Compositions and applications having acid gas absorption functionality

Abstract

The present application relates to the field of gas separation and purification, discloses a kind of composition and application with acid gas absorption function.The composition includes amino acid salt, organic amine and water;The organic amine is the compound with formula (I) shown in structure, A1-A4 each independently be H, -CR 1 R 2 CHR 3 (CH2) n COM, -CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2, -CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2)2 and CR 1 R 2 CHR 3 (CH2) n CONHN structure is 2 m -1 one of group, m is 1-20 integer.The composition provided by the present application has good gas purification and separation effect, and has strong industrial application and operability.

Description

Technical Field

[0001] This invention relates to the field of gas separation and purification, and more specifically to a composition and its application that has the function of absorbing acidic gases. Background Technology

[0002] Using MEA (ethanolamine) aqueous solution for gas decarbonization is one of the more mature methods, but a common problem is that its absorption performance needs improvement. To address this issue, current research focuses on developing new absorbents and improving or researching new processes. The main research approach for new absorbents is to develop novel chemical absorbents.

[0003] According to existing literature, the industrial operating data of MEA (Metal Absorber) shows that when the capture rate reaches 80%, the absorption capacity is 18 L / L, indicating that the absorption performance still needs improvement. Therefore, the search for new absorbents with good decarbonization performance (such as the absorption of acidic gases) remains a hot topic of research. Summary of the Invention

[0004] The purpose of this invention is to overcome the above-mentioned technical problems and provide a composition and application with acid gas absorption function.

[0005] To achieve the above objectives, a first aspect of the present invention provides a composition having an acid gas absorption function, the composition comprising an amino acid salt, an organic amine, and water;

[0006] The organic amine is a compound having the structure shown in formula (I).

[0007]

[0008] in,

[0009] A1-A4 are each independently H, -CR 1 R 2 CHR 3 (CH2) n COM, -CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2、-CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2)n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2)2 and CR derived from this pattern 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m One of the groups with -1, where m is an integer from 1 to 20;

[0010] Among them, R 1 R 2 and R 3 Each is independently an H or C1-C4 alkyl group, n is an integer from 0 to 6, and M is an NHNH2 or C1-C4 alkoxy group;

[0011] Among them, A1-A4 are not all H and at least one of A1-A4 contains -NHNH2.

[0012] A second aspect of the present invention provides the application of the composition described in the first aspect above in gas absorption, particularly in the absorption of acidic gases;

[0013] Preferably, the acidic gas is an inorganic acidic gas, more preferably at least one of carbon dioxide, sulfur dioxide, and hydrogen sulfide.

[0014] A third aspect of the present invention provides a method for absorbing gas, the method comprising: contacting the composition described in the first aspect above or an aqueous solution containing a compound with the structure shown in formula (I) with the gas to be absorbed;

[0015] Preferably, in the aqueous solution containing the compound with the structure shown in formula (I), the mass fraction of the solute of the compound with the structure shown in formula (I) is 0.1-20 wt%.

[0016] A fourth aspect of the present invention provides the application of a compound with the structure shown in formula (I) in gas absorption, particularly in the absorption of acidic gases.

[0017] Compared with the prior art, the technical solution provided by the present invention has at least the following advantages:

[0018] (1) The composition provided by the present invention (with gas absorption function) has good gas purification and separation effect, and is highly operable and applicable to industrial applications.

[0019] (2) In the composition of this invention, the organic amine (the compound with the structure shown in formula (I)) is a type of compound independently developed by this invention. It is prepared by reacting an acrylate with hydrazine (hydrazine) and is a novel compound molecule with high Y-type and high order. From the molecular structure, this compound is similar to a Y-type compound, which is obtained by continuously repeating Y-type radial growth outward from a dual-core molecule (hydrazine). When the above compound is used as a component of a gas absorbent (especially an acidic gas absorbent), it can significantly improve the gas purification efficiency.

[0020] (3) The present invention also provides a method for preparing organic amines (compounds with the structure shown in formula (I)), which has the advantages of simple steps, high efficiency, environmental friendliness and high yield and purity, and is conducive to industrialization. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] To achieve the above objectives, a first aspect of the present invention provides a composition having an acid gas absorption function, the composition comprising an amino acid salt, an organic amine, and water;

[0023] The organic amine is a compound having the structure shown in formula (I).

[0024]

[0025] in,

[0026] A1-A4 are each independently H, -CR 1 R 2 CHR 3 (CH2) n COM, -CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2、-CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2)2 and CR derived from this pattern 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m One of the groups with -1, where m is an integer from 1 to 20;

[0027] Among them, R 1 R 2 and R 3 Each is independently an H or C1-C4 alkyl group, n is an integer from 0 to 6, and M is an NHNH2 or C1-C4 alkoxy group;

[0028] Among them, A1-A4 are not all H and at least one of A1-A4 contains -NHNH2.

[0029] In this invention, the C1-C4 alkyl groups include straight-chain or branched alkyl groups of C1-C4.

