Compositions and applications having acid gas absorption functionality

Abstract

The present application relates to the field of gas separation and purification, and discloses a composition with acid gas absorption function.The composition comprises an absorbent and an additive; wherein the absorbent comprises at least one of an organic amine, a polyether and a C7-C10 fatty alcohol; and the additive is a compound with demulsification function.The composition has good purification and separation effect, is strong in industrial application and operability, can regenerate more adsorbed gas (such as carbon dioxide) per unit time, effectively reduces the energy consumption required for regenerating unit adsorbed gas, and can provide strong guarantee for application of the absorbent to gas removal and realization of continuous absorption and regeneration industrialization device.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of gas separation and purification, in particular to a composition with acid gas absorption function and application. BACKGROUND

[0002] The chemical absorption method is one of the most mature methods for gas decarburization technology, but it generally faces the problem of high regeneration energy consumption. In view of this problem, current work is mainly carried out from the aspects of new absorbent development, process improvement or new process research.

[0003] Among them, the research idea of new absorbent is mainly to develop new chemical absorbents. In recent years, some researchers have changed their way of thinking and started to study phase change absorbents for decarburization process to solve the problem of high regeneration energy consumption. According to the literature, compared with the traditional chemical absorption method, under the same treatment effect, this process can reduce the liquid amount entering the regeneration tower, thereby reducing the regeneration energy consumption.

[0004] However, the phase change absorbent used for decarburization generally has the problem that the separation process of the organic phase and the carrier phase in the rich liquid phase after absorption is relatively slow due to the characteristics of the absorbent, such as high viscosity and surface tension, which affects the regeneration process of the subsequent carrier phase and the absorption performance of the lean liquid after regeneration. Therefore, it is necessary to develop an absorbent formula with high purification efficiency and low energy consumption. SUMMARY

[0005] The purpose of the present application is to overcome the above technical problems, and provide a composition with acid gas absorption function and application.

[0006] In order to achieve the above purpose, the first aspect of the present application provides a composition with acid gas absorption function, characterized in that the composition comprises an absorbent and an additive; wherein the absorbent comprises at least one of an organic amine, a polyether and a C7-C10 fatty alcohol; and the additive comprises a compound with demulsification function.

[0007] The second aspect of the present application provides an application of the composition of the first aspect in gas absorption, in particular in acid gas absorption.

[0008] The third aspect of the present application provides a method for absorbing gas, which comprises contacting the composition of the first aspect with the gas to be absorbed.

[0009] Compared with the prior art, the technical scheme provided by the present application at least has the following advantages:

[0010] (1) The provided composition (with gas absorption function) has good purification and separation effect, strong industrial application and operability, and can regenerate more adsorbed gas (such as acidic gas carbon dioxide) per unit time, that is, the energy consumption required for regeneration of unit adsorbed gas is effectively reduced, which can provide strong guarantee for the application of the absorbent in gas removal and the realization of continuous absorption and regeneration industrial devices. And it will be applied to different degrees in the fields of industry, agriculture, medicine, wastewater treatment and chemical industry, especially in the fields of chemical engineering, wastewater treatment, gas purification or separation, etc. It has good application prospect.

[0011] (2) The application also provides a compound with demulsification function, which is a compound independently developed by the application and prepared from enoic acid ester and hydrazine (hydrazine). It is a new compound molecule with high Y and high order. From the molecular structure, the compound is obtained by continuously growing outward from the double-core molecule (hydrazine) in the form of Y-type. When the above compound is used as an additive of a gas absorbent (especially an acidic gas absorbent), the absorbent after absorbing the gas (especially the acidic gas) can effectively break the interface properties of the organic phase-carrier phase under the action of the additive (the compound provided by the application), that is, break the interface balance, rapidly realize the transition from homogeneous phase to heterogeneous phase, reduce the influence of the intermediate transition state on the separation effect of the absorbent, and thus ensure the regeneration and a series of continuous reactions of the absorbent after phase separation, and improve the gas purification efficiency.

[0012] (3) The application also provides a method for preparing the compound with demulsification function, which has the advantages of simple steps, high efficiency, environmental friendliness, and high yield and purity, and is beneficial to industrialization. DETAILED DESCRIPTION

[0013] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The exact numerical values of the endpoints of the ranges and the separate points are not to be construed as being strictly limited to the exact numerical values reported, but rather to have the weight of the values as approximations. Any numerical range recited herein is intended to include all sub-ranges of the same numbers. For a numerical range recited in the format "from X to Y", any numerical value that is within the indicated range is to be construed as being expressly stated. For a numerical range recited in the format "X to Y", any numerical value that is within the indicated range is to be construed as being expressly stated. For a numerical range recited in the format "X, Y", any numerical value that is within the indicated range is to be construed as being expressly stated.

