; and / or (f2) React methanol from step (c) with carbon monoxide to form acetic acid; and (g1) React acetic acid from step (f1) and / or step (f2) with methanol from step (c) to form methyl acetate; (g2) React the methyl acetate from step (g1) with carbon monoxide to form acetic anhydride; and / or (h1) Producing ketene from acetic acid from step (f1) and / or step (f2); (h2) React the ketene from step (h1) with the acetic acid from step (f1) and / or step (f2) to obtain acetic anhydride; (i) React the acetic anhydride from step (g2) and / or step (h2) with the acetaldehyde from step (e) to form ethylene diacetate; (k) React diacetene with acetic acid to obtain vinyl acetate by thermal elimination of acetic acid.

6. A vinyl acetate having a deuterium content of less than 90 ppm based on a total hydrogen content, the vinyl acetate being obtainable by the method according to any one of claims 1 to 5.

7. The vinyl acetate according to claim 6, having a δ value corresponding to -10‰ to -2.5‰. 13 C value 13 C content.

8. A method for producing vinyl acetate from biomass, the method comprising the step of reacting (I) ethylene with (II) acetic acid to obtain vinyl acetate, wherein, (I) Providing ethylene from biomass or ambient air through methods including: (a) Producing carbon oxides from biomass or capturing carbon dioxide from ambient air, optionally followed by electrochemically reducing carbon dioxide to carbon monoxide; (b) Electrochemically reducing the carbon oxides from step (a) to obtain ethylene; and / or (c1) Hydrogen gas and carbon oxides from step (a) are reacted in the presence of a catalyst to give methanol. (c2) React the methanol from step (c1) to form ethylene; and / or (d1) Ethanol is produced from biomass through fermentation. (d2) Dehydrogenating the ethanol from step (d1) to obtain ethylene; and / or (e) Direct production of ethylene from biomass through fermentation; (II) Providing acetic acid from biomass or carbon dioxide captured from ambient air by methods including the following (f) Reacting methanol from step (c1) with carbon monoxide to give acetic acid; and / or (g1) React a portion of the ethylene from steps (b), (c2), (d2), or (e) with oxygen and water to give acetaldehyde, and (g2) React the acetaldehyde from step (g1) with oxygen to give acetic acid; and / or (h) oxidize the ethanol from step (d1) by fermentation to obtain acetic acid; and / or (i) Acetic acid is produced from biomass through biomass pyrolysis.

9. The method according to claim 8, wherein, The carbon oxides in step (a) are produced by the gasification or combustion of biomass, preferably lignocellulosic biomass.

10. The method according to claim 8 or 9, wherein, In step (a), carbon dioxide is electrochemically reduced to carbon monoxide by carbon dioxide electrolysis.

11. The method according to any one of claims 8 to 10, wherein, In step (c2), methanol is reacted in a methanol-to-olefins process to form ethylene, the methanol-to-olefins process comprising the following steps: A) A feed stream A containing methanol and optionally ethanol is fed into a dimethyl ether fixed-bed reactor and the methanol is catalytically converted to dimethyl ether, wherein a product stream A1 containing dimethyl ether, methanol, water vapor and optionally ethanol and ethylene is obtained. B) Mix the stream A1 with at least one hydrocarbon recycling stream R containing C2-C6 hydrocarbons and catalytically convert it in an olefin fixed-bed reactor to produce C2-C4 olefins, C5-C6 hydrocarbons and C7 hydrocarbons. + Crude hydrocarbon stream B; C) Cool the crude product stream B to obtain a crude hydrocarbon product stream C; D) Separate the crude hydrocarbon stream C into a valuable product stream containing propylene, optionally a valuable product stream containing ethylene, a product stream containing butene, at least one recycling stream containing C5-C6 hydrocarbons, and at least one C6 hydrocarbon-containing stream. + Hydrocarbon byproduct streams; E) Recycle a portion of the C2-C4 olefin and at least a portion of the C5-C6 hydrocarbon as one or more hydrocarbon recycling streams R into step B); F) Recover valuable product streams containing propylene, valuable product streams containing ethylene, and optionally valuable product streams containing butene. G) Excretion of C6-containing substances + Hydrocarbon byproduct stream.

12. The method according to any one of claims 8 to 11, wherein, In step (d1), ethanol is produced by fermentation of lignocellulose biomass.