[0030] In this invention, the C1-C4 alkoxy groups include straight-chain or branched-chain alkoxy groups of C1-C4.

[0031] According to some embodiments of the present invention, A1-A4 are each independently -CR 1 R 2 CHR 3 (CH2) n COM or -CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2、-CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2)2 and CR derived from this pattern 1 R2 CHR 3 (CH2) n CONHN consists of m groups, where m is an integer from 1 to 10.

[0032] According to some embodiments of the present invention, R 1 R 2 and R 3 Each can be independently one of H, methyl, and ethyl.

[0033] According to some embodiments of the present invention, n is an integer from 0 to 4.

[0034] According to some embodiments of the present invention, m ≤ 5.

[0035] According to some embodiments of the present invention, M is NHNH2.

[0036] According to some embodiments of the present invention, A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, where R 1 =H,R 2 =H,R 3 =H, n is 0, M is NHNH2; or,

[0037] A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, where R 1 =H,R 2 =H,R 3 =H, n is 1, M is NHNH2; or,

[0038] A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, where R 1 =Me,R 2 =H,R 3 =H, n is 0, M is NHNH2; or,

[0039] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R2 =H,R 3 =H, n is 0, m is 1, M is NHNH2; or,

[0040] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 1, M is NHNH2; or,

[0041] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 1, M is NHNH2; or,

[0042] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 2, M is NHNH2; or,

[0043] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 2, M is NHNH2; or,

[0044] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R1 =Me,R 2 =H,R 3 =H, n is 0, m is 2, M is NHNH2; or,

[0045] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 3, M is NHNH2; or,

[0046] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 3, M is NHNH2; or,

[0047] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 3, M is NHNH2; or,

[0048] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 4, M is NHNH2; or,

[0049] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m-1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 4, M is NHNH2; or,

[0050] A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 4, M is NHNH2.

[0051] The inventors of this invention discovered that, based on the Michael addition reaction principle, grafting groups of different lengths (e.g., acrylate chains) can be reacted with hydrazine (as the initiating nucleus) to continuously grow radially outward, yielding compounds containing different or identical substituted grafting groups. These compounds are well-suited for gas absorption. However, considering factors such as cost and ease of operation, it is preferable to use the same grafting groups to obtain highly symmetrical molecules resembling Y-type compounds.

[0052] Therefore, preferably, in this invention, the compound with the structure shown in formula (I) is prepared according to a method comprising the following steps:

[0053] (1) In the presence of the first solvent, hydrazine reacts with CR 1 R 2 =CR 3 (CH2) n COOR 4 The first contact was performed to obtain the first-generation matrix compound (1G matrix compound); wherein, R 1 R 2 R 3 and R 4 Each is independently an H or C1-C4 alkyl group, and n is an integer from 0 to 6;

[0054] (2) In the presence of a second solvent, the first-generation matrix compound is subjected to a second contact with hydrazine to obtain the first-generation target compound (1G target compound);

[0055] (3) Optionally, in the presence of a third solvent, the first-generation target compound is reacted with CR. 1 R 2 =CR 3 (CH2) n COOR 4A third contact was made to obtain the second-generation matrix compound (2G matrix compound);

[0056] (4) Optionally, in the presence of a fourth solvent, the second-generation matrix compound is subjected to a fourth contact with hydrazine to obtain the second-generation target compound (2G target compound);

[0057] (5) Optionally, following this pattern, steps (3) and (4) are repeated to obtain a product containing the target compound of generation q; where q is an integer from 3 to 20. The product containing the target compound of generation q can be used directly as an organic amine, or it can be used as an organic amine after a simple solvent removal step (such as distillation).

[0058] According to some embodiments of the present invention, R 1 R 2 R 3 and R 4 Each can be independently one of H, methyl, and ethyl.

[0059] According to some embodiments of the present invention, n is an integer from 0 to 4.

[0060] According to some embodiments of the present invention, in step (1), the first solvent may be selected from water and / or C1-C4 alcohols, preferably methanol and / or water.

[0061] According to some embodiments of the present invention, the amount of the first solvent used relative to 1g of hydrazine can be 2-20mL, preferably 3-15mL.

[0062] According to some embodiments of the present invention, in step (1), in order to make the reaction proceed better, CR is... 1 R 2 =CR 3 (CH2) n COOR 4 There are certain requirements for the amount of hydrazine used, and under preferred conditions, CR 1 R 2 =CR 3 (CH2) n COOR 4 Excessive, for example, CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio of hydrazine to hydrazine can be (4-12):1, preferably (6-10):1.

[0063] According to some embodiments of the present invention, the first contact is carried out by adding hydrazine and / or hydrazine solution to CR at 20-40°C.1 R 2 =CR 3 (CH2) n COOR 4 in solution.

[0064] In this invention, in step (1), the hydrazine solution is obtained by dissolving hydrazine in the first solvent; the CR 1 R 2 =CR 3 (CH2) n COOR 4 The solution is composed of CR 1 R 2 =CR 3 (CH2) n COOR 4 It is obtained by dissolving in the first solvent; wherein, there are no special requirements for the amount of the first solvent used for dissolution, as long as it can meet the requirements of the present invention.

