High-efficiency decarburizer and preparation method thereof

Abstract

The application relates to the technical field of natural gas decarburization, and particularly discloses a high-efficiency decarburization agent and a preparation method thereof. The high-efficiency decarburization agent is prepared from the following raw materials: 40-60 parts of double-modified 3-(diethoxymethylsilyl)propylamine; 10-25 parts of N-methyl monoethanolamine; 13-30 parts of sulfolane; 5-15 parts of piperazine; 3-10 parts of an activating component; 5-10 parts of deionized water; 0.5-3 parts of a stabilizer; and 0.1-1 part of an antioxidant. The double-modified 3-(diethoxymethylsilyl)propylamine is obtained by modifying 3-(diethoxymethylsilyl)propylamine with gamma-aminopropyl triethoxysilane and polyethylene glycol diglycidyl ether. The activating component comprises a metal-organic framework material and N-vinyl pyrrolidone. The high-efficiency decarburization agent can be used for decarburization of natural gas, petroleum gas and the like, and has the advantages of high adsorption capacity, fast adsorption rate and strong high-temperature resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of natural gas decarburization, and more particularly to an efficient decarburization agent and a preparation method thereof. BACKGROUND

[0002] Natural gas, as an important part of clean energy, plays a key role in energy structure transformation and carbon neutralization. However, natural gas often contains 0.5%-8% of carbon dioxide and other acidic components by volume fraction. These substances not only reduce the calorific value of natural gas, but also exacerbate the corrosion of metal pipelines during pipeline transportation, and affect the stability of subsequent liquefaction processes. Through decarburization treatment, the CO2 content in natural gas can be reduced to ≤2% or ≤50ppm, thereby improving energy utilization efficiency, prolonging equipment service life, and meeting the quality requirements of natural gas.

[0003] In related technologies, a patent document with publication number CN114540089B discloses a natural gas desulfurization and decarburization agent and a use method thereof. The decarburization agent components include 40 parts of 3-(diethoxymethylsilyl)propylamine, 60 parts of diethylene glycol dimethyl ether, or 50 parts of 3-(diethoxymethylsilyl)propylamine, 40 parts of diethylene glycol dimethyl ether, 10 parts of isopropyl alcohol, or 60 parts of 3-(diethoxymethylsilyl)propylamine, 20 parts of cyclobutane sulfone, 10 parts of isopropyl alcohol, and 10 parts of diethylene glycol dimethyl ether. In the decarburization agent, the silicon-based amine compound is the core active ingredient, which realizes adsorption through acid-base neutralization or salt formation reaction between the amino group and CO2; and the organic solvent is used to adjust the viscosity of the system and improve the mass transfer efficiency.

[0004] However, in actual use, when the operating temperature of the decarburization tower exceeds 60℃, the hydrolysis rate of the silicon-based amine compound increases, resulting in a decrease in the concentration of the active ingredient, and further causing the adsorption capacity of CO2 to decrease. In addition, the silicon-based amine forms long-chain polymers or network macromolecules through hydrolysis-condensation, resulting in an increase in the viscosity of the solution, thus reducing the mass transfer efficiency of the decarburization system, and further reducing the adsorption rate of CO2. In summary, the decarburization agent in related technologies has the defect of insufficient high-temperature stability. SUMMARY

[0005] In order to improve the high-temperature stability of the decarburization agent and ensure that the decarburization agent has better adsorption capacity and adsorption rate under high-temperature conditions, the present application provides an efficient decarburization agent and a preparation method thereof.

[0006] The efficient decarburization agent provided by the present application adopts the following technical solution:

[0007] An efficient decarburization agent includes the following raw materials by weight:

[0008] bis-modified 3-(diethoxymethylsilyl)propylamine 40-60 parts;

[0009] N-methyl monoethanolamine 10-25 parts;

[0010] sulfolane 13-30 parts;

[0011] piperazine 5-15 parts;

[0012] activating component 3-10 parts;

[0013] deionized water 5-10 parts;

[0014] stabilizer 0.5-3 parts;

[0015] antioxidant 0.1-1 part;

[0016] The bis-modified 3-(diethoxymethylsilyl)propylamine is obtained by modifying 3-(diethoxymethylsilyl)propylamine with γ-aminopropyl triethoxysilane and polyethylene glycol diglycidyl ether;

[0017] The activating component comprises a metal organic framework material and N-vinyl pyrrolidone.

[0018] By using the above technical solution, the aminopropyl silane group is introduced to the surface of the 3-(diethoxymethylsilyl)propylamine molecule by γ-aminopropyl triethoxysilane. The aminopropyl silane group has certain chemical activity, and its structural characteristics are helpful for subsequent modification reaction and enhancement of the adsorption capacity of carbon dioxide. At the same time, this modification changes the electron cloud distribution and spatial structure of the original molecule to a certain extent, laying the foundation for preventing hydrolysis at high temperature. The amino group in the preliminary modified product undergoes ring-opening reaction with the epoxy group of the polyethylene glycol diglycidyl ether. The polyethylene glycol segment has hydrophilicity and can form a wrapping layer on the surface of the molecule. This wrapping layer has a large steric hindrance effect, which can prevent water molecules from approaching the core structure of the silane amine compound, thereby effectively preventing the hydrolysis of the silane amine compound at high temperature, avoiding the problem of increased solution viscosity caused by the formation of long-chain polymers or network macromolecules due to hydrolysis-condensation, thereby ensuring the mass transfer efficiency of the decarburization system at high temperature. On the other hand, the hydrophilicity of the polyethylene glycol segment enables it to interact with carbon dioxide molecules to some extent, increasing the adsorption capacity of carbon dioxide. The metal organic framework material in the activating component has a high specific surface area and a regular pore structure, which can provide a large number of adsorption sites and has a strong adsorption capacity for carbon dioxide molecules; N-vinyl pyrrolidone can improve the dispersibility of the metal organic framework material in the decarburization agent system, making it better to play the adsorption role, and the two together increase the adsorption capacity of the decarburization agent for carbon dioxide. Therefore, the decarburization agent of the present application has good high-temperature stability and can ensure that the decarburization agent has a better adsorption capacity and adsorption rate at high temperature.

[0019] Optionally, the double modified 3- (diethoxymethylsilyl) propylamine is prepared by the following method:

[0020] A, mixing 3- (diethoxymethylsilyl) propylamine with γ-aminopropyl triethoxysilane solution, then adding toluene sulfonic acid, stirring at 40-60℃ for 2-4 hours under nitrogen protection to obtain a preliminary modified product;

[0021] B, stirring the preliminary modified product with polyethylene glycol diglycidyl ether solution at 