13. The method according to any one of claims 8 to 12, wherein, Ethylene is produced in step (b).

14. The method according to any one of claims 8 to 13, wherein, Ethylene is produced in steps (c1) and (c2).

15. The method according to any one of claims 8 to 14, wherein, Ethylene is produced in steps (d1) and (d2).

16. The method according to any one of claims 8 to 15, wherein, Acetic acid is produced in step (f).

17. The method according to any one of claims 8 to 16, wherein, Acetic acid is produced in steps (g1) and (g2).

18. The method according to any one of claims 8 to 17, wherein, Acetic acid is produced in step (h).

19. The method according to any one of claims 8 to 18, wherein, Acetic acid is produced in step (i).

20. A vinyl acetate having a natural abundance of C-14, which is obtained by the method according to any one of claims 8 to 19.

21. A polymer or copolymer of vinyl acetate and a polymer dispersion comprising vinyl acetate, wherein the vinyl acetate has a natural abundance of C-14.

22. The use of vinyl acetate with natural abundance of C-14 for determining the content of bio-based vinyl acetate or vinyl alcohol derived therefrom in polymers or copolymers containing vinyl acetate or vinyl alcohol.

23. The use of vinyl acetate with natural abundance of C-14 for determining the source of decay products released during the decomposition of polymers or copolymers containing vinyl acetate or vinyl alcohol.

24. A method for preparing an alkoxylated compound, the alkoxylated compound comprising... i) 20 wt% to < 100 wt% ethylene oxide units and / or propylene oxide units, ii) at least one alkylene oxide unit, different from ethylene oxide and propylene oxide units, ranging from 0 wt% to 30 wt%. iii) > 0 wt% to 80 wt% of at least one starting unit having a Zelevitinov active hydrogen atom, The sum of the units mentioned under i), ii) and iii) is 100 wt% The method includes the following steps: (a This allows hydrogen to react with carbon dioxide to form methanol. (b ) will come from step (a) The methanol is converted into ethylene and / or propylene. (c ) make from step (b) The ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide, and (d In one or more steps, make step (c) The ethylene oxide and / or propylene oxide obtained in the process, and optionally at least one alkyl oxide different from ethylene oxide and propylene oxide, react with the at least one starting unit having a Zelevithinov active hydrogen atom to form the alkoxylated compound. Among them, step (a) The carbon dioxide in the substance is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

25. The method according to claim 24, wherein, Step (c) The propylene oxide in the present invention is obtained by oxidizing propylene with hydrogen peroxide as an oxidant, preferably in the presence of a zeolite catalyst, more preferably in the presence of titanium silicate zeolite-1 (TS-1).

26. The method according to claim 24 or 25, wherein, Step (c) The oxygen in the solution is obtained at least in part by water splitting, preferably by electrolysis, which preferably uses energy generated at least in part from non-fossil resources.

27. An alkoxylated compound, which can be obtained by the method according to any one of claims 24 to 26.

28. A method for preparing ethylene oxide or propylene oxide, the method comprising the following steps: (a This allows hydrogen to react with carbon dioxide to form methanol. (b ) will come from step (a) The methanol is converted into ethylene and / or propylene. (c ) make from step (b) The ethylene and / or propylene react with oxygen or an oxidizing agent to form ethylene oxide and / or propylene oxide. Among them, step (a) The carbon dioxide in the substance is at least partially captured or obtained from industrial flue gas, from the air, or from seawater or other natural water by biological processes, such as fermentation processes from waste or biomass.

29. Use of the alkoxylated compound according to claim 27 or obtained by the method according to any one of claims 24 to 26 in: home care products, cosmetic products, pharmaceutical products, the food industry, building materials, lubricants such as engine oils, bearing oils, gear oils, compressor oils, greases, heat transfer fluids, metalworking fluids and transmission fluids, defoamers, softeners, rheology modifiers, emulsifiers, dispersants, thickeners, stabilizers, metalworking fluids, agricultural chemicals such as pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages, and poly(urethane) applications.

