Amine polymers for carbon scavenging

Abstract

The present invention relates to a method for using an optionally alkoxylated nitrogen-containing polymer in the capture of carbon dioxide, said optionally alkoxylated nitrogen-containing polymer comprising the following steps: a) a step of reacting (i) a di- or oligoamine (A) with (ii) a crosslinking compound (BC) to provide a nitrogen-containing polymer (NP), wherein the crosslinking compound (BC) is (I) phosgene; or (II) comprises at least two amine-reactive groups (ARG), the crosslinking compound (BC) being capable of binding to the amine groups of at least two di- or oligoamine (A) molecules, the nitrogen-containing polymer (NP) comprising the molecular components of the crosslinking compound (BC) that bind to at least two molecular components of the di- or oligoamine (A), the proportion of the crosslinking compound (BC) molecules bound to at least two di- or oligoamine (A) molecules being the crosslinking factor (BF) of the nitrogen-containing polymer (NP), the crosslinking factor (BF) exceeding 50%, the sum of the primary and secondary amine groups of the nitrogen-containing polymer (NP) being at least 600 mg KOH / g, the number average molecular weight (Mn) of the nitrogen-containing polymer (NP) exceeding 600 g / mol, and b) a step of reacting the nitrogen-containing polymer (NP) with an alkylene oxide (AO), wherein the molar ratio of the alkylene oxide (AO) to the NH functionality of the nitrogen-containing polymer (NP) is 0.25 or less, obtainable by a method comprising. The present invention further relates to a method for capturing carbon dioxide from a gas mixture using an optionally alkoxylated nitrogen-containing polymer.

Description

[Technical Field]

[0001] The present invention relates to a method for using nitrogen-containing polymers (NPs) that are optionally alkoxylated in the field of carbon capture, such as in direct air capture (DAC) applications, particularly when carbon dioxide is directly absorbed from the air. Specifically, the amine-containing polymers are based on condensation products of polyamines such as tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) with a bifunctional or polyfunctional crosslinking compound (BC) having the ability to bind polyamine molecules. The bifunctional or polyfunctional crosslinking compound (BC) contains two or more amine-reactive groups (ARGs). These amine-containing polymers are optionally alkoxylated, for example, by the action of one or more alkylene oxides to produce alkoxylated nitrogen-containing polymers (ANPs). [Background technology]

[0002] Rising concentrations of greenhouse gases in the atmosphere are a global concern due to their predicted impact on climate change. The increase in carbon dioxide concentrations, in particular, is a major concern. It is widely acknowledged that current atmospheric carbon dioxide levels are causing dramatic environmental changes worldwide, including droughts, floods, and ecosystem destruction. Further increases in carbon dioxide concentrations are predicted to lead to a significant rise in average atmospheric and ocean temperatures, accelerating the melting of polar and glacial ice, resulting in sea-level rise and lowland flooding. Rising atmospheric temperatures are also expected to increase the global probability of powerful cyclone-type storms.

[0003] Many governments are taking legislative measures aimed at reducing greenhouse gas emissions, particularly carbon dioxide, and ultimately curbing global warming. Many countries have adopted the Paris Agreement, a legally binding international treaty on climate change. Its goal is to limit global warming to below 2°C, and ideally to 1.5°C, compared to pre-industrial levels.

[0004] In recent years, considerable effort has been invested in developing technologies to achieve targets for reducing atmospheric carbon dioxide concentrations and gaseous emissions. Methods of capturing carbon dioxide at its source are generally considered the most cost-effective. Specifically, these include large-scale carbon-based energy facilities, natural gas processing plants, synthetic fuel plants, industries with high carbon dioxide emissions such as steel manufacturing and cement production, and hydrogen production facilities that use fossil fuels.

[0005] The most common carbon dioxide capture technologies are absorption or sequestration. Amine chemistry is the most widely used active material for carbon dioxide absorption. Amines commonly used for this purpose include alkanolamines, such as monoethanolamine, diethanolamine, diisopropanolamine, pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, tetraethylenetetramine, bis(2-hydroxypropyl)amine, N,N'-bis(2-hydroxyethyl)ethylenediamine, alkylamines, methylamines, linear polyethyleneimines, branched polyethyleneimines, dimethylamines, diethylamines, methyldiethanolamine, methylethanolamine, polyethylenepolyamines, diethylenetriamine, and N,N'-bis(3-aminopropyl)ethylenediamine.

[0006] U.S. Patent No. 9,084,960 B2 discloses a method for reducing the CO2 content of a gas, and the CO2 scavenger may include monoamines (particularly secondary amines such as diethanolamine), polyamines, monoguanidines, polyguanidines, and mixtures thereof.

[0007] U.S. Patent No. 9,533,250 B2 relates to the reduction of CO2 from indoor air in a closed space. The document describes amine compounds, which are suggested to include any suitable amine, including primary amines, secondary amines, or combinations thereof. The disclosure reveals that amine compounds range from simple single molecules such as ethanolamine to high molecular weight amine polymers such as polyethyleneimine. The document proposes several polyamines, or combinations thereof, such as monoethanolamine, ethanolamine, methylamine, branched polyethyleneimine, linear polyethyleneimine, diethanolamine, dimethylamine, diethylamine, diisopropanolamine, tetraethylenepentamine, methyldiethanolamine, methylethanolamine, and polyethyleneimine.

[0008] U.S. Patent No. 11,229,897 B2 discloses a gas absorbent containing a polyamine produced by a process that does not include formaldehyde as a reaction product and / or reactant. The disclosure describes a method for producing a reaction solution of a first amine compound and a reactant. The reactant is said to include a carbonate ester compound or a ketone compound. The first amine compound reacts with the reactant to produce a second amine compound.

[0009] U.S. Patent No. 10,010,861 B2 and its corresponding publication application U.S. 2018 / 0008958 A1 describe polymeramines intended for carbon dioxide absorption. These polymeramines consist of a nitrogen atom-containing polymer backbone and branched chains bonded to the nitrogen atoms of the polymer backbone. Each branched chain contains at least one nitrogen atom, and the polymeramines are modified by substituting at least one nitrogen atom of the polymer backbone or branched chain with a carbon-containing hydroxyl group. Example 1 describes the synthesis of polyethyleneimine modified by partial substitution with butylene oxide. This synthesis involves dissolving polyethyleneimine (MN=1200, 19 mmolN / g) in methanol. The disclosure reveals that different amounts of butylene oxide are added to the polyethyleneimine / methanol solution to adjust the molar ratio of butylene oxide to nitrogen atoms in polyethyleneimine to 0.15:1, 0.37:1, and 0.54:1. The disclosure reveals that the solvent is removed by heating a solution of modified polyethyleneimine in a vacuum oven.

[0010] U.S. Patent No. 10,751,689 B2 and its corresponding publication application U.S. 2016 / 0199810 A1 disclose modified polyamines for carbon dioxide absorption. Modified polyamines are reaction products of amines and epoxides. The amines described are relatively low molecular weight amines, such as pentaethylenehexamine (PEHA) and tetraethylenepentamine (TEPA), which are known as oligoamines. Example 1 describes a method for preparing a modified polyamine species based on pentaethylenehexamine (PEHA) and propylene oxide (PO). The preparation involves dissolving 10 g of PEHA in 40 mL of water, adding 5 g of PO to the PEHA solution, and stirring at room temperature for 20 hours. The temperature of the reaction mixture is gradually increased to 60°C and maintained for 2 hours. The water is removed using a rotary evaporator and the mixture is dried overnight under a vacuum of less than 1 mmHg.

[0011] U.S. Patent Application Publication US 2019 / 0076820 A1 describes a method and apparatus for removing volatile components from a mixture, the method and apparatus using a crosslinked elastomer having a glass transition temperature of +25°C or lower as an adsorbent. Paragraph

[0029] of the disclosure describes, in one embodiment, the VOC is an organic monomer used for polymerization or crosslinking, such as ethylene, propylene, and various hydrophilic vinyl addition monomers, and this list further includes amine compounds such as glycidyl methacrylate, phosgene, isocyanates, and ethylenediamine, and epoxy compounds such as oligomeric liquid epoxy resins. The VOC may be a petroleum-derived fuel or fuel mixture such as diesel fuel, or the VOC may be an organic hazardous substance or odor-causing compound such as an organosulfur compound. Furthermore, the VOC may be CO2.