[0065] According to some embodiments of the present invention, in order to obtain better results, in step (1), there are certain requirements for the addition rate of hydrazine and / or hydrazine solution. Preferably, the addition rate is 1-10 mL / min relative to 100 mL of hydrazine and / or hydrazine solution, more preferably 1-5 mL / min.

[0066] According to some embodiments of the present invention, the first contact time can be 12-72 hours, preferably 24-48 hours. Specifically, when hydrazine and / or hydrazine solution begins to be added dropwise, hydrazine reacts with CR... 1 R 2 =CR 3 (CH2) n COOR 4 A reaction begins.

[0067] According to some embodiments of the present invention, in step (2), the second solvent may be selected from water and / or C1-C4 alcohols, preferably methanol and / or water.

[0068] According to some embodiments of the present invention, the amount of the second solvent used relative to 1g of hydrazine can be 2-20mL, preferably 3-15mL.

[0069] According to some embodiments of the present invention, in step (2), in order to make the reaction proceed better, there are certain requirements on the amount of the first-generation matrix compound and hydrazine, and preferably, the first-generation matrix compound is in excess. For example, the molar ratio of hydrazine to the first-generation matrix compound can be (4-20):1, preferably (8-16):1.

[0070] According to some embodiments of the present invention, the second contact is carried out by adding a solution of the first-generation matrix compound to hydrazine and / or a hydrazine solution at 20-40°C.

[0071] In this invention, in step (2), the hydrazine solution is obtained by dissolving hydrazine in the second solvent; the solution of the first-generation matrix compound is obtained by dissolving the first-generation matrix compound in the second solvent; there are no special requirements for the amount of the second solvent used for dissolution, as long as it meets the requirements of this invention.

[0072] According to some embodiments of the present invention, in step (2), in order to make the reaction proceed better, there are certain requirements on the addition rate of the solution of the first-generation matrix compound. Preferably, the addition rate is 1-20 mL / min relative to 100 mL of the solution of the first-generation matrix compound, more preferably 1-10 mL / min.

[0073] According to some embodiments of the present invention, the second contact time can be 12-72 hours, preferably 24-48 hours. Specifically, the first-generation matrix compound begins to react with hydrazine when the solution of the first-generation matrix compound is added dropwise.

[0074] According to some embodiments of the present invention, in step (3), in order to make the reaction proceed better, the first-generation target compound is reacted with CR 1 R 2 =CR 3 (CH2) n COOR 4 The dosage has certain requirements, and under preferred conditions, CR 1 R 2 =CR 3 (CH2) n COOR 4 Excess, for example, the first-generation target compound with CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio can be 1:(8-20), preferably 1:(12-18).

[0075] According to some embodiments of the present invention, the third contact is carried out by adding a solution of the first-generation target compound to CR at 20-40°C. 1 R 2 =CR 3 (CH2) n COOR 4 in solution.

[0076] In this invention, in step (3), the solution of the first-generation target compound is obtained by dissolving the first-generation target compound in the third solvent; the CR 1 R 2 =CR 3 (CH2) n COOR 4 The solution is composed of CR 1 R 2 =CR 3 (CH2) n COOR 4 It is obtained by dissolving in the third solvent; wherein, there are no special requirements for the amount of the third solvent used for dissolution, as long as it can meet the requirements of the present invention.

[0077] According to some embodiments of the present invention, in order to make the reaction proceed better, there are certain requirements on the addition rate of the solution of the first-generation target compound. Preferably, the addition rate is 1-20 mL / min relative to 100 mL of the solution of the first-generation target compound, more preferably 1-10 mL / min.

[0078] According to some embodiments of the present invention, the third contact time is 12-72 hours, preferably 24-48 hours. Specifically, when the solution of the first-generation target compound is started to be added dropwise, the first-generation target compound reacts with CR... 1 R 2 =CR 3 (CH2) n COOR 4 A reaction begins.

[0079] According to some embodiments of the present invention, the amount of the third solvent used is 2-20 mL, preferably 3-15 mL, relative to 1 g of the first-generation target compound.

[0080] According to some embodiments of the present invention, in step (4), there are certain requirements for the amount of the second-generation matrix compound and hydrazine, and preferably, hydrazine is in excess, and the molar ratio of the second-generation matrix compound to hydrazine is 1:(16-32), preferably 1:(18-24).

[0081] According to some embodiments of the present invention, the fourth contact is carried out by adding a solution of the second-generation matrix compound to hydrazine and / or a hydrazine solution at a temperature of 20-40°C.

[0082] In this invention, in step (4), the hydrazine solution is obtained by dissolving hydrazine in the fourth solvent; the solution of the second-generation matrix compound is obtained by dissolving the second-generation matrix compound in the fourth solvent; there are no special requirements for the amount of the fourth solvent used for dissolution, as long as it meets the requirements of this invention.