[0014] In order to achieve the above-mentioned purpose, the first aspect of the application provides a composition with acidic gas absorption function, characterized in that the composition comprises an absorbent and an additive; wherein the absorbent comprises at least one of an organic amine, a polyether and a C7-C10 fatty alcohol; and the additive comprises a compound with demulsification function.

[0015] According to some embodiments of the present application, the weight ratio of the absorbent and the additive is 100:(0.1-10), preferably 100:(0.5-5).

[0016] According to some embodiments of the present application, the absorbent is selected from organic amines and polyethers.

[0017] According to some embodiments of the present application, the content of the organic amine is 1-50wt%, the content of the polyether is 40-99wt%, and the content of the additive is 0.005-10wt%, based on the total weight of the absorbent and the additive in the composition.

[0018] According to some embodiments of the present application, the content of the organic amine is 5-50wt%, the content of the polyether is 45-95wt%, and the content of the additive is 0.01-5wt%, based on the total weight of the absorbent and the additive in the composition.

[0019] According to some embodiments of the present application, the organic amine is a C1-C6 alcohol amine, selected from at least one of monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, mono-isopropanolamine, di-isopropanolamine and tri-isopropanolamine, preferably selected from at least one of monoethanolamine, diethanolamine and triethanolamine.

[0020] According to some embodiments of the present application, the polyether has a weight average molecular weight of 200-600, preferably 250-270; and is selected from polyethylene glycol dimethyl ether and / or polyethylene glycol monomethyl ether.

[0021] wherein the C7-C10 fatty alcohol can be, for example, n-heptyl alcohol, n-octanol, nonanol or decanol.

[0022] According to some embodiments of the present application, the compound having the demulsification function has a structure shown in formula (I),

[0023]

[0024] wherein,

[0025] 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 R2 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;

[0026] 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;

[0027] Among them, A1-A4 are not all H and at least one of A1-A4 contains -NHNH2.

[0028] In this invention, the C1-C4 alkyl groups include straight-chain or branched alkyl groups of C1-C4.

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

[0030] 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(CR1 R 2 CHR 3 (CH2) n COM)2)2 and CR 1 R 2 CHR 3 (CH2) n one of the groups CONHN having m number of H, m being an integer from 1 to 10.

[0031] According to some embodiments of the application, R 1 , R 2 and R 3 are each independently one of H, methyl and ethyl.

[0032] According to some embodiments of the application, n is an integer from 0 to 4.

[0033] According to some embodiments of the application, m < 5.

[0034] According to some embodiments of the application, M is NHNH2.

[0035] According to some embodiments of the application, A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, wherein R 1 = H, R 2 = H, R 3 = H, n is 0 and M is NHNH2; or,

[0036] A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, wherein R 1 = H, R 2 = H, R 3 = H, n is 1 and M is NHNH2; or,

[0037] A1-A4 are the same and are -CR 1 R 2 CHR 3 (CH2) n COM, wherein R 1 = Me, R 2 = H, R 3 = H, n is 0 and M is NHNH2; or,

[0038] A1-A4 are the same and are CR 1 R 2 CHR3 (CH2) n The number of CONHN structures is 2 m -1, wherein R 1 = H, R 2 = H, R 3 = H, n is 0, m is 1, and 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, wherein R 1 = Me, R 2 = H, R 3 = H, n is 1, m is 1, and 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, wherein R 1 = Me, R 2 = H, R 3 = H, n is 0, m is 2, and 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, wherein R 1 = H, R 2 = H, R 3 = H, n is 1, m is 2, and 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, wherein R 1 = Me, R 2 = H, R 3 = H, n is 1, m is 2, and M is NHNH2; or,

[0043] A1-A4 are the same and are CR 1 R2 CHR 3 (CH2) n CONHN structure 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,

[0044] A1-A4 are the same and are CR 1 R 2 CHR 3 (CH2) n CONHN structure 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,

[0045] A1-A4 are the same and are CR 1 R 2 CHR 3 (CH2) n CONHN structure 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,

[0046] A1-A4 are the same and are CR 1 R 2 CHR 3 (CH2) n CONHN structure 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,

[0047] A1-A4 are the same and are CR 1 R 2 CHR 3 (CH2) n CONHN structure 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,

[0048] A1-A4 are the same and are CR1 R 2 CHR 3 (CH2) n CONHN structure 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,

[0049] A1-A4 are the same and are CR 1 R 2 CHR 3 (CH2) n CONHN structure is 2 m -1 group, wherein R 1 =Me, R 2 =H, R 3 =H, n is 0, m is 4, M is NHNH2.