[0012] International patent application publication WO 2021 / 168498 A1 describes a process for removing carbon dioxide (CO2) from a gas stream having a low CO2 concentration. This process involves bringing the gas stream into contact with a hydrogel. 、 It is stated that this includes absorbing at least some of the CO2 from the gas flow. The hydrogel is said to contain a crosslinked hydrophilic polymer, which is a hydrophilic polymer crosslinked with a crosslinking agent. Example 1 describes the production of crosslinked polyethyleneimine (PEI) hydrogel particles by adding a 1,3-butadiene diepoxide crosslinking solution at different concentrations. Example 5 describes direct air capture (DAC) using PEI hydrogel and evaluates the DAC capacity.

[0013] U.S. Patent Application Publication US 2022 / 0347654 A1 describes a method for producing CHEFS (chemical adsorbent fiber) from a dope. One or more examples describe a method for producing CHEFS having amine functional groups, comprising the steps of producing a dope comprising a BIAS (basic immobilized amine adsorbent) having amine groups, at least one polymer, and at least one solvent, and forming CHEFS from the dope. CHEFS is said to be suitable for CO2 capture. The disclosure is 、Paragraph

[0036] states that BIAS generally comprises about 60% by mass of silica and 40% by mass of a combination of polyamine and a crosslinking agent, the crosslinking agent comprising epoxysilane, polyepoxide, aminosilane, acrylamide-based crosslinking agents, and combinations thereof. The document describes an example of BIAS containing silica particles with an average particle size of 25 μm and polyethyleneimine, where the polyethyleneimine is crosslinked polyethyleneimine (Mw=800) and N,N-diglycidyl-4-glycidyloxyaniline.

[0014] Polyethyleneimines (PEI) and other polyalkyleneimines, such as polypropyleneimines (PPI), are known to exhibit excellent performance in terms of stability as CO2 adsorbents in DACs and as CO2 capture agents from post-combustion processes and CO2 point sources. These sources are typically found in three areas: fuel combustion activities, industrial processes, and natural gas processing.

[0015] Linear PEI and linear PPI are known to be superior to branched PEI and branched PPI, which is thought to be due to the relatively high content of secondary amino groups in linear products. A low content of primary NH functional groups is known to be advantageous for CO2 adsorption. This can be improved by alkoxylation of PEI or PPI, but such improvements tend to be limited.

[0016] Low molecular weight oligoamines, such as tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA), are known as excellent CO2 adsorbents. Patents and literature have proposed using these polyamines for CO2 capture in various carbon capture applications such as DAC. However, such low molecular weight polyamines have the disadvantage of high vapor pressure, which leads to increased polyamine loss, particularly in the reuse of adsorbents at high temperatures, such as in CO2 desorption processes. [Prior art documents] [Patent Documents]

[0017]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0018] The object of the present invention is to develop a nitrogen-based product having good or improved ability to absorb CO2, and the inventors particularly aimed to provide a product showing a more beneficial ratio of secondary NH functional groups to primary NH functional groups. Further, the object of the present invention was to develop a product that can be recycled more easily during the CO2 desorption process that usually involves high temperatures.

Means for Solving the Problems

[0019] The present invention provides a method of using an optionally alkoxylated nitrogen-containing polymer in the capture of carbon dioxide, and the optionally alkoxylated nitrogen-containing polymer comprises the following steps: a) A step of providing a nitrogen-containing polymer (NP) by reacting (i) a di- or oligoamine (A) with (ii) a crosslinked compound (BC), wherein the crosslinked compound (BC) is (i) Is it phosgene; or (II) comprising at least two amine-reactive groups (ARGs), The crosslinked compound (BC) can bond to at least two amine groups of di- or oligoamine (A) molecules. The nitrogen-containing polymer (NP) contains molecular components of a crosslinking compound (BC) that are bound to at least two molecular components of a di- or oligoamine (A), and the proportion of crosslinking compound (BC) molecules bound to at least two di- or oligoamine (A) molecules is the crosslinking factor (BF) of the nitrogen-containing polymer (NP), and the crosslinking factor (BF) exceeds 50%. The total amount of primary and secondary amine groups in the nitrogen-containing polymer (NP) is at least 600 mg KOH / g. The process and the nitrogen-containing polymer (NP) having a number-average molecular weight (Mn) exceeding 600 g / mol. b) Optionally, a step to obtain alkylene oxide side chains (AB) bonded to the nitrogen atom of a nitrogen-containing polymer (NP) and to provide an alkoxylated nitrogen-containing polymer (ANP), wherein the nitrogen-containing polymer (NP) is reacted with an alkylene oxide (AO) preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of alkylene oxide (AO) to the NH functional group of the nitrogen-containing polymer (NP) is 0.25 or less. It can be obtained by a method that includes [a specific method].

[0020] The present invention further includes a method for capturing carbon dioxide, comprising contacting a gas mixture containing carbon dioxide with an optionally alkoxylated nitrogen-containing polymer in carbon dioxide capture, and contacting the optionally alkoxylated nitrogen-containing polymer with carbon dioxide, wherein the optionally alkoxylated nitrogen-containing polymer is provided in the following steps: a) A step of providing a nitrogen-containing polymer (NP) by reacting (i) a di- or oligoamine (A) with (ii) a crosslinked compound (BC), wherein the crosslinked compound (BC) is (i) Is it phosgene; or (II) comprising at least two amine-reactive groups (ARGs), The crosslinked compound (BC) can bond to at least two amine groups of di- or oligoamine (A) molecules. The nitrogen-containing polymer (NP) contains molecular components of a crosslinking compound (BC) that are bound to at least two molecular components of a di- or oligoamine (A), and the proportion of crosslinking compound (BC) molecules bound to at least two di- or oligoamine (A) molecules is the crosslinking factor (BF) of the nitrogen-containing polymer (NP), and the crosslinking factor (BF) exceeds 50%. The total amount of primary and secondary amine groups in the nitrogen-containing polymer (NP) is at least 600 mg KOH / g. The process and the nitrogen-containing polymer (NP) having a number-average molecular weight (Mn) exceeding 600 g / mol. b) Optionally, a step to obtain alkylene oxide side chains (AB) bonded to the nitrogen atom of a nitrogen-containing polymer (NP) and to provide an alkoxylated nitrogen-containing polymer (ANP), wherein the nitrogen-containing polymer (NP) is reacted with an alkylene oxide (AO) preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of alkylene oxide (AO) to the NH functional group of the nitrogen-containing polymer (NP) is 0.25 or less. It can be obtained by a method that includes [a specific method]. [Modes for carrying out the invention]

[0021] A crosslinking compound (BC) is a compound that binds to at least two amine groups, i.e., at least two different di- or oligoamine (A) molecules, to form a crosslink, thereby constructing the structure of a nitrogen-containing polymer (NP). Such a crosslinking compound (BC) is a compound that contains phosgene or at least two amine-reactive groups (ARG) and can bind to at least two amine groups to bind at least two molecules of di- or oligoamine (A).

[0022] Phosgene reacts with the primary amine group of di- or oligoamine (A) to form an isocyanate group, and then reacts with the amine group of another di- or oligoamine to form intermolecular crosslinks of the di- or oligoamine.

[0023] Preferably, the crosslinking compound (BC) comprises at least two amine reactive groups (ARG) and can bond to at least two amine groups of the di- or oligoamine (A).

[0024] The crosslinked compound (BC) may preferably be a reaction product formed by reacting (i) a diol or polyol with (ii) an epihalohydrin, preferably an epichlorohydrin.

[0025] Diols or polyols are organic compounds containing two or more hydroxyl groups. These include diols, triols, or compounds containing four or more hydroxyl groups.

[0026] Suitable examples of diols include aliphatic compounds containing 2 to 14 carbon atoms. Specific examples include ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), propane-1,3-diol (trimethylene glycol), butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, cyclopentane-1,2-diol, 4-methylcyclopentane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, and 2-ethylhexane-1,3-diol. Preferred diols include ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), and propane-1,3-diol (trimethylene glycol). Examples of triols include propane-1,2,3-triol (glycerol), butane-1,2,3-triol, butane-1,2,4-triol, pentane-1,2,3-triol, pentane-1,2,4-triol, pentane-1,2,5-triol, and pentane-1,3,5-triol. The preferred polyol is propane-1,2,3-triol (glycerol). Other polyols include pentaerythritol.

[0027] Suitable polyols typically include sugar alcohols derived from sugars. These are characterized by having one hydroxyl group bonded to each carbon atom. Examples of sugar alcohols include erythritol, xylitol, sorbitol, mannitol, tretitol, arabitol, ribitol, galactol, fucitol, isitol, inositol, and boremitol.