[0083] According to some embodiments of the present invention, the fourth contact time can be 12-72 hours, preferably 24-48 hours. Specifically, the second-generation matrix compound begins to react with hydrazine when the solution of the second-generation matrix compound is started to be added dropwise.

[0084] According to some embodiments of the present invention, the amount of the fourth solvent relative to 1g of hydrazine can be 2-20mL, preferably 3-15mL.

[0085] According to some embodiments of the present invention, in step (4), in order to make the reaction proceed better, there are certain requirements on the addition rate of the solution of the second-generation matrix compound. Preferably, the addition rate is 1-20 mL / min relative to 100 mL of the solution of the second-generation matrix compound, more preferably 1-10 mL / min.

[0086] In this invention, in step (5), there are no particular limitations on the ratio of the amount of each substance and the contact time during the repeated steps (3) and (4), as long as the requirements of this invention can be met.

[0087] In this invention, steps (1) and (3) are preferably carried out in the presence of a polymerization inhibitor, wherein the polymerization inhibitor is selected from hydroquinone monomethyl ether and / or hydroquinone monomethyl ether. The amount of the polymerization inhibitor added accounts for a percentage of the total CR. 1 R 2 =CR 3 (CH2) n COOR 4 0.1-1 wt%.

[0088] In this invention, preferably, the method further includes a purification step. For example, in step (1), the reaction solution after the first contact is subjected to a first post-treatment (purification treatment). The first post-treatment step is not particularly limited, as long as it meets the requirements of this invention. For example, it can be carried out by subjecting the reaction solution after the first contact to vacuum distillation at 30-50°C and a vacuum degree of 50-70 kPa for 10-20 hours.

[0089] In this invention, preferably, step (2) further includes a second post-treatment (purification treatment) of the reaction solution after the second contact. The second post-treatment step is not particularly limited, as long as it meets the requirements of this invention. For example, it can be carried out by subjecting the reaction solution after the second contact to vacuum distillation at 40-80°C and a vacuum degree of 60-90 kPa for 10-30 hours.

[0090] Similarly, steps (3), (4) and (5) can be separated and purified by referring to the purification steps in step (1) or (2) above.

[0091] In this invention, the first solvent, the second solvent, the third solvent, and the fourth solvent can all be the same or different, as long as they can provide a medium for the first contact, the second contact, the third contact, and the fourth contact to promote the addition reaction or the reaction between the amine group and the ester group.

[0092] According to some embodiments of the present invention, the amino acid salt is selected from sodium and / or potassium salts of amino acids, and the amino acid salt is selected from at least one of potassium glycinate, potassium alanine, potassium sarcosine, sodium glycinate, sodium alanine, and sodium sarcosine, preferably from at least one of potassium glycinate, potassium alanine, and potassium sarcosine, and more preferably, the amino acid salt is selected from at least two of potassium glycinate, potassium alanine, potassium sarcosine, sodium glycinate, sodium alanine, and sodium sarcosine.

[0093] According to some embodiments of the present invention, the weight ratio of the amino acid salt to the organic amine is (0-400):1 (e.g., any value between 0:1, 2:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, 60:1, 100:1, 200:1, 300:1, 400:1 or more), preferably (10-100):1. The weight of the organic amine is preferably measured as the component obtained after a simple desolvation step (e.g., distillation).

[0094] According to some embodiments of the present invention, the content of the amino acid salt is 0-40 wt%, the content of the organic amine is 0.2-30 wt%, and the content of water is 50-90 wt% based on the total weight of the composition;

[0095] Preferably, based on the total weight of the composition, the content of the amino acid salt is 10-30 wt%, the content of the organic amine is 0.4-30 wt%, and the content of water is 50-90 wt%.

[0096] A second aspect of the present invention provides the use of the composition described in the first aspect above in gas absorption, particularly in the absorption of acidic gases.

[0097] According to some embodiments of the present invention, the acidic gas may be an inorganic acidic gas, preferably at least one of carbon dioxide, sulfur dioxide and hydrogen sulfide.

[0098] A third aspect of the present invention provides a method for absorbing gas, the method comprising: contacting the composition described in the first aspect or an aqueous solution containing a compound with the structure shown in formula (I) with the gas to be absorbed.

[0099] Preferably, in the aqueous solution containing the compound with the structure shown in formula (I), the mass fraction of the solute of the compound with the structure shown in formula (I) is 0.1-20 wt%, preferably 1-15 wt%.

[0100] According to some embodiments of the present invention, the contact conditions may include a temperature of 30-50°C, preferably 35-45°C.

[0101] According to some embodiments of the present invention, the flow rate of the gas to be absorbed is 50-200 mL / min, preferably 80-150 mL / min, relative to 100 g of the composition.

[0102] A fourth aspect of the present invention provides the application of a compound with the structure shown in formula (I) in gas absorption, particularly in the absorption of acidic gases.

[0103] The present invention will be described in detail below through embodiments.

[0104] In the following examples, unless otherwise specified, all raw materials are commercially available products.