[0050] The inventors of the present application have found that, based on the principle of Michael addition reaction, different lengths of grafting groups (such as alkenoate chains) can be reacted with hydrazine (as an initiation core), which can continuously grow radially outward, obtaining compounds containing different or same substituted grafting groups, which can be well used in gas absorption. However, based on the cost and the difficulty of operation, it is preferred to graft the same grafting group to obtain highly symmetrical Y-like compounds.

[0051] Therefore, preferably, in the present application, the additive is prepared according to a method comprising the following steps:

[0052] (1) hydrazine is contacted with CR 1 R 2 =CR 3 (CH2) n COOR 4 in the presence of a first solvent to obtain a first generation of base compounds (1G base compounds); wherein R 1 , R 2 , R 3 and R 4 are each independently H or C1-C4 alkyl, and n is an integer from 0 to 6;

[0053] (2) the first generation of base compounds are contacted with hydrazine in the presence of a second solvent to obtain a first generation of target compounds (1G target compounds);

[0054] (3) optionally, the first generation of target compounds are contacted with CR 1 R2 =CR 3 (CH2) n COOR 4 a third contact to obtain a second generation of the base compound (2G base compound) ;

[0055] (4) optionally, a fourth contact of the second generation of the base compound with hydrazine in the presence of a fourth solvent to obtain a second generation of the target compound (2G target compound) ;

[0056] (5) optionally, repeating the step (3) and the step (4) regularly to obtain a product containing a qth generation of the target compound; wherein q is an integer from 3 to 20. The product containing the qth generation of the target compound obtained can be used as an additive directly, or can be used as an additive after a simple solvent removal step (such as distillation).

[0057] According to some embodiments of the present application, R 1 , R 2 , R 3 and R 4 are each independently one of H, methyl and ethyl.

[0058] According to some embodiments of the present application, n is an integer from 0 to 4.

[0059] According to some embodiments of the present application, in the step (1), the first solvent can be selected from water and / or C1-C4 alcohol, preferably methanol and / or water.

[0060] According to some embodiments of the present application, the amount of the first solvent can be 2-20 mL, preferably 3-15 mL, relative to 1 g of hydrazine.

[0061] According to some embodiments of the present application, in the step (1), in order to make the reaction proceed better, the amount of CR 1 R 2 =CR 3 (CH2) n COOR 4 is required to a certain extent, and preferably, CR 1 R 2 =CR 3 (CH2) n COOR 4 is in excess, for example, the molar ratio of CR 1 R 2 =CR 3 (CH2) n COOR 4 to hydrazine can be (4-12): 1, preferably (6-10): 1.

[0062] According to some embodiments of the present application, the first contacting is performed by adding hydrazine and / or hydrazine solution to CR 1 R 2 =CR 3 (CH2) n COOR 4 solution at 20-40°C.

[0063] In the present application, in step (1), the hydrazine solution is obtained by dissolving hydrazine in the first solvent; and the CR 1 R 2 =CR 3 (CH2) n COOR 4 solution is obtained by dissolving CR 1 R 2 =CR 3 (CH2) n COOR 4 in the first solvent; wherein the amount of the first solvent used for dissolving is not particularly limited as long as it meets the requirements of the present application.

[0064] According to some embodiments of the present application, in order to achieve better results, the adding speed of hydrazine and / or hydrazine solution in step (1) is required to be certain, preferably, the adding speed of 100 mL of hydrazine and / or hydrazine solution is 1-10 mL / min, more preferably 1-5 mL / min.

[0065] According to some embodiments of the present application, the first contacting can be performed for 12-72 h, preferably 24-48 h. Wherein, when the adding of hydrazine and / or hydrazine solution starts, the reaction of hydrazine and CR 1 R 2 =CR 3 (CH2) n COOR 4 starts.

[0066] According to some embodiments of the present application, in step (2), the second solvent can be selected from water and / or C1-C4 alcohol, preferably methanol and / or water.

[0067] According to some embodiments of the present application, the amount of the second solvent can be 2-20 mL, preferably 3-15 mL, relative to 1 g of hydrazine.