[0028] Other polyols include polyethers or polyester polyols that generally have at least two hydroxyl groups as terminal groups. Polyethers generally contain repeating alkylene oxide units having hydroxyl groups as terminal groups. Polyester polyols generally contain repeating alkylene ester bonds but have hydroxyl groups at the terminals. The number of repeating units in polyethers and polyester polyols is 6 or less, for example, 2 to 6, preferably 2 to 3. Preferred polyethers as polyols include diethylene glycol and triethylene glycol. Preferably, the di- or polyol is selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, 1,3-neopentyl glycol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

[0029] Epihalohydrins are typically known as epichlorohydrins. Epichlorohydrins are also known as (chloromethyl)oxirane, 1-chloro-2,3-epoxypropane, γ-chloropropylene oxide, glycidyl chloride, or ECH.

[0030] (i) The reaction product of a diol or polyol and (ii) an epihalohydrin, preferably an epichlorohydrin, contains a glycidyl group, which is usually bonded to the diol or polyol radical by an ether linkage instead of a hydroxyl group. Such a reaction product containing at least two glycidyl groups is a useful crosslinking compound (BC).

[0031] Preferably, the reaction product of (i) a diol or polyol and (ii) an epihalohydrin, preferably an epichlorohydrin, is a reaction product having a reaction product molecule containing at least 55 mol%, preferably more than 60 mol%, preferably more than 70 mol%, and more than 80 mol% of two epoxide groups. In a further preferred embodiment, the reaction product is formed by the reaction of a mixture of (i) a diol or polyol and (ii) an epihalohydrin, preferably an epichlorohydrin, where the reaction product has a reaction product molecule containing more than 90 mol% of two epoxide groups. Depending on the purity of the diol or polyol, the reaction product contains a maximum of 45 mol%, preferably less than 40 mol%, preferably less than 30 mol%, and more preferably less than 20 mol% of one epoxide group. Particularly preferably, less than 10 mol%, e.g. less than 5 mol%, usually less than 1 mol%, e.g. less than 0.5 mol%, e.g. less than 0.1 mol%, of the reaction product molecule contains one epoxide group. Reaction products containing three or more epoxide groups can also be used as crosslinking compounds (BC) for reaction with di- or oligoamines. Preferably, the reaction product may include a mixture of molecules containing mainly two epoxide groups, molecules containing three or more epoxide groups, and molecules containing one epoxide group. Preferably, such a reaction product contains molecules containing three or more epoxide groups in an amount of 40 mol% or less, more preferably molecules containing three or more epoxide groups in an amount of 30 mol% or less. Furthermore, it is particularly preferable that less than 20 mol%, and especially preferably less than 10 mol%, of the reaction product molecules contain three or more epoxide groups.

[0032] The crosslinked compound (BC) is preferably a compound comprising at least two amine-reactive groups (ARGs). The amine-reactive groups (ARGs) in the present invention can be any group that is reactive to an amine group. Typically, such amine-reactive groups (ARGs) include functional groups such as epoxides, isocyanates, blocked isocyanates, esters, and acid anhydrides.

[0033] In a preferred embodiment, the crosslinked compound (BC) comprises at least two epoxide groups. These at least two epoxide groups readily react as amine reactant groups (ARGs) with the amine groups of the diamine or oligoamine (A), particularly primary amine groups, to form an amino alcohol bond between the diamine or oligoamine (A). Preferably, the two epoxide groups can be part of an aliphatic molecule, such as 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, and 1,2,7,8-diepoxyoctane. More preferably, each epoxide is part of a glycidyl group, and even more preferably, at least two glycidyl groups are glycidyl ether groups. Suitable examples of crosslinked compounds (BC) containing at least two glycidyl ether groups include diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and 5,5-dimethyl-3,7-dioxa-1,9(2)-bis(oxyrana)-4,6(2,4)-dibenzenanonaphane.

[0034] Another suitable group of crosslinking compounds (BC) are diisocyanates, where the amine reactive group (ARG) consists of two isocyanate groups. Isocyanates readily react with amine groups to produce urea derivatives. Thus, the two isocyanate groups of a diisocyanate readily react with the amine groups of two di- or oligoamine (A) molecules, particularly primary amine groups, and can link them together by a urea bond. Examples of suitable diisocyanates include methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylenedicyclohexyl diisocyanate or hydrogenated MDI (HMDI), and isophorone (IPDI).

[0035] To control the reaction between the diisocyanate group and the amino group of a di- or oligoamine (A), it may be desirable to use blocked diisocyanates. This allows for the reaction to occur with a specific trigger, such as at a particular temperature or after UV irradiation. Examples of blocking agents used to block diisocyanates include methyl ethyl ketone oxime. In most cases, it may not be necessary to use blocked diisocyanates.

[0036] A more suitable group of crosslinking compounds (BC) are diesters. Suitable examples include carbonate esters that react with two di- or oligoamine (A) molecules to form urea that crosslinks the di- or oligoamine (A) moieties by aminolysis. Even more suitable examples include terephthalic acid esters that react with two di- or oligoamine (A) molecules to form terephthalic acid diamide crosslinks between the di- or oligoamine molecules.

[0037] The crosslinked compound (BC) may contain at least two acid anhydride groups as amine reactive groups (ARGs). The acid anhydride groups are reactive with amines and react with them to form amide bonds.

[0038] Preferably, the crosslinking compound (BC) is a compound comprising at least two amine-reactive groups (ARGs) selected from the group consisting of compounds comprising at least two glycidyl ether groups and at least two diisocyanate groups. More preferably, the crosslinking compound (BC) is a compound comprising at least two glycidyl ether groups.

[0039] More preferably, the crosslinked compound (BC) is a compound comprising at least two glycidyl ether groups, and the compound is (i) containing at least two structures according to formula (I) [ka] (In the formula, the dotted line indicates the bond with the rest of the compound containing at least two glycidyl ether groups), preferably, the compound containing at least two glycidyl ether groups has two structures according to formula (I), and / or (ii) Selected from 1,4-butanediol bisglycidyl ether, 1,6-hexanediol bisglycidyl ether, diglycidyl ether, 1,3-neopentyl glycol bisglycidyl ether, 1,4-cyclohexanedimethanol bisglycidyl ether, ethylene glycol bisglycidyl ether, glycerin triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0040] The crosslinking compound (BC) contains at least two amine reactive groups (ARG) to properly form molecular crosslinks between di- or oligoamine molecules (A).

[0041] The crosslinked compound (BC) may include a mixture of crosslinked compound (BC) molecules containing at least two amine-reactive groups (ARGs) and molecules containing only one amine-reactive group (ARG). Generally, the amine-reactive groups (ARGs) of the crosslinked compound (BC) molecules contained in such a mixture must be of the same, the same category, or at least non-reactive to each other. Typically, these amine-reactive groups (ARGs) are identical to each other. Preferably, the crosslinked compound (BC) is primarily composed of crosslinked compound (BC) molecules containing at least two amine-reactive groups (ARGs). In some cases, the crosslinked compound (BC) may contain up to 45 mol% monofunctional molecules, i.e., only one amine-reactive group (ARG). This can depend on the purity of the crosslinked compound. For example, bisglycidyl ether may include a monofunctional compound containing up to 45 mol% of only one epoxide group and bisglycidyl ether molecules containing at least 55 mol% of two epoxide groups.

[0042] Preferably, the crosslinked compound (BC) comprises a crosslinked compound (BC) molecule mainly containing two amine-reactive groups (ARGs) (preferably both being epoxide groups). Appropriately, the crosslinked compound (BC) comprises a compound having more than 60 mol% of two amine-reactive groups (ARGs) (preferably both being epoxide groups), and preferably less than 40 mol% of one amine-reactive group (ARG), preferably an epoxide group; preferably more than 70 mol% of two amine-reactive groups (ARGs) (preferably both being epoxide groups), and preferably less than 30 mol% of one amine-reactive group (ARG), preferably an epoxide group; more preferably more than 80 mol% of two amine-reactive groups (ARGs) (preferably both being epoxide groups), and preferably less than 20 mol% of one amine-reactive group (ARG), preferably an epoxide group. Particularly preferably, less than 10 mol% of the crosslinked compound (BC) molecule may contain only one amine-reactive group (ARG), preferably an epoxide group. Particularly preferred, the crosslinked compound (BC) substantially does not contain molecules containing only one amine-reactive group (ARG).