30. A grafted polymer based on an ethylene oxide backbone, wherein the ethylene oxide backbone is grafted with an olefinically polymerizable monomer, preferably a vinyl monomer, and more preferably with... a) Vinyl esters and optionally additional monomers, preferably selected from vinyl lactams, more preferably vinyl pyrrolidones, and free radical polymerizable olefinic unsaturated amine monomers such as vinylamines, more preferably vinylimidazoles, and even more preferably, such monomers are at least one vinyl ester, at least one lactam, and optionally at least one vinylamine, and even more preferably, such monomers are vinyl acetate, vinyl pyrrolidone, and vinylimidazoles, or b) Vinyl lactam, more preferably vinylpyrrolidone and free radical polymerizable olefinic unsaturated amine monomers such as vinylamine, more preferably vinylimidazole; Such graft polymers are at least partially based on hydrogen from non-fossil-based sources, wherein the molar fraction of deuterium in such graft polymers is lower than that in the same compounds when derived solely from fossil-based sources, and wherein such graft polymers may contain other monomers in the chain derived from epoxides, preferably ethylene oxide, and such other monomers are preferably selected from lactones and / or other epoxides other than or besides ethylene oxide.

31. A method for manufacturing the grafted polymer according to claim 30, wherein, The method includes the following steps: Hydrogen gas with a molar fraction of deuterium of ≤100 ppm, preferably in the range of 10 to ≤95 ppm, more preferably in the range of 10 to ≤90 ppm, and most preferably in the range of 10 to ≤80 ppm, is provided by electrolysis based on electricity generated at least partially from non-fossil energy sources. (a) The hydrogen gas from step (a) is reacted with carbon oxides, preferably carbon dioxide, to form methanol. (b) The methanol from step (c) is converted into ethylene and further into ethylene oxide. (c) In one or more steps, the ethylene oxide from step (d) is converted into a polymer or mixture of polymers using a known method such as alkoxylation, the polymer comprising ethylene oxide and optionally other monomers selected from alkyl oxidases other than ethylene oxide. (d) Using standard means, the polymer from step (d) is further reacted with at least one vinyl monomer, preferably with: a) at least one vinyl ester and optionally at least one additional monomer, preferably at least one monomer selected from vinyl lactams and free-radical polymerizable olefinically unsaturated amine monomers, more preferably vinylpyrrolidone and / or vinylimidazole, or b) at least one vinyl lactam, preferably vinylpyrrolidone and optionally at least one vinylamine, preferably vinylimidazole. To obtain grafted polymers containing deuterium with a lower total hydrogen content compared to grafted polymers obtained solely from fossil-based sources with the same chemistry.

32. The use of the molar fraction of deuterium contained in hydrogen-based compounds according to claim 30, or compounds obtainable or preferably obtainable by the method according to claim 31, for tracing the source of preparation of such hydrogen-based compounds.

33. A method for tracing the source of hydrogen preparation contained in a compound according to claim 30, or a compound obtainable or preferably obtainable by the method according to claim 31, by determining the molar fraction of deuterium in hydrogen and the hydrogen-based compound.

34. Use of the compound of claim 30, or a compound obtainable or preferably obtainable by the method of claim 31, preferably in a composition, more preferably a fabric and household care product, a cleaning composition, or an industrial and institutional cleaning product.

35. A composition, which is a laundry detergent, cleaning composition, or fabric and household care product, comprising at least one compound according to claim 30, or a compound obtainable or preferably obtainable by the method according to claim 31, comprising at least one compound in a concentration of preferably about 0.1% to about 20% by weight relative to the total weight of such composition or product, and optionally further comprising at least one of a) to c). a. At least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, deoxyribonucleases, dispersases, pectinases, oxidoreductases, keratinases, lactases, and peroxidases, more preferably at least two of the foregoing types, and where an enzyme is included, preferably also containing at least one enzyme stabilizing system. b. A surfactant system comprising approximately 1% to approximately 70% by weight. c. An effective amount of at least one additional cleaning aid, preferably at least one compound selected from alkoxylated diamines, oligoamines and polyamines, and alkoxylated polyethylimide, wherein alkoxylation is preferably performed using EO and / or propylene oxide. It may also optionally exhibit improved washing performance and / or dye transfer inhibition properties in primary cleaning (i.e., stain removal).

36. A method for preserving the composition according to claim 35 against microbial contamination or growth, the method comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition, the composition being an aqueous composition containing water as a solvent.

37. A method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with the composition according to 35, wherein the composition comprises 4,4'-dichloro-2-hydroxydiphenyl ether, preferably comprising 0.001% to 3%, more preferably 0.002% to 1%, more preferably 0.01% to 0.6% of 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration based on the weight of the composition.

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