[0105] The reaction process was monitored by HPLC; yield = conversion × selectivity.

[0106] Conversion rate = percentage of the amount of reactants participating in the reaction (the amount of reactants in the reaction) to the amount of reactants entering the reactor (the initial amount of reactants);

[0107] Selectivity = Amount of key components consumed in producing the target product (mol) / Amount of key components participating in the reaction (mol); Purity is obtained by HPLC detection;

[0108] HPLC analytical conditions: Phenomenex C18 column (250 mm × 4.6 mm, 4 μm); mobile phase: acetonitrile-water (70:30 v / v); detection wavelength: 350 nm; flow rate: 0.8 mL / min; injection volume: 20 μL.

[0109] Preparation Example 1

[0110] 1G matrix compound:

[0111]

[0112] 1G target compound:

[0113]

[0114] (1) In a three-necked flask, 344.36 g of methyl acrylate (MA) was dissolved in 100 mL of methanol, and 3.5 g of hydroquinone monomethyl ether was added to obtain a methanol solution of methyl acrylate (MA solution); then 16.02 g of hydrazine (AH) was dissolved in 50 mL of methanol to obtain a methanol solution of hydrazine (AH solution), and the AH solution was placed in a constant pressure dropping funnel; the AH solution was slowly added dropwise to the MA solution under stirring at 25 °C, and the addition was completed in 0.5 h, wherein the molar ratio of MA:AH was 8:1, and the reaction was continued at a constant temperature for 24 h; after monitoring the reaction to be complete, the product after the reaction was subjected to vacuum distillation at 35 °C and a vacuum degree of 60 kPa for 16 h to remove methanol and excess MA, and the light yellow product obtained was 1 G of matrix compound with a purity of 98.5 wt% and a yield of 93.9%.

[0115] (2) Dissolve the 1G matrix product obtained in step (1) in 100mL of methanol. After the 1G matrix compound is completely dissolved, place it in a constant pressure dropping funnel to obtain a methanol solution of the 1G matrix compound. Add excess AH to a three-necked reaction flask so that the molar ratio of AH to the 1G matrix compound is 16:1. Slowly add the methanol solution of the 1G matrix compound dropwise under stirring at 25℃. The addition is completed in 0.5h. Then continue to keep the reaction at the temperature for 24h. After monitoring the reaction to be complete, distill the product under reduced pressure at 55℃ and 80kPa for 16h to remove methanol and excess AH. Finally, the viscosity of the liquid in the distillation flask increases and becomes a light yellow viscous liquid, which is the 1G target compound with a purity of 95.2wt% and a yield of 87.1%.

[0116] Preparation Example 2

[0117] 2G matrix compounds:

[0118]

[0119] 2G target compound:

[0120]

[0121] Repeat steps (1) and (2) in Preparation Example 1 to obtain 1G of matrix compound and 1G of target compound, respectively;

[0122] (3) Following the method in step (1), 137.74 g of methyl acrylate (MA) was dissolved in 100 mL of methanol in a three-necked flask, and 0.2 g of hydroquinone monomethyl ether was added to obtain a methanol solution of methyl acrylate (MA solution); then 37.6 g of 1G target compound was dissolved in 50 mL of methanol to obtain a methanol solution of 1G target compound, which was placed in a constant pressure dropping funnel; the methanol solution of 1G target compound was slowly added dropwise to the MA solution under stirring at 25 °C, and the addition was completed in 0.5 h, wherein the molar ratio of MA to 1G target compound was 16:1, and then the reaction was continued at a constant temperature for 24 h; after monitoring the reaction to be complete, the product after the reaction was subjected to vacuum distillation at 35 °C and a vacuum degree of 60 kPa for 16 h to remove methanol and excess MA, and the light yellow product obtained was the 2G matrix compound with a purity of 98.3 wt% and a yield of 80.0%.

[0123] (4) Dissolve the 2G matrix product obtained in step (3) in 100 mL of methanol. After the 2G matrix compound is completely dissolved, place it in a constant pressure dropping funnel to obtain a methanol solution of the 2G matrix compound. Add excess AH to a three-necked reaction flask so that the molar ratio of AH to the 2G matrix compound is 16:1. Slowly add the methanol solution of the 2G matrix compound dropwise under stirring at 25 °C. The addition is completed in 1 h. Then continue to keep the reaction at the temperature for 24 h. After monitoring the reaction to be complete, distill the product under reduced pressure at 55 °C and 80 kPa for 16 h to remove methanol and excess AH. Finally, the viscosity of the liquid in the distillation flask increases and becomes a light yellow viscous liquid, which is the 2G target compound with a purity of 93.6 wt% and a yield of 71.3%.

[0124] Preparation Example 3

[0125] 3G matrix compounds:

[0126]

[0127] 3G target compounds:

[0128]

[0129] Following the method of Preparation Example 2, steps (3) and (4) were repeated using the 2G target compound as a reactant to prepare the 3G matrix compound and the 3G target compound.