[0043] Therefore, it is possible for a relatively small amount of a compound containing only one amine-reactive group (ARG) to be present in the crosslinking compound (BC). However, it is desirable to minimize this amount, as a high level of a compound containing only one amine-reactive group (ARG) may adversely affect the construction of the molecular structure of the nitrogen-containing polymer (NP). Generally, the amount of a compound containing only one amine-reactive group (ARG) is less than 10 mol%, usually less than 5 mol%, typically less than 1 mol%, preferably less than 0.5 mol%, and more preferably less than 0.1 mol%. Particularly preferably, the crosslinking compound (BC) is substantially free of or free of a compound containing only one amine-reactive group (ARG).

[0044] A crosslinked compound (BC) containing three or more amine-reactive groups (ARGs), preferably epoxide groups, can also be used in reactions with di- or oligoamines (A). Preferably, the crosslinked compound (BC) may consist of a mixture of a crosslinked compound (BC) molecule containing mainly two amine-reactive groups (ARGs) and a remainder consisting of molecules containing three or more amine-reactive groups (ARGs) and / or molecules containing one amine-reactive group (ARG). In a preferred form, the mixture is a mixture of molecules containing a crosslinked compound (BC) molecule containing mainly two epoxide groups and molecules containing three or more epoxide groups and / or molecules containing one epoxide group.

[0045] Particularly preferably less than 20%, and especially preferably less than 10%, of the crosslinking compound (BC) molecules contain three or more amino reactive groups (ARG). This is to avoid undesirable levels of crosslinking of nitrogen-containing polymers (NP), which could adversely affect the solubility of the polymer in water.

[0046] Crosslinking of nitrogen-containing polymers (NPs) is acceptable as long as it does not adversely affect the water solubility of the nitrogen-containing polymers (NPs). In general, crosslinking is acceptable because it can reduce the volatility of nitrogen-containing polymers (NPs) and offset any small effect on water solubility. The degree of crosslinking can be controlled by adjusting the ratio of reaction product molecules containing two epoxide groups, reaction product molecules containing three or more epoxide groups, and reaction product molecules containing only one epoxide group.

[0047] The di- or oligoamine (A) preferably contains at least two amino groups, and more preferably 2 to 12 amino groups. Preferably, the di- or oligoamine (A) contains 2 to 8 amino groups, for example 3, 4, 5, 6, 7, or 8 amino groups, and more preferably 4 to 8 amino groups.

[0048] Generally, di- or oligoamines (A) have at least one carbon atom per nitrogen atom, preferably 1 to 5 carbon atoms per nitrogen atom, and more preferably 1 to 3 carbon atoms per nitrogen atom. Typically, the nitrogen atoms are separated from each other by at least one saturated hydrocarbon radical, such as an alkylene or alkanetriyl radical with 2 to 6 carbon atoms, preferably an alkylene radical with 2 to 4 carbon atoms.

[0049] Preferably, the di- or oligoamine (A) has at least two primary and / or secondary amino groups. Preferably, the di- or oligoamine (A) has at least two primary amino groups, and more preferably, the secondary amino groups are dominant over the primary amino groups.

[0050] The mass-average molecular weight (M) of di- or oligoamine (A) W The g / mol concentration is preferably in the range of 50 to 500 g / mol, more preferably 60 to 300 g / mol, more preferably 80 to 250 g / mol, more preferably 120 to 250 g / mol, and particularly preferably 150 to 250 g / mol.

[0051] Preferably, at least one di- or oligoamine (A) is (i) having at least two amino groups, preferably two to twelve amino groups, more preferably two to eight amino groups, and even more preferably three, four, five, six, seven, or eight amino groups; and, (ii) Each nitrogen atom has at least one carbon atom, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms; and, (iii) comprising at least two primary and / or secondary amino groups, preferably comprising at least two primary amino groups; and (iv) The molecular weight (Mw) is in the range of 50 to 500 g / mol, preferably 60 to 300 g / mol, more preferably 80 to 250 g / mol, even more preferably 120 to 250 g / mol, and particularly preferably 150 to 250 g / mol.

[0052] Independently of or in addition to the above features (i), (ii), (iii), and (iv), the di- or oligoamine (A) is selected from the group consisting of ethylenediamine, hexamethylenediamine, methylcyclohexanediamine (MCDA), propylenediamine (PDA), tetramethylenediamine (TMDA), pentamethylenediamine (PMDA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tris(2-aminoethyl)amine (TAEA), tetrapropylenepentamine (TPPA), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), 3-(2-aminoethylamino)propylamine (N3-amine), spermine, spermidine, triaminononane, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and compounds according to formulas (II) to (X).

[0053] [ka]

[0054] In some cases, it may be desirable for the di- or oligoamine (A) to contain a certain degree of alkoxylation. Such alkoxylated di- or oligoamine (A) is reacted with the crosslinking compound (BC) in step (a). Generally, the degree of alkoxylation should be partial and should not hinder or adversely affect the reaction of the di- or oligoamine (A) with the crosslinking compound (BC) in step (a). For example, the molar ratio of the alkylene oxide (AO) to the NH functional value of the di- or oligoamine (A) is 0.25 or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.20. Preferably, the di- or oligoamine (A) is substantially not alkoxylated. For example, the molar ratio of the alkylene oxide (AO) to the NH functional value of the di- or oligoamine (A) is less than 0.05, for example less than 0.01, and particularly less than 0.001. Most preferably, the di- or oligoamine (A) does not contain alkoxylation.

[0055] Preferably, the molar ratio of the crosslinking compound (BC) to the di- or oligoamine (A) is in the range of 0.35 to 0.85, preferably 0.4 to 0.8, more preferably 0.45 to 0.75, and particularly in the range of 0.5 to 0.7.

[0056] Particularly preferred is a molar ratio of the epoxide group of the crosslinked compound (BC) to the NH functional value of the di- or oligoamine (A) being less than 0.5, preferably 0.45 or less, more preferably 0.4 or less, for example 0.1 to 0.45, preferably 0.15 to 0.4, and even more preferably 0.15 to 0.3, in order to form a nitrogen-containing polymer (NP) that is optionally alkoxylated.

[0057] The NH functional value represents the number of amines and is calculated by determining the number of secondary and primary amine groups, where NH = (number of secondary amine groups) + (2 × (number of primary amine groups)). The NH value is determined by titrating each polyalkylene imine with trifluoromethanesulfonic acid.

[0058] In one example of an arbitrarily alkoxylated nitrogen-containing polymer (NP), the proportion of di- or oligoamine molecular components having fewer than two amine groups bonded to the crosslinked compound (BC) molecular component is less than 25%.

[0059] However, the optionally alkoxylated nitrogen-containing polymer (NP) has a proportion of di- or oligoamine molecular components having fewer than two amino groups bonded to the crosslinked compound (BC) molecular component that is at least 20%, preferably 25% to 90%, more preferably 30% to 85%, more preferably 35% to 80%, usually 40% to 80%, often 45% to 75%, and preferably 50% to 75%.

[0060] Optionally alkoxylated nitrogen-containing polymers (NPs) are preferably produced by reacting a di- or oligoamine compound with a crosslinking compound (BC) under other suitable reaction conditions to form the nitrogen-containing polymer (NP). When preparing alkoxylated nitrogen-containing polymers (NPs), alkoxylation can be performed using a suitable alkoxyling agent, usually alkylene oxide.

[0061] Appropriately, nitrogen-containing polymers (NPs) can be prepared by mixing a di- or oligoamine compound with a crosslinking compound (BC) in a suitable vessel. The reaction can be carried out under anhydrous conditions or in the presence of a suitable solvent. When a solvent is used, it may be a water-soluble solvent, but preferably an organic solvent, more preferably a polar organic solvent, such as methanol, ethanol, isopropanol, acetone, DMF, or chloroform, and more preferably methanol. If the reaction product increases viscosity, it is desirable to use a solvent for such a reaction. If the ratio of the crosslinking compound to the di- or oligoamine (amine compound) is higher, for example, at least 1.3 equivalents of the crosslinking compound and 2 equivalents of the amine compound, it is desirable to use a solvent, especially a polar organic solvent, most preferably methanol. The reaction can be carried out at a suitable temperature. Preferably, the temperature can be above 25°C, usually at least 30°C, for example 30°C to 90°C, preferably 35°C to 85°C. When the reaction is carried out in the presence of a solvent, especially methanol, the reaction temperature is, for example 30°C to 45°C, usually 30°C to 40°C. When the reaction is carried out in the absence of a solvent, i.e., in an anhydrous state, the reaction temperature is 35°C to 90°C, for example 45°C to 85°C, preferably 50°C to 85°C, for example 60°C to 85°C, more preferably 70°C to 85°C, and even more preferably 75°C to 85°C. The reaction time depends on the mass of the reactants, the presence or absence of a solvent, and the reaction temperature. Generally, the reaction is completed in a period of 1 to 3 hours, for example 1.5 to 2.5 hours. If a solvent, especially an organic solvent such as methyl alcohol, is used, the solvent is removed from the nitrogen-containing polymer (NP) formed at the end of the reaction. This can be achieved by using high temperature and / or reduced pressure. Typically, this involves using temperatures above 60°C, for example 75°C to 95°C. When reduced pressure is used, the pressure is less than 1.0 bar, for example less than 500 millibars, usually less than 250 millibars.