[0068] According to some embodiments of the present application, in step (2), in order to make the reaction proceed better, there are certain requirements for the amount of the first generation base compound and hydrazine, and preferably, the first generation base compound is in excess, for example, the molar ratio of hydrazine to the first generation base compound can be (4-20):1, preferably (8-16):1.

[0069] According to some embodiments of the present application, the second contact is performed by adding a solution of the first generation base compound to hydrazine and / or a hydrazine solution at 20-40°C.

[0070] In the present application, in step (2), the hydrazine solution is obtained by dissolving hydrazine in the second solvent; and the solution of the first generation base compound is obtained by dissolving the first generation base compound in the second solvent; wherein the amount of the second solvent used for dissolution is not particularly limited, as long as it can meet the requirements of the present application.

[0071] According to some embodiments of the present application, in step (2), in order to make the reaction proceed better, there are certain requirements for the addition rate of the solution of the first generation base compound, preferably, the addition rate is 1-20 mL / min, more preferably 1-10 mL / min, relative to 100 mL of the solution of the first generation base compound.

[0072] According to some embodiments of the present application, the second contact can be performed for 12-72 h, preferably 24-48 h. Wherein the reaction of the first generation base compound and hydrazine starts when the solution of the first generation base compound starts to be added.

[0073] According to some embodiments of the present application, in step (3), in order to make the reaction proceed better, there are certain requirements for the amount of the first generation target compound and CR 1 R 2 =CR 3 (CH2) n COOR 4 , and preferably, CR 1 R 2 =CR 3 (CH2) n COOR 4 is in excess, for example, the molar ratio of the first generation target compound to CR 1 R 2 =CR 3 (CH2) n COOR 4 can be 1:(8-20), preferably 1:(12-18).

[0074] According to some embodiments of the present application, the third contacting is performed by adding the solution of the first generation target compound to the CR 1 R 2 =CR 3 (CH2) n COOR 4 solution at 20-40°C.

[0075] In the present application, in step (3), the solution of the first generation target compound is obtained by dissolving the first generation target compound in the third solvent; and the CR 1 R 2 =CR 3 (CH2) n COOR 4 solution is obtained by dissolving the CR 1 R 2 =CR 3 (CH2) n COOR 4 in the third solvent; wherein the amount of the third solvent used for dissolving is not particularly limited, as long as it meets the requirements of the present application.

[0076] According to some embodiments of the present application, in order to make the reaction proceed better, the adding speed of the solution of the first generation target compound is required to be within a certain range, preferably, the adding speed is 1-20 mL / min, more preferably 1-10 mL / min, relative to 100 mL of the solution of the first generation target compound.

[0077] According to some embodiments of the present application, the third contacting is performed for 12-72 h, preferably 24-48 h; wherein the reaction between the first generation target compound and the CR 1 R 2 =CR 3 (CH2) n COOR 4 begins when the solution of the first generation target compound starts to be added.

[0078] According to some embodiments of the present application, the amount of the third solvent is 2-20 mL, preferably 3-15 mL, relative to 1 g of the first generation target compound.

[0079] According to some embodiments of the present application, in step (4), the amount of the second generation base compound and the hydrazine is required to be within a certain range, and preferably, the hydrazine is in excess, and the molar ratio of the second generation base compound to the hydrazine is 1:(16-32), preferably 1:(18-24).

[0080] According to some embodiments of the present application, the fourth contacting is performed by adding the solution of the second generation base body compound into the hydrazine and / or the hydrazine solution at 20-40°C.

[0081] In the present application, in step (4), the hydrazine solution is obtained by dissolving hydrazine in the fourth solvent; and the solution of the second generation base body compound is obtained by dissolving the second generation base body compound in the fourth solvent; wherein the amount of the fourth solvent used for dissolving is not particularly limited, as long as it can meet the requirements of the present application.

[0082] According to some embodiments of the present application, the fourth contacting can be performed for 12-72h, preferably for 24-48h. Wherein the reaction between the second generation base body compound and the hydrazine starts when the solution of the second generation base body compound starts to be added.

[0083] According to some embodiments of the present application, the amount of the fourth solvent used can be 2-20mL, preferably 3-15mL, relative to 1g of hydrazine.

[0084] According to some embodiments of the present application, in step (4), in order to make the reaction proceed better, there are certain requirements for the adding speed of the solution of the second generation base body compound, preferably, the adding speed of 100mL of the solution of the second generation base body compound is 1-20mL / min, more preferably 1-10mL / min.

[0085] In the present application, in step (5), the amount ratio of each substance and the contacting time during the repeating of steps (3) and (4) are not particularly limited, as long as they can meet the requirements of the present application.