[0130] The 3G matrix compound had a purity of 97.6 wt% and a yield of 65.7%; the 3G target compound had a purity of 93.2 wt% and a yield of 55.8%.

[0131] Preparation Example 4

[0132] Following the method of Preparation Example 3, steps (3) and (4) were repeated using the 3G target compound as a reactant to prepare the 4G matrix compound and the 4G target compound.

[0133] The 4G matrix compound had a purity of 97.2 wt% and a yield of 49.1%; the 4G target compound had a purity of 92.8 wt% and a yield of 42.3%.

[0134] Preparation Example 5

[0135] Following the method of Preparation Example 4, steps (3) and (4) were repeated using the 2G target compound as a reactant to prepare the 5G matrix compound and the 5G target compound.

[0136] The 5G matrix compound had a purity of 96.3 wt% and a yield of 37.2%; the 5G target compound had a purity of 92.2 wt% and a yield of 32.7%.

[0137] Preparation Example 6

[0138] The preparation was carried out in the same manner as in Example 2, except that 400.48 g of ethyl acrylate was used instead of 344.36 g of methyl acrylate (MA).

[0139] Ultimately, 1G of the matrix compound had a purity of 98.4 wt% and a yield of 92.5%; 1G of the target compound had a purity of 95.8 wt% and a yield of 84.6%.

[0140] Preparation Example 7

[0141] The preparation was carried out in the same manner as in Example 2, except that 400.44 g of methyl methacrylate was used instead of 344.36 g of methyl acrylate (MA).

[0142] Ultimately, 1G of the matrix compound had a purity of 98.2 wt% and a yield of 93.3%; 1G of the target compound had a purity of 94.2 wt% and a yield of 85.8%.

[0143] Preparation Example 8

[0144] The preparation was carried out in the same manner as in Example 2, except that 456.56 g of ethyl butenoate was used instead of 344.36 g of methyl acrylate (MA).

[0145] Ultimately, 1G of the matrix compound had a purity of 98.8 wt% and a yield of 91.4%; 1G of the target compound had a purity of 93.2 wt% and a yield of 82.3%.

[0146] The following test examples illustrate the acid gas absorption performance of the compositions of the present invention.

[0147] A composition formulation is prepared by adding water, amino acid salts, and / or organic amines (compounds with the structure shown in Formula (I)) in the amounts shown in Table 1, and used as an absorbent for absorbing acidic gases.

[0148] Specific absorption steps: The raw gas (acidic CO2, volume concentration 12.8%) passes through a hygroscopic bottle and a buffer bottle, then enters the absorption tube containing the absorbent at 40℃±0.5℃. The gas flow rate of the raw gas is controlled at 100mL / min, and bubbling absorption is performed. The absorption temperature is controlled by a constant temperature bath. After a period of time, the CO2 content in the vented tail gas is monitored and analyzed using a flue gas analyzer. Then, the gas source is shut off, and the absorbent solution after absorbing the acidic gas is taken for liquid phase analysis. A raw gas pipeline is reserved to adjust the acidic gas content in the raw gas. The CO2 absorbed by the absorbent is analyzed using a gas generation method. Specifically, a certain amount of sample is placed in a neutralization reaction bottle, and an excess of dilute sulfuric acid solution is placed in the straight tube inside the reaction bottle. The stopper is tightened, and the reading V is recorded when the liquid level in the solution bottle is equal to the liquid level in the graduated straight tube. o The liquids in the reaction flask come into contact and react, CO2 is released, and the liquid levels are equal. Record the value V1. V1 and V o The difference is the volume of CO2 produced after the reaction, from which the CO2 content in the solution (i.e., the amount of CO2 absorbed, V) can be calculated. CO2 / V 组合物 (mL / mL). The test results are shown in Table 1.

[0149] Table 1

[0150]

[0151] The composition provided by this invention has a significantly better absorption effect on acidic gases compared with the use of amino acid salts alone.

[0152] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition having acid gas absorption function, characterized in that, The composition contains amino acid salts, organic amines, and water; The organic amine is a compound having the structure shown in formula (I). （I）， in, A1-A4 are each independently -CR 1 R 2 CHR 3 (CH2) n COM or -CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2、-CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n CONHN(CR 1 R 2 CHR 3 (CH2) n COM)2)2 and CR derived from this pattern 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m One of the groups with -1, where m is an integer from 1 to 10; Among them, R 1 R 2 and R 3 Each is independently an H or C1-C4 alkyl group, n is an integer from 0 to 6, and M is NHNH2; Among them, A1-A4 all contain -NHNH2.

2. The composition according to claim 1, wherein, R 1 R 2 and R 3 Each is independently one of H, methyl, and ethyl; And / or, where n is an integer from 0 to 4; And / or, m≤5.