[0062] The nitrogen-containing polymer (NP) used in this invention is typically liquid at 25°C.

[0063] Nitrogen-containing polymers (NPs) can be alkoxylated by the methods described herein.

[0064] Methods of use according to the present invention include the use of nitrogen-containing polymers (NPs), i.e., non-alkoxylated polymers.

[0065] In a preferred embodiment, the optionally alkoxylated nitrogen-containing polymer is an alkoxylated nitrogen-containing polymer (ANP). Alkoxylation of the nitrogen-containing polymer (NP) is usually achieved by reacting the nitrogen-containing polymer (NP) with an alkylene oxide. Preferably, the alkoxylation process is carried out in an aqueous medium. The alkylene oxide (AO) reacts with the NH group of the nitrogen-containing polymer (NP) to produce an alkoxylated substituent bonded to the nitrogen atom. Alternatively, the alkoxylated nitrogen-containing polymer may originate from the reaction of a di- or oligoamine (A) that has already been alkoxylated before the reaction with the crosslinking compound (BC). Pre-alkoxylation of the di- or oligoamine (A) may eliminate the need for post-alkoxylation of the nitrogen-containing polymer. In some cases, it may be desirable to further alkoxylate the nitrogen-containing polymer derived from a pre-alkoxylated di- or oligoamine (A). If alkoxylation of the nitrogen-containing polymer (NP) is desired, the alkoxylation step (b) is carried out after the nitrogen-containing polymer (NP) has been formed in step (a).

[0066] Preferably, the molar ratio of alkylene oxide (AO) to the NH functional value of the nitrogen-containing polymer (NP) is 0.25 or less, preferably in the range of 0.05 to 0.25, more preferably in the range of 0.05 to 0.2, and more preferably in the range of 0.05 to 0.15, for example, in the range of 0.075 to 0.125.

[0067] As described above, NH represents the number of amines and is calculated by determining the number of secondary and primary amine groups, where NH = (number of secondary amine groups) + (2 × (number of primary amine groups)). NH is determined by titrating each polyalkylene imine with trifluoromethanesulfonic acid.

[0068] In a typical representation, alkoxylated nitrogen-containing polymers (ANPs) contain structural elements according to formula (XI), [ka] (In the formula, the dotted line indicates the bond with the rest of the alkoxylated nitrogen-containing polymer; and (AB represents one alkylene oxide side chain).

[0069] Alkylene oxides (AOs) are any alkylene oxides suitable for alkoxylation of nitrogen-containing polymers (NPs). In preferred embodiments of the alkylene oxide, one or more C2-C2 12 -Alkylene oxide, preferably C2-C 10 - Alkylene oxide, more preferably a mixture of C2-C8-alkylene oxides, preferably ethylene oxide, propylene oxide or butylene oxide, more preferably propylene oxide or butylene oxide. Preferred embodiments of alkylene oxide (AO) are C2-C4-alkylene oxide and C8-C 12 - Containing a mixture of alkylene oxides, preferably in a ratio of 2:1 to 20:1, more preferably 5:1 to 10:1 of C2-C4 alkylene oxides and C8-C 12 -A mixture of alkylene oxides having a molar ratio with alkylene oxide. However, it is most preferable that the alkylene oxide (AO) is substantially a single alkylene oxide, for example, a single alkylene oxide in an amount exceeding 90% by mass, preferably exceeding 95% by mass, and more preferably exceeding 99% by mass.

[0070] Optionally alkoxylated nitrogen-containing polymers typically have a mass-average molecular weight (MW ) is at least 70% more than the mass average molecular weight (M W ) of the di- or oligoamine (A). Usually, the mass average molecular weight (M W ) of the optionally alkoxylated nitrogen-containing polymer is at least 150% more, preferably at least 300% more than the mass average molecular weight (M W ) of the di- or oligoamine (A).

[0071] Preferably, the number average molecular weight (Mn) of the optionally alkoxylated nitrogen-containing polymer is in the range of 600 to 50,000 g / mol, such as 600 to 20,000 g / mol, preferably 600 to 10,000 g / mol, more preferably 800 to 5,000 g / mol, even more preferably 600 to 2,500 g / mol, and most preferably 1,000 to 2,500 g / mol.

[0072] In a preferred embodiment, the fraction of the optionally alkoxylated nitrogen-containing polymer having a molecular weight exceeding 15,000 g / mol is less than 10%, and more preferably the fraction having a molecular weight exceeding 15,000 g / mol is less than 10%.

[0073] The polydispersity index (Mw / Mn) of the non-alkoxylated nitrogen-containing polymer (including the nitrogen-containing polymer (NP) before alkoxylation) is 7 or less, preferably in the range of 2 to 7, such as in the range of 3 to 7.

[0074] The ratio of the secondary amine to the primary amine in the non-alkoxylated nitrogen-containing polymer or the nitrogen-containing polymer before alkoxylation is in the range of 1.3:1 to 2.2:1, such as 1.4:1 to 2.1:1.

[0075] The total of the primary amine groups and the secondary amine groups of the non-alkoxylated nitrogen-containing polymer (NP) (including the polymer before alkoxylation) is at least 600 mg KOH / g. For example, this is at least 603 mg KOH / g.

[0076] The NH functional value of unalkoxylated nitrogen-containing polymers (NPs) (including polymers before alkoxylation) is at least 800 mg KOH / g. For example, this is at least 804 mg KOH / g.

[0077] The OH number of unalkoxylated nitrogen-containing polymers (NPs) (including polymers before alkoxylation) is in the range of 160-260 mg KOH / g, for example, 170-250 mg KOH / g.

[0078] Optionally alkoxylated nitrogen-containing polymers (NPs) are liquid at 25°C.

[0079] Preferably, optionally alkoxylated nitrogen-containing polymers are water-soluble. Water solubility means that optionally alkoxylated nitrogen-containing polymers can be dissolved or miscible with deionized water at a concentration of 350 g / l or less at a temperature of 25°C. Alkoxylated nitrogen-containing polymers are considered water-soluble if their aqueous solution does not show turbidity or phase separation and remains clear, especially after storage (e.g., after storage for at least 7 days).

[0080] The optionally alkoxylated nitrogen-containing polymer can be linear or branched. In one preferred embodiment, the alkoxylated nitrogen-containing polymer is branched. In this preferred embodiment, the branched alkoxylated nitrogen-containing polymer is preferably water-soluble. In another preferred embodiment, the alkoxylated nitrogen-containing polymer is linear. In this preferred embodiment, the linear alkoxylated nitrogen-containing polymer is water-soluble.

[0081] In a preferred embodiment, the optionally alkoxylated nitrogen-containing polymer is substantially not quaternized. For example, less than 10%, preferably less than 5%, more preferably less than 1%, particularly preferably less than 0.5%, and even more preferably less than 0.1% of the nitrogen atoms present in the optionally alkoxylated nitrogen-containing polymer are quaternized. In this embodiment, it is particularly preferred that the optionally alkoxylated nitrogen-containing polymer is not quaternized.

[0082] In preferred embodiments, the optionally alkoxylated nitrogen-containing polymer is alkoxylated, the molar ratio of alkylene oxide (AO) to the NH functional value of the nitrogen-containing polymer (NP) is less than 0.25, preferably 0.05 to 0.24, more preferably 0.05 to 0.2, and 50 mol% or more of the alkylene is derived from ethylene oxide, propylene oxide and / or butylene oxide, preferably butylene oxide.