[0086] In the present application, steps (1) and (3) are preferably performed in the presence of a polymerization inhibitor selected from hydroquinone monomethyl ether and / or hydroquinone monomethyl ether. Wherein the amount of the polymerization inhibitor added is 0.1-1wt% of CR 1 R 2 =CR 3 (CH2) n COOR 4 .

[0087] In the present application, preferably, the method further comprises a purification step, for example, in step (1), the reaction liquid after the first contacting is subjected to a first post-treatment (purification treatment). Wherein the step of the first post-treatment is not particularly limited, as long as it can meet the requirements of the present application, for example, it can be performed by the following way: the reaction liquid after the first contacting is subjected to vacuum distillation at 30-50°C and a vacuum degree of 50-70kPa for 10-20h.

[0088] In the present application, preferably, the step (2) further comprises a second post-treatment (purification treatment) of the reaction solution after the second contact. The step of the second post-treatment is not particularly limited as long as it can meet the requirements of the present application, for example, it can be performed by the following way: the reaction solution after the second contact is subjected to vacuum distillation at 40-80℃ and a vacuum degree of 60-90kPa for 10-30h.

[0089] Similarly, the step (3), the step (4) and the step (5) can be separated and purified by referring to the purification step in the aforementioned step (1) or step (2).

[0090] In the present application, the first solvent, the second solvent, the third solvent and the fourth solvent can be the same or different as long as they can provide a medium to promote the addition reaction or the reaction between the amine group and the ester group.

[0091] The second aspect of the present application provides an application of the composition of the aforementioned first aspect in gas absorption, particularly in acid gas absorption.

[0092] According to some embodiments of the present application, the acid gas is an inorganic acid gas, preferably at least one selected from carbon dioxide, sulfur dioxide and hydrogen sulfide.

[0093] The third aspect of the present application provides a method for absorbing gas, which comprises: contacting the composition of the aforementioned first aspect with the gas to be absorbed.

[0094] According to some embodiments of the present application, the conditions of the contacting can comprise: a temperature of 30-50℃, preferably 35-45℃.

[0095] According to some embodiments of the present application, the flow rate of the gas to be absorbed is 50-200mL / min, preferably 80-150mL / min, per 100g of the composition.

[0096] In the present application, when the composition is used for absorbing the gas to be absorbed, preferably, the composition further comprises a solvent (for example, water), and preferably, the amount of the solvent is such that the concentration of the absorbent in the composition is 1-15mol / L, preferably 3-8mol / L.

[0097] In the present application, during the absorption of the gas to be absorbed (for example, acid gas) by the composition, the solution forms an organic phase and a carrier phase, wherein the organic phase is polyether and organic amine, and the carrier phase is the salt generated after the reaction of the organic amine and the gas to be absorbed (for example, acid gas).

[0098] According to some embodiments of the present application, the method further comprises regenerating the carrier phase of the composition after absorbing the gas to be absorbed. Through regeneration, the adsorbent can be recycled for reuse.

[0099] In the present application, preferably, the regeneration is performed by desorbing the gas to be absorbed (e.g. acid gas CO2) from the carrier phase of the composition after absorbing the gas to be absorbed at 80-150°C, 100-200 rpm, 500-1500 W, preferably at 90-120°C, 130-160 rpm, 800-1200 W.

[0100] In the present application, the parameter measured during regeneration is the acid gas value in the carrier phase, i.e. the relative content of CO2 absorbed in the carrier phase (V CO2 / V 溶液 , mL / mL).

[0101] The present application will be described in detail below by way of examples.

[0102] In the following examples, the raw materials are commercially available unless otherwise specified.

[0103] The reaction progress is monitored by HPLC; yield = conversion x selectivity;

[0104] Conversion = percentage of the amount of reactant participating in the reaction (amount of raw material reacted) to the amount entering the reactor (starting amount of raw material);

[0105] Selectivity = amount (mol) of key component consumed to produce the target product / amount (mol) of key component participating in the reaction; purity is determined by HPLC;

[0106] Analysis conditions for HPLC: chromatographic column is Phenomenex C18 column (250 mm x 4.6 mm, 4 μm); mobile phase is acetonitrile-water (volume ratio 70:30), detection wavelength is 350 nm, flow rate is 0.8 mL / min, injection volume is 20 μL.