3. The composition according to claim 1 or 2, wherein, A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, where R 1 =H,R 2 =H,R 3 =H, n is 0, M is NHNH2; or... A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, where R 1 =H,R 2 =H,R 3 =H, n is 1, M is NHNH2; or... A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, where R 1 =Me,R 2 =H,R 3 =H, n is 0, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 1, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 1, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 1, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 2, M is NHNH2; or, A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 2, M is NHNH2; or, A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 2, M is NHNH2; or, A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 3, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 3, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 3, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 0, m is 4, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =H,R 2 =H,R 3 =H, n is 1, m is 4, M is NHNH2; or... A1-A4 are the same and are CR. 1 R 2 CHR 3 (CH2) n The number of CONHN structures is 2. m -1 group, wherein R 1 =Me,R 2 =H,R 3 =H, n is 0, m is 4, M is NHNH2.

4. The composition according to claim 1, wherein, The compound with the structure shown in formula (I) is prepared by a method comprising the following steps: (1) In the presence of the first solvent, hydrazine reacts with CR 1 R 2 =CR 3 (CH2) n COOR 4 The first contact yields a product containing a first-generation matrix compound; wherein, R 1 R 2 R 3 and R 4 Each is independently an H or C1-C4 alkyl group, and n is an integer from 0 to 6; (2) In the presence of a second solvent, the product containing the first-generation matrix compound is subjected to a second contact with hydrazine to obtain a product containing the first-generation target compound.

5. The composition according to claim 1, wherein, The compound with the structure shown in formula (I) is prepared by a method comprising the following steps: (1) In the presence of the first solvent, hydrazine reacts with CR 1 R 2 =CR 3 (CH2) n COOR 4 The first contact yields a product containing a first-generation matrix compound; wherein, R 1 R 2 R 3 and R 4 Each is independently an H or C1-C4 alkyl group, and n is an integer from 0 to 6; (2) In the presence of a second solvent, the product containing the first-generation matrix compound is subjected to a second contact with hydrazine to obtain a product containing the first-generation target compound; (3) In the presence of a third solvent, the product containing the first-generation target compound is reacted with CR. 1 R 2 =CR 3 (CH2) n COOR 4 A third contact is performed to obtain a product containing a second-generation matrix compound; (4) In the presence of a fourth solvent, the product containing the second-generation matrix compound is subjected to a fourth contact with hydrazine to obtain a product containing the second-generation target compound.

6. The composition according to claim 1, wherein, The compound with the structure shown in formula (I) is prepared by a method comprising the following steps: (1) In the presence of the first solvent, hydrazine reacts with CR 1 R 2 =CR 3 (CH2) n COOR 4 The first contact yields a product containing a first-generation matrix compound; wherein, R 1 R 2 R 3 and R 4 Each is independently an H or C1-C4 alkyl group, and n is an integer from 0 to 6; (2) In the presence of a second solvent, the product containing the first-generation matrix compound is subjected to a second contact with hydrazine to obtain a product containing the first-generation target compound; (3) In the presence of a third solvent, the product containing the first-generation target compound is reacted with CR. 1 R 2 =CR 3 (CH2) n COOR 4 A third contact is performed to obtain a product containing a second-generation matrix compound; (4) In the presence of a fourth solvent, the product containing the second-generation matrix compound is subjected to a fourth contact with hydrazine to obtain a product containing the second-generation target compound; (5) Following this pattern, repeat steps (3) and (4) to obtain products containing the target compound of generation q; where q is an integer from 3 to 10.

7. The composition according to any one of claims 4-6, wherein, R 1 R 2 R 3 and R 4 Each is independently one of H, methyl, and ethyl, and / or n is an integer from 0 to 4.

8. The composition according to any one of claims 4-6, wherein, In step (1), the first solvent is selected from water and / or C1-C4 alcohols; And / or, relative to 1g of hydrazine, the amount of the first solvent used is 2-20mL; And / or, CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio of hydrazine to ammonia is (4-12):1; And / or, the first contact is made by adding hydrazine and / or hydrazine solution to CR at 20-40°C. 1 R 2 =CR 3 (CH2) n COOR 4 in solution; And / or, the duration of the first contact is 12-72 hours; And / or, in step (2), the second solvent is selected from water and / or C1-C4 alcohols; And / or, relative to 1g of hydrazine, the amount of the second solvent used is 2-20mL; And / or, the molar ratio of hydrazine to the first-generation matrix compound is (4-20):1; And / or, the second contact is made by adding a solution of the first-generation matrix compound to hydrazine and / or a hydrazine solution at 20-40°C; And / or, in step (3), the first-generation target compound is reacted with CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio is 1:(8-20); And / or, the third contact is made by adding a solution of the first-generation target compound to CR at 20-40°C. 1 R 2 =CR 3 (CH2) n COOR 4 in solution; And / or, the duration of the third contact is 12-72 hours; And / or, relative to 1g of the first-generation target compound, the amount of the third solvent is 2-20mL; And / or, in step (4), the molar ratio of the second-generation matrix compound to hydrazine is 1:(16-32). And / or, the fourth contact method is: the second contact method is: adding a solution of the second-generation matrix compound to hydrazine and / or a hydrazine solution at 20-40°C; And / or, the fourth contact time is 12-72 h; and / or, the amount of the fourth solvent used is 2-20 mL relative to 1 g of hydrazine.