[0083] In the following preferred embodiments, (1) In step a), the di- or oligoamine (A) is TPTA or PEHA, and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (2) In step a), the di- or oligoamine (A) is 3-(2-aminoethylamino)propylamine (N3-amine), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (3) In step a), the di- or oligoamine (A) is N,N'-bis-(3-aminopropyl)-ethylenediamine (N4-amine), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether, ethylene glycol diglycidyl ether, or 1,6-hexanediol bisglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (4) In step a), the di- or oligoamine (A) is triethyltetramine (TETA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (5) In step a), the di- or oligoamine (A) is tris(2-aminoethyl)amine (TAEA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (6) In step a), the di- or oligoamine (A) is diethylenetriamine (DETA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether, 1,3-neopentyl glycol bisglycidyl ether or 1,4-cyclohexanedimethanol bisglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (7) In step a), the di- or oligoamine (A) is a triaminononane, and the compound containing at least two glycidyl ether groups is ethylene glycol diglycidyl ether or 1,4-butanediol bisglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (8) In step a), the di- or oligoamine (A) is tetraethylenepentamine (TEPA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,4-butanediol bisglycidyl ether or diglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide per mole of nitrogen-containing polymer (NP) with NH functional value is used; or, (9) In step a), the di- or oligoamine (A) is pentaethylenehexamine (PEHA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol bisglycidyl ether; and in step b), 0.25 moles or less, preferably 0.05 to 0.25, more preferably 0.05 to 0.2 moles of propylene oxide or butylene oxide are used per mole of nitrogen-containing polymer (NP) with an NH functional value.

[0084] Optionally alkoxylated nitrogen-containing polymers can be used as appropriate to capture carbon dioxide from gas mixtures. A gas mixture refers to a mixture of carbon dioxide and at least one other gas. Preferably, the gas mixture is air from the atmosphere or any kind of exhaust gas. Typically, the exhaust gas is gas emitted from industrial processes, such as power plants. Furthermore, the exhaust gas may be generated from a variety of other devices, such as heat generators, e.g., commercial and household boilers, or kinetic generators, e.g., combustion engines of vehicles.

[0085] In a preferred form of use, an optionally alkoxylated nitrogen-containing polymer can be incorporated into a formulation for direct carbon dioxide capture. Preferably, the formulation is an alkoxylated nitrogen-containing polymer on a solid support, or the optionally alkoxylated nitrogen-containing polymer is present in a liquid composition (e.g., an aqueous solution).

[0086] Preferably, the optionally alkoxylated nitrogen-containing polymer is supported on a solid inorganic support (SIS). The solid inorganic support (SIS) preferably has a primary particle size in the range of 5 to 200 nm, for example, 5 to 50 nm, and exhibits a secondary size structure of 5 to 500 μm, preferably 30 to 300 μm.

[0087] The solid inorganic carrier (SIS) is preferably a particulate or macroscopic carrier. The solid inorganic carrier (SIS) can be a porous carrier. Such a porous solid inorganic carrier (SIS) may include clay. Typically, such clay may include one or more of bentonite, attapulgite, kaolinite, montmorillonite, ball clay, fluss earth, hectorite, palygorskite, saponite, sepiolite, and halloysite. Preferably, the porous solid inorganic carrier (SIS) may include silica, e.g., nanosilica, especially fumed silica or precipitated silica; titania; magnesia (MgO); alumina, e.g., γ-alumina; silica-alumina (SiO2-Al2O3); hydrated zinc chloride; calcium sulfate; and zeolites, e.g., natural zeolites or synthetic zeolites.

[0088] Preferably, the solid inorganic support (SIS) may be commercially available silica, such as fumed silica, AEROSIL® from Evonik, CAB-O-SIL® from Cabot, REOLOSIL® from Tokuyama; precipitated silica, HI-SIL® from PPG Industries, SIPENNAT® from Evonik, and FIESIL® and TOKUSIL® from Tokuyama.

[0089] Alternatively, the optionally alkoxylated nitrogen-containing polymer may be supported on an organic solid support, such as activated carbon, such as activated charcoal; an organic nonpolymer support; or a polymer support. In yet another embodiment, the optionally alkoxylated nitrogen-containing polymer may be supported on an inorganic-organic solid support containing both inorganic and organic components, for example, as a composite.

[0090] Solid inorganic carriers (SIS), solid organic carriers, or solid inorganic-organic solid carriers can take the form of cavities or solid particles, beads, microspheres, sheets, cavities or solid fibers, monolithic structures, films, or honeycomb structures. Preferably, solid inorganic carriers (SIS), organic solid carriers, or solid inorganic-organic carriers are particulate and can take the form of powders or granules. The average particle size (D50) is in the range of 0.002 mm to 5 mm, for example, 0.01 mm to 4 mm, typically 0.25 mm to 4 mm.

[0091] In one embodiment, the solid inorganic support (SIS), solid organic support, or solid inorganic-organic solid support, preferably the solid inorganic support (SIS), is porous, and 50m 2 It has a surface area exceeding / g. In a particular embodiment, the surface area is 10m 2 Exceeding / g, 5000m 2 It is less than / g. In other specific embodiments, the surface area is 25m². 2 Exceeding / g, 1000m 2 In other embodiments, the surface area is 50 m². 2 / g~500m 2 / g, for example, 75m 2 / g~300m 2 / g, for example, 100m 2 / g~120m 2 It is / g. In a particular embodiment, the surface area is 200m². 2 / g~400m 2 / g, for example 200m 2 / g~300m 2 It is / g.

[0092] The surface area of ​​the porous support can be measured by the Brunauer-Emmett-Teller (BET) method according to DIN ISO 9277:2003-05 (a revised version of DIN 66131). The specific surface area can be determined by multipoint BET measurements in the relative pressure range of 0.05 to 0.3 p / p0.

[0093] In another embodiment, the solid inorganic support (SIS), solid organic support, or solid inorganic-organic solid support, preferably the solid inorganic support (SIS), is porous, and 0.1 cm 3 / g~3.0cm 3 / g, for example, 0.2cm 3 / g~0.8cm 3 It has an average pore volume in the range of / g. The average pore volume can be measured according to the Barrett-Joyner-Halenda (BGH) method for measuring pore volume.

[0094] The preferred solid inorganic support (SIS) is selected from silica supports or alumina supports. Preferably, the silica support or alumina support may encompass any of the embodiments described above.

[0095] An optionally alkoxylated nitrogen-containing polymer can be impregnated in any embodiment onto or within a solid carrier, preferably a solid inorganic carrier (SIS), more preferably a solid inorganic carrier (SIS) selected particularly from silica carriers or alumina carriers, by any known prior art for impregnating such solid carriers with amines or polyamines.

[0096] In one embodiment, an optionally alkoxylated nitrogen-containing polymer can be impregnated into a particulate solid carrier, such as porous silica, by introducing the particulate solid carrier into a suitable container typically used to prepare granules or pellets of porous solids such as silica impregnated with amines or polyamines. Such a container is typically a disc pelletizer or ball pelletizer. This allows the optionally alkoxylated nitrogen-containing material to be introduced into the container and mixed with the porous solid, such as silica, by, for example, rotating the container. This mixing is typically performed by rotating the disc of a disc pelletizer or the drum of a ball pelletizer, as a pelletizing device. Preferably, this process forms moist granules, which can be dried at a high temperature, e.g., 40-70°C, for 1-4 hours in an inert atmosphere, typically under nitrogen. The granules thus formed, impregnated with the optionally alkoxylated nitrogen-containing polymer, can be used to capture carbon dioxide from a mixed gas.

[0097] A particularly preferred embodiment relates to a method for using optionally alkoxylated nitrogen-containing polymers in direct air capture (DAC). Direct air capture (DAC) relates to a technique for directly extracting carbon dioxide from the atmosphere. Such techniques typically use carbon dioxide adsorbents that directly adsorb carbon dioxide from the air, then desorb it under a controlled environment, and further process it to convert it into a form that can be used for permanent storage of carbon dioxide.

[0098] The optionally alkoxylated nitrogen-containing polymer of the present invention can be used as an adsorbent for directly capturing carbon dioxide from air in direct air capture (DAC). The optionally alkoxylated nitrogen-containing polymer is preferably used in an appropriate formulation form, such as a liquid formulation or preferably in a form impregnated with a suitable solid carrier, more preferably a porous inorganic adsorbent (SIS), such as granules.

[0099] The following examples are illustrative of the present invention and do not limit its scope. [Examples]

[0100] Procedure A When the proportion of the crosslinking compound is high (1.3 equivalents), the amine compound is diluted with methanol to obtain a 50% solution.

[0101] One mole of the amine compound was placed in a 500 mL four-necked flask equipped with an anchor stirrer, a recirculating condenser, and a dropping funnel. The solution was heated to 35°C and stirred at 150 rpm. The crosslinking compound was added via the funnel within 90 minutes. After another 30 minutes, the viscous liquid was transferred to a rotary evaporator (Buechi), and the solvent was removed at 90°C to obtain a viscous liquid.