[0107] Preparation Example 1

[0108] 1G base compound:

[0109]

[0110] 1G target compound:

[0111]

[0112] (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 p-benzene diol monomethyl ether was added to obtain a methyl acrylate methanol solution (MA solution); then 16.02 g of hydrazine (AH) was dissolved in 50 mL of methanol to obtain a hydrazine methanol solution (AH solution), and the AH solution was placed in a constant pressure dropping funnel; the AH solution was slowly added to the MA solution under stirring at 25°C, and the dropping was completed in 0.5 h, wherein the molar ratio of MA:AH was 8:1, and then the reaction was continued for 24 h; after the reaction was completed, the product after 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 obtained light yellow product was the 1G matrix compound, with a purity of 98.5 wt% and a yield of 93.9%.

[0113] (2) The 1G matrix product obtained in step (1) was dissolved in 100 mL of methanol, and after the 1G matrix compound was completely dissolved, it was placed in a constant pressure dropping funnel to obtain a 1G matrix compound methanol solution, and an excess of AH was added to a three-necked reaction flask to make the molar ratio of AH to 1G matrix compound 16:1; the 1G matrix compound methanol solution was slowly added under stirring at 25°C, and the dropping was completed in 0.5 h, and then the reaction was continued for 24 h; after the reaction was completed, the product after reaction was subjected to vacuum distillation at 55°C and a vacuum degree of 80 kPa for 16 h to remove methanol and excess AH, and finally the viscosity of the distillation bottle became large, and a light yellow viscous liquid was obtained as the 1G target compound, with a purity of 95.2 wt% and a yield of 87.1%.

[0114] Preparation Example 2

[0115] 2G matrix compound:

[0116]

[0117] 2G target compound:

[0118]

[0119] Steps (1) and (2) in Preparation Example 1 were repeated to obtain the 1G matrix compound and the 1G target compound, respectively;

[0120] (3) In a three-neck flask, 137.74 g of methyl acrylate (MA) was dissolved in 100 mL of methanol and 0.2 g of p-benzene diol monomethyl ether was added to obtain a methyl acrylate methanol solution (MA solution) in the same manner as in step (1); then 37.6 g of the 1G target compound was dissolved in 50 mL of methanol to obtain a methanol solution of the 1G target compound, which was placed in a constant pressure dropping funnel; the methanol solution of the 1G target compound was slowly added dropwise to the MA solution under stirring at 25°C, and the dropping was completed in 0.5 h, wherein the molar ratio of MA to the 1G target compound was 16:1, and then the reaction was continued for 24 h; after the completion of the reaction was monitored, 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 obtained light yellow product was the 2G base compound, with a purity of 98.3 wt% and a yield of 80.0%.

[0121] (4) The 2G base product obtained in step (3) was dissolved in 100 mL of methanol, and after the 2G base compound was completely dissolved, it was placed in a constant pressure dropping funnel to obtain a methanol solution of the 2G base compound; an excess of AH was added to a three-neck reaction flask to make the molar ratio of AH to the 2G base compound 16:1; the methanol solution of the 2G base compound was slowly added dropwise under stirring at 25°C, and the dropping was completed in 1 h, and then the reaction was continued for 24 h; after the completion of the reaction was monitored, the product after the reaction was subjected to vacuum distillation at 55°C and a vacuum degree of 80 kPa for 16 h to remove methanol and excess AH, and finally the viscosity of the distillation bottle became large, and the nearly light yellow viscous liquid was the 2G target compound, with a purity of 93.6 wt% and a yield of 71.3%.

[0122] Preparation Example 3

[0123] 3G base compound:

[0124]

[0125] 3G target compound:

[0126]

[0127] The 3G base compound and the 3G target compound were prepared by repeating steps (3) and (4) using the 2G target compound as the reactant in the same manner as in Preparation Example 2.

[0128] The 3G base compound had a purity of 97.6 wt% and a yield of 65.7%, and the 3G target compound had a purity of 93.2 wt% and a yield of 55.8%.

[0129] Preparation Example 4

[0130] The steps (3) and (4) were repeated in the same manner as in Preparation Example 3 using the 3G target compound as a reactant to prepare the 4G base compound and the 4G target compound.

[0131] The 4G base compound had a purity of 97.2 wt% and a yield of 49.1%, and the 4G target compound had a purity of 92.8 wt% and a yield of 42.3%.

[0132] Preparation Example 5

[0133] The steps (3) and (4) were repeated in the same manner as in Preparation Example 4 using the 2G target compound as a reactant to prepare the 5G base compound and the 5G target compound.

[0134] The 5G base compound had a purity of 96.3 wt% and a yield of 37.2%, and the 5G target compound had a purity of 92.2 wt% and a yield of 32.7%.