9. The composition according to claim 8, wherein, In step (1), the first solvent is methanol and / or water.

10. The composition according to claim 8, wherein, The amount of the first solvent used is 3-15 mL relative to 1 g of hydrazine.

11. The composition according to claim 8, wherein, CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio of hydrazine to hydrazine is (6-10):

1.

12. The composition according to claim 8, wherein, The addition rate is 1-10 mL / min relative to 100 mL of hydrazine and / or hydrazine solution.

13. The composition according to claim 8, wherein, The addition rate is 1-5 mL / min relative to 100 mL of hydrazine and / or hydrazine solution.

14. The composition according to claim 8, wherein, The first contact time is 24-48 hours.

15. The composition according to claim 8, wherein, In step (2), the second solvent is methanol and / or water.

16. The composition according to claim 8, wherein, The amount of the second solvent used is 3-15 mL relative to 1 g of hydrazine.

17. The composition according to claim 8, wherein, The molar ratio of hydrazine to the first-generation matrix compound is (8-16):

1.

18. The composition according to claim 8, wherein, The addition rate is 1-20 mL / min relative to 100 mL of the first-generation matrix compound solution.

19. The composition according to claim 8, wherein, The addition rate is 1-10 mL / min relative to 100 mL of the first-generation matrix compound solution.

20. The composition according to claim 8, wherein, The second contact time is 12-72 hours.

21. The composition according to claim 8, wherein, The second contact time is 24-48 hours.

22. The composition according to claim 8, wherein, In step (3), the first-generation target compound and CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio is 1:(12-18).

23. The composition according to claim 8, wherein, The addition rate is 1-20 mL / min relative to 100 mL of the first-generation target compound solution.

24. The composition according to claim 8, wherein, The addition rate is 1-10 mL / min relative to 100 mL of the first-generation target compound solution.

25. The composition according to claim 8, wherein, The duration of the third contact is 24-48 hours.

26. The composition according to claim 8, wherein, The amount of the third solvent used is 3-15 mL relative to 1 g of the first-generation target compound.

27. The composition according to claim 8, wherein, In step (4), the molar ratio of the second-generation matrix compound to hydrazine is 1:(18-24).

28. The composition according to claim 8, wherein, The fourth contact time is 24-48 hours.

29. The composition according to claim 8, wherein, The amount of the fourth solvent used is 3-15 mL relative to 1 g of hydrazine.

30. The composition according to claim 8, wherein, The addition rate is 1-20 mL / min relative to 100 mL of the second-generation matrix compound solution.

31. The composition according to claim 8, wherein, The addition rate is 1-10 mL / min relative to 100 mL of the second-generation matrix compound solution.

32. The composition according to claim 1, wherein, The amino acid salt is selected from sodium and / or potassium salts of amino acids, and the amino acid salt is selected from at least one of potassium glycinate, potassium alanine, potassium sarcosine, sodium glycinate, sodium alanine, and sodium sarcosine. And / or, the weight ratio of the amino acid salt to the organic amine is (0-400):

1.

33. The composition according to claim 1, wherein, The amino acid salt is selected from at least one of potassium glycinate, potassium alanine, and potassium sarcosine.

34. The composition according to claim 1, wherein, The weight ratio of the amino acid salt to the organic amine is (10-100):

1.

35. The composition according to claim 1, wherein, The content of the amino acid salt is 0-40 wt%, the content of the organic amine is 0.2-30 wt%, and the content of water is 50-90 wt% based on the total weight of the composition.

36. The composition according to claim 1, wherein, The content of the amino acid salt is 10-30 wt%, the content of the organic amine is 0.4-30 wt%, and the content of water is 50-90 wt% based on the total weight of the composition.

37. Use of the composition according to any one of claims 1-36 in gas absorption.

38. The use of the composition according to any one of claims 1-36 in the absorption of acidic gases.

39. The application according to claim 38, wherein, The acidic gas is an inorganic acidic gas.

40. The application according to claim 38 or 39, wherein, The acidic gas is at least one of carbon dioxide, sulfur dioxide, and hydrogen sulfide.

41. A method for absorbing gas, characterized in that, The method comprises contacting the gas to be absorbed with an aqueous solution of the composition of any one of claims 1-36 or a compound containing the structure shown in formula (I).

42. The method according to claim 41, wherein, In the aqueous solution containing the compound with the structure shown in formula (I), the mass fraction of the solute of the compound with the structure shown in formula (I) is 0.1-20 wt%.

43. The method according to claim 41, wherein, The contact conditions include a temperature of 30-50°C; And / or, relative to 100 grams of the composition, the flow rate of the gas to be absorbed is 50-200 mL / min.

44. The method according to claim 41 or 43, wherein, The contact conditions include a temperature of 35-45°C.

45. The method according to claim 41 or 43, wherein, The flow rate of the gas to be absorbed is 80-150 mL / min relative to 100 g of the composition.

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