[0102] [Table 1]

[0103] Procedure B One mole of the amine compound was placed in a 500 mL three-necked flask equipped with an anchor stirrer and a dropping funnel. The amine compound was heated to 50°C, and the crosslinking compound was added via the funnel within 90 minutes while stirring at 150 rpm. During this time, the temperature was maintained below 85°C. The reaction mixture was held at 80°C for a further hour, and then cooled to room temperature (RT) to obtain a viscous product.

[0104] [Table 2]

[0105] Step C

[0106] [Table 3]

[0107] Comparative Example Step D A 50% aqueous solution of PEHA and TEPA was added to a 1-liter autoclave equipped with a stirrer. Alkylene oxide was added within 90 minutes at 40°C. The reaction temperature was maintained at 95°C for 2 hours, then stirred overnight at room temperature (RT). The mixture was placed in a 2-liter Buechi flask, and the water was removed at 80°C and 100 millibars. A yellowish liquid was obtained.

[0108] [Table 4] TIFF2026512522000008.tif250146

[0109] Examples 6 and 9 were propoxylated with 1.5 mmol of PO per gram of polymer to obtain Examples 19 and 20.

[0110] Example 19 250 g of the polymer from Example 6 was packed into a 1 L stainless steel reactor with a stirrer, followed by the addition of 250 g of water. The reactor was evacuated to 60 mmbar and purged three times with nitrogen while raising the temperature to 100°C. The reactor was pressurized to 2 bar, and 21.8 g of propylene oxide (PO) was added over 5 minutes. The temperature was raised to 115°C over 3.5 hours with stirring at 150 rpm, and then maintained at that temperature. The reactor was then cooled to 60°C and the pressure was reduced. Finally, the reactor was treated at 100 mmbar for 10 minutes and purged with nitrogen. 520 g of a slightly yellowish liquid was obtained.

[0111] Example 20 The procedure of Example 19 was repeated using 250 g of the polymer from Example 9.

[0112] Furthermore, the amine adsorbent was supported on silica, and the absorption of CO2 was investigated before and after storage in air at 90°C for 14 days.

[0113] Determination of the equilibrium load of CO2 The equilibrium load was measured in a bubble column reactor, as described in BRECHTEL, K. Einfluss der Molekuelstruktur auf die -Abtrennung mit waessrigen Aminloesungen aus Rauchgasen fossil befeuerter Kraftwerke. Dissertation / PhD, Universitaet Stuttgart, 2011; A. Schaeffer, Amine und Aminmischungen zur-Absorption aus Kraftwerksrauchgasen und ihr Energiebedarf zur Regeneration Dissertation / PhD, Universitaet Stuttgart, 2013.

[0114] In this process, 0.15 kg of sample was diluted with 0.15 kg of water to obtain a 50% aqueous solution. The sample was heated in a water bath equipped with an adjustable heating plate, and a synthesized flue gas with a composition of 15 vol% CO2, 5 vol% O2, and 80 vol% N2 was flowed through it at a flow rate of 2 l / min. The flue gas was injected into the sample via glass frit (pore size 1) using a mass flow controller, thereby achieving good mixing and a large mass area. The discharged (excess) low CO2 gas flow was supplied to the infrared gas analyzer via a return flow rate and a sample gas condenser. The reflux condenser condensed the evaporated water or solvent and returned it to the sample. The gas composition was continuously measured with the infrared gas analyzer and recorded via a computer interface.

[0115] Therefore, the sample mass [kg] is in equilibrium with the CO2 concentration or dominant CO2 partial pressure in the exhaust gas. The volume of CO2 absorbed into the solvent [m³] is obtained from integral calculations over time [minutes]. The inflowing exhaust gas flow rate [l / min] is constant. Therefore, the equilibrium load was calculated as the mass percentage of CO2 relative to the mass of a 50% sample solution. For this purpose, the equilibrium load was determined at a temperature of 50°C.

[0116] [Table 5]

[0117] To measure resistance to evaporation, the amines from Examples 1-20 and the Comparative Examples were adsorbed onto a silica compound (using silica described in the University of California patent, which is Sipernat 50S2 from Evonik Resource Efficiency GmbH).

[0118] Examples of silica-supported adsorbents were obtained by treating 50% aqueous solutions of Examples 1-20 and Comparative Examples with Sipernat 50S2 in a 1:1 ratio. After evaporation of the solvent (90°C, 100 mg / L), 100 g of adsorbent was stored at 90°C for 14 days in an atmosphere containing 95% CO2 and 5% O2. Every 48 hours, the adsorbent was vacuumed at 40 mg / L, exposed to the desorption temperature at 105°C for 90 minutes, and then stored again in a CO2 / O2 atmosphere. This operation was repeated for 10 cycles over 20 days.

[0119] [Table 6]

Claims

1. A method for using an optionally alkoxylated nitrogen-containing polymer in carbon dioxide capture, wherein the optionally alkoxylated nitrogen-containing polymer is used in the following steps: a) A step of providing a nitrogen-containing polymer (NP) by reacting (i) a di- or oligoamine (A) with (ii) a crosslinking compound (BC), wherein the crosslinking compound (BC) is (i) is phosgene; or (II) comprising at least two amine-reactive groups (ARGs), The crosslinked compound (BC) can bond to at least two amine groups of di- or oligoamine (A) molecules. The nitrogen-containing polymer (NP) contains molecular components of a crosslinking compound (BC) that are bound to at least two molecular components of a di- or oligoamine (A), and the proportion of crosslinking compound (BC) molecules bound to at least two di- or oligoamine (A) molecules is the crosslinking factor (BF) of the nitrogen-containing polymer (NP), and the crosslinking factor (BF) exceeds 50%. The total amount of primary and secondary amine groups in the nitrogen-containing polymer (NP) is at least 600 mg KOH / g. The process involves the nitrogen-containing polymer (NP) having a number-average molecular weight (Mn) exceeding 600 g / mol, and b) A step to obtain an alkylene oxide side chain (AB) bonded to the nitrogen atom of the nitrogen-containing polymer (NP) and to provide an alkoxylated nitrogen-containing polymer (ANP), wherein the nitrogen-containing polymer (NP) is reacted with an alkylene oxide (AO) preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of the alkylene oxide (AO) to the NH functional group of the nitrogen-containing polymer (NP) is 0.25 or less. A method of use that can be obtained by a method including the following.

2. The aforementioned crosslinking compound (BC) (1) A reaction product formed by reacting (i) a diol or polyol with (ii) an epihalohydrin; or (2) A compound comprising at least two amine-reactive groups (ARGs), selected from a compound comprising at least two glycidyl ether groups or a compound comprising at least two isocyanate groups; or (3) Phosgene The method of use according to claim 1.

3. The crosslinked compound (BC) is a compound containing at least two glycidyl ether groups, and the compound is (i) containing at least two structures according to formula (I) 【Chemistry 1】 (In the formula, the dotted line indicates the bond with the rest of the compound containing at least two glycidyl ether groups), preferably the compound containing at least two glycidyl ether groups has two structures according to formula (I), and / or (ii) Selected from 1,4-butanediol bisglycidyl ether, 1,6-hexanediol bisglycidyl ether, diglycidyl ether, 1,3-neopentyl glycol bisglycidyl ether, 1,4-cyclohexanedimethanol bisglycidyl ether, ethylene glycol bisglycidyl ether, glycerin triglycidyl ether, and trimethylolpropane triglycidyl ether, The method of use according to claim 1 or 2.

4. The method of use according to claim 2, wherein the diol or polyol is selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, 1,3-neopentyl glycol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

5. The at least one di- or oligoamine (A) is (i) Having at least two amino groups, preferably two to twelve amino groups, more preferably two to eight amino groups, and more preferably three, four, five, six, seven, or eight amino groups; (ii) Having at least one carbon atom per nitrogen atom, preferably 1 to 5 carbon atoms per nitrogen atom, more preferably 1 to 3 carbon atoms per nitrogen atom; (iii) comprising at least two primary and / or secondary amino groups, preferably at least two primary amino groups; (iv) Having a molecular weight (Mw) in the range of 50 to 500 g / mol, preferably 60 to 300 g / mol, more preferably 80 to 250 g / mol, even more preferably 120 to 250 g / mol, and particularly preferably 150 to 250 g / mol; and / or (v) Selected from the group consisting of ethylenediamine, hexamethylenediamine, methylcyclohexanediamine (MCDA), propylenediamine (PDA), tetramethylenediamine (TMDA), pentamethylenediamine (PMDA), dipropylenetriamine (DPTA), tripylenetetramine (TPTA), tris(2-aminoethyl)amine (TAEA), tetrapropylenepentamine (TPPA), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), 3-(2-aminoethylamino)propylamine (N3-amine), spermine, spermidine, triaminononane, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and compounds according to formulas (II) to (X), 【Chemistry 2】 The method of use according to any one of claims 1 to 4.