[0135] Preparation Example 6

[0136] The procedure of Preparation Example 2 was followed, except that 400.48 g of ethyl acrylate was used instead of 344.36 g of methyl acrylate (MA).

[0137] Finally, the 1G base compound had a purity of 98.4 wt% and a yield of 92.5%, and the 1G target compound had a purity of 95.8 wt% and a yield of 84.6%.

[0138] Preparation Example 7

[0139] The procedure of Preparation Example 2 was followed, except that 400.44 g of methyl butenoate was used instead of 344.36 g of methyl acrylate (MA).

[0140] Finally, the 1G base compound had a purity of 98.2 wt% and a yield of 93.3%, and the 1G target compound had a purity of 94.2 wt% and a yield of 85.8%.

[0141] Preparation Example 8

[0142] The procedure of Preparation Example 2 was followed, except that 456.56 g of ethyl butenoate was used instead of 344.36 g of methyl acrylate (MA).

[0143] Finally, the 1G base compound had a purity of 98.8 wt% and a yield of 91.4%, and the 1G target compound had a purity of 93.2 wt% and a yield of 82.3%.

[0144] The following test example was used to demonstrate the acid gas absorption of the composition of the present application

[0145] The organic amine, polyether and additive were prepared into a composition formula with the content shown in Table 1, and an acid gas absorbent (solvent is water) of the organic amine with a molar concentration of 3 mol / L was prepared. Among them, the weight average molecular weight of the polyethylene glycol dimethyl ether used is 260; the polyoxyethylene polyoxypropylene octadecanol ether is purchased from Daqing Weide Chemical Co., Ltd.

[0146] Gas absorption experiment: the raw gas (acid gas CO2, volume concentration is 12.8%) enters the absorption tube containing the absorbent after passing through the moisture absorption bottle and the buffer bottle at 40℃±0.5℃, wherein the gas flow of the raw gas is controlled to be 100mL / min, the absorption temperature is controlled by the constant temperature tank, after a period of time, the CO2 content in the exhaust tail gas is monitored and analyzed by using the flue gas analyzer, then the gas source is closed, and the carrier phase after absorbing the acid gas is subjected to liquid phase analysis. Among them, the raw gas pipeline is reserved to adjust the acid gas content in the raw gas. Among them, the CO2 absorbed in the absorbent is analyzed by using the gas generation method, specifically, a certain amount of sample is put into a neutralization reaction bottle, and an excess of dilute sulfuric acid solution is put into the straight pipe in the reaction bottle, the plug is tightly covered, and when the liquid surface of the solution bottle is level with the liquid surface of the straight pipe with a scale, the reading V o is recorded. The liquid in the reaction bottle is allowed to contact and react, CO2 is precipitated, and when the two liquid surfaces are level, the reading V1 is recorded. The difference between V1 and V o is the volume of CO2 generated after the reaction, from which the CO2 content in the solution can be calculated.

[0147] Regeneration experiment: according to the absorption reaction time of 6h, the absorption reaction is completed, and the carrier phase is taken for regeneration test. Among them, the regeneration temperature is controlled to be 110℃, the rotating speed of mechanical stirring is 150rpm, the power of heating device is 1000W, and after 30min, the CO2 content in the solution is measured to determine the amount of desorbed CO2.

[0148] The results of the gas absorption experiment and the regeneration experiment of the above test examples and the comparative test examples are shown in Table 2.

[0149] Table 1

[0150]

[0151] Table 2

[0152]

[0153]

[0154] In Table 2, t1 represents "the time at which the carrier phase droplets first settle after aeration", and the smaller t1 is, the stronger the phase change ability of the absorbent, i.e. the easier the phase change; t2 represents "the standing time required for the carrier phase and the organic phase to be completely separated after the absorption reaction is completed", and the smaller t2 is, the better the phase change process effect of the absorbent, which is beneficial to the reduction of the regeneration energy consumption of the absorbent;

[0155] The regeneration energy consumption represents "the energy consumption required for regenerating unit volume of CO2", and the calculation formula is: regeneration energy consumption = 1 x 30 x 60 / (L0-L 30 ), unit: kJ / mL; wherein, L0 represents the initial (at 0 min of regeneration) acid gas value in the carrier phase during the regeneration process; L 30 represents the acid gas value in the carrier phase at 30 min during the regeneration process.

[0156] The above detailed the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all fall within the protection scope of the present application.