6. The method of use according to any one of claims 1 to 5, wherein the molar ratio of the bridge compound (BC) to the di- or oligoamine is 0.35 to 0.85, preferably 0.4 to 0.8, and more preferably 0.45 to 0.

75.

7. The method of use according to any one of claims 1 to 6, wherein the molar ratio of the epoxide group of the crosslinked compound (BC) to the NH functional value of the di- or oligoamine is less than 0.5, preferably 0.45 or less, and more preferably 0.15 to 0.

4.

8. The method of use according to any one of claims 1 to 7, wherein the optionally alkoxylated nitrogen-containing polymer is an alkoxylated nitrogen-containing polymer (ANP), and the molar ratio of alkylene oxide (AO) to NHNH functional value is 0.05 to 0.25, more preferably 0.05 to 0.

2.

9. The alkoxylated nitrogen-containing polymer (ANP) comprises a structural element according to formula (XI), 【Transformation 3】 (In the formula, the dotted line indicates the bond with the rest of the alkoxylated nitrogen-containing polymer; and The method of use according to any one of claims 1 to 8 (where AB represents one alkylene oxide side chain).

10. Optionally, the alkoxylated nitrogen-containing polymer has a mass-average molecular weight (M) of the di- or oligoamine (A). Ｗ ) is at least 70% larger than the mass-average molecular weight (M Ｗ A method of use according to any one of claims 1 to 9, comprising:

11. The method of use according to any one of claims 1 to 10, wherein the optionally alkoxylated nitrogen-containing polymer has a number average molecular weight (Mn) in the range of 600 to 150,000 g / mol, more preferably 600 to 75,000 g / mol, more preferably 600 to 50,000 g / mol, for example 600 to 20,000 g / mol, preferably 600 to 10,000 g / mol, more preferably 600 to 5,000 g / mol, more preferably 600 to 2,500 g / mol, and more preferably 1,000 to 2,500 g / mol.

12. The aforementioned optionally alkoxylated nitrogen-containing polymer (i) water-soluble; and / or (ii) It is a branched polymer. The method of use according to any one of claims 1 to 11.

13. The method of use according to any one of claims 1 to 12, wherein less than 10%, preferably less than 5%, of the nitrogen atoms present in the optionally alkoxylated nitrogen-containing polymer are quaternized.

14. The method of use according to any one of claims 1 to 13, wherein the optionally alkoxylated nitrogen-containing polymer is alkoxylated, the molar ratio of alkylene oxide (AO) to the NH functional value of the nitrogen-containing polymer (NP) is 0.05 to 0.25, preferably 0.05 to 0.2, and more than 50 mol% of the alkylene oxide is based on ethylene oxide, propylene oxide and / or butylene oxide, preferably propylene oxide or butylene oxide.

15. (1) In step a), the di- or oligoamine (A) is TPTA or PEHA, and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide are used per mole of NH functional value of the nitrogen-containing polymer (NP); or, (2) In step a), the di- or oligoamine (A) is 3-(2-aminoethylamino)propylamine (N3-amine), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of nitrogen-containing polymer (NP) is used; or, (3) In step a), the di- or oligoamine (A) is N,N'-bis-(3-aminopropyl)-ethylenediamine (N4-amine), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or 1,6-hexanediol bisglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of nitrogen-containing polymer (NP) is used; or, (4) In step a), the di- or oligoamine (A) is triethyltetramine (TETA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of nitrogen-containing polymer (NP) is used; or, (5) In step a), the di- or oligoamine (A) is tris(2-aminoethyl)amine (TAEA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether, ethylene glycol diglycidyl ether, or 1,6-hexanediol bisglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of nitrogen-containing polymer (NP) is used; or, (6) In step a), the di- or oligoamine (A) is diethylenetriamine (DETA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether or 1,6-hexanediol bisglycidyl ether, 1,3-neopentyl glycol bisglycidyl ether or 1,4-cyclohexanedimethanol bisglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of nitrogen-containing polymer (NP) is used; or, (7) In step a), the di- or oligoamine (A) is a triaminononane, and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol diglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of the nitrogen-containing polymer (NP) is used; or, (8) In step a), the di- or oligoamine (A) is tetraethylenepentamine (TEPA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or diglycidyl ether or ethylene glycol diglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide per mole of NH functional value of nitrogen-containing polymer (NP) is used; or, (9) In step a), the di- or oligoamine (A) is pentaethylenehexamine (PEHA), and the compound containing at least two glycidyl ether groups is 1,4-butanediol bisglycidyl ether or ethylene glycol bisglycidyl ether; and in step b), less than 0.25 moles of propylene oxide or butylene oxide are used per mole of NH functional value of the nitrogen-containing polymer (NP). The method of use according to any one of claims 1 to 14.

16. The method of use according to any one of claims 1 to 15, wherein the optionally alkoxylated nitrogen-containing polymer is used to capture carbon dioxide from a gas mixture.

17. The aforementioned optionally alkoxylated nitrogen-containing polymer is incorporated into a formulation for direct capture of carbon dioxide. Preferably, the above-mentioned composition is (i) The alkoxylated nitrogen-containing polymer on a solid support; or (ii) The optionally alkoxylated nitrogen-containing polymer in a liquid composition, for example, in an aqueous solution. A method of use according to any one of claims 1 to 16, including the method of use described in any one of claims 1 to 16.

18. The method of use according to claim 16 or 17, wherein the gas mixture is air from the atmosphere or exhaust gas.

19. The method of use according to any one of claims 1 to 18, wherein the optionally alkoxylated nitrogen-containing polymer is supported on a solid inorganic carrier (SIS), preferably the solid inorganic carrier (SIS) is particulate or macroscopic, preferably the solid inorganic carrier (SIS) is particulate, preferably powder or granules.

20. The method of use according to claim 19, wherein the solid inorganic support (SIS) is selected from silica or alumina support.

21. The method of use according to any one of claims 1 to 20, wherein the optionally alkoxylated nitrogen-containing polymer is used directly for air collection (DAC).

22. A method for capturing carbon dioxide, comprising contacting a gas mixture containing carbon dioxide with an optionally alkoxylated nitrogen-containing polymer in carbon dioxide capture, and contacting the optionally alkoxylated nitrogen-containing polymer with carbon dioxide, wherein the optionally alkoxylated nitrogen-containing polymer is: a) A step of providing a nitrogen-containing polymer (NP) by reacting (i) a di- or oligoamine (A) with (ii) a crosslinking compound (BC), wherein the crosslinking compound (BC) is (i) is phosgene; or (II) comprising at least two amine-reactive groups (ARGs), The crosslinked compound (BC) can bond to at least two amine groups of di- or oligoamine (A) molecules. The nitrogen-containing polymer (NP) contains molecular components of a crosslinking compound (BC) that are bound to at least two molecular components of a di- or oligoamine (A), and the proportion of crosslinking compound (BC) molecules bound to at least two di- or oligoamine (A) molecules is the crosslinking factor (BF) of the nitrogen-containing polymer (NP), and the crosslinking factor (BF) exceeds 50%. The total amount of primary and secondary amine groups in the nitrogen-containing polymer (NP) is at least 600 mg KOH / g. The process involves the nitrogen-containing polymer (NP) having a number-average molecular weight (Mn) exceeding 600 g / mol, and b) A step to obtain an alkylene oxide side chain (AB) bonded to the nitrogen atom of the nitrogen-containing polymer (NP) and to provide an alkoxylated nitrogen-containing polymer (ANP), wherein the nitrogen-containing polymer (NP) is reacted with an alkylene oxide (AO) preferably selected from the group consisting of at least one of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BuO), wherein the molar ratio of the alkylene oxide (AO) to the NH functional group of the nitrogen-containing polymer (NP) is 0.25 or less. A method that can be obtained by a method including the following.

23. The method according to claim 22, wherein the optionally alkoxylated nitrogen-containing polymer (NP) has the characteristics described in any one of claims 2 to 21.

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