Claims

1. A composition having acid gas absorption function, characterized in that, The composition comprises an absorbent and an additive; wherein the absorbent comprises at least one of an organic amine, a polyether, and a C7-C10 fatty alcohol; and the additive comprises a compound having a demulsifying function. The compound with demulsifying function has 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 the weight ratio of the absorbent to the additive is 100:(0.1-10). And / or, the absorbent is selected from organic amines and polyethers.

3. The composition according to claim 1, wherein the weight ratio of the absorbent to the additive is 100:(0.5-5).

4. The composition according to claim 1 or 2, wherein, Based on the total weight of the absorbent and additives in the composition, the content of the organic amine is 1-50 wt%, the content of the polyether is 40-99 wt%, and the content of the additives is 0.005-10 wt%.

5. The composition according to claim 1 or 2, wherein, Based on the total weight of the absorbent and additives in the composition, the content of the organic amine is 5-50 wt%, the content of the polyether is 45-95 wt%, and the content of the additives is 0.01-5 wt%.

6. The composition according to claim 1, wherein, The organic amine is a C1-C6 alcohol amine, selected from at least one of monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine; And / or, the polyether is selected from polyethylene glycol dimethyl ether and / or polyethylene glycol monomethyl ether.

7. The composition according to claim 1, wherein, The organic amine is at least one of monoethanolamine, diethanolamine, and triethanolamine.

8. 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.

9. The composition according to claim 1 or 8, 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.

10. The composition according to claim 1, wherein, The additive is prepared according to 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.

11. The composition according to claim 1, wherein, The additive is prepared according to 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 made 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.

12. The composition according to claim 1, wherein, The additive is prepared according to 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 made 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.

13. The composition according to any one of claims 10-12, 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.

14. The composition according to any one of claims 10-12, 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 combined 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 duration of the fourth contact is 12-72 hours; And / or, relative to 1g of hydrazine, the amount of the fourth solvent used is 2-20mL.

15. The composition according to claim 14, wherein, In step (1), the first solvent is methanol and / or water.

16. The composition according to claim 14, wherein, The amount of the first solvent used is 3-15 mL relative to 1 g of hydrazine.

17. The composition according to claim 14, wherein, CR 1 R 2 =CR 3 (CH2) n COOR 4 The molar ratio of hydrazine to hydrazine is (6-10):

1.

18. The composition according to claim 14, wherein, The addition rate is 1-10 mL / min relative to 100 mL of hydrazine and / or hydrazine solution.

19. The composition according to claim 18, wherein, The addition rate is 1-5 mL / min relative to 100 mL of hydrazine and / or hydrazine solution.

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

21. The composition according to claim 14, wherein, In step (2), the second solvent is methanol and / or water.

22. The composition according to claim 14, wherein, The amount of the second solvent used is 3-15 mL relative to 1 g of hydrazine.

23. The composition according to claim 14, wherein, The molar ratio of hydrazine to the first-generation matrix compound is (8-16):

1.

24. The composition according to claim 14, wherein, The addition rate is 1-20 mL / min relative to 100 mL of the first-generation matrix compound solution.

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

26. The composition according to claim 14, wherein, The second contact time is 12-72 hours.

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

28. The composition according to claim 14, 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).

29. The composition according to claim 14, wherein, The addition rate is 1-20 mL / min relative to 100 mL of the first-generation target compound solution.

30. The composition according to claim 14, wherein, The addition rate is 1-10 mL / min relative to 100 mL of the first-generation target compound solution.

31. The composition according to claim 14, wherein, The duration of the third contact is 24-48 hours.

32. The composition according to claim 14, wherein, The amount of the third solvent used is 3-15 mL relative to 1 g of the first-generation target compound.

33. The composition according to claim 14, wherein, In step (4), the molar ratio of the second-generation matrix compound to hydrazine is 1:(18-24).

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

35. The composition according to claim 14, wherein, The amount of the fourth solvent used is 3-15 mL relative to 1 g of hydrazine.

36. The composition according to claim 14, wherein, The addition rate is 1-20 mL / min relative to 100 mL of the second-generation matrix compound solution.

37. The composition according to claim 14, wherein, The addition rate is 1-10 mL / min relative to 100 mL of the second-generation matrix compound solution.

38. The use of the composition according to any one of claims 1-37 in gas absorption.

39. The use of the composition according to any one of claims 1-37 in the absorption of acidic gases.

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

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

42. A method for absorbing gas, characterized in that, The method comprises contacting the composition of any one of claims 1-37 with the gas to be absorbed.

43. The method according to claim 42, 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 42, wherein, The contact conditions include a temperature of 35-45°C.

45. The method according to claim 42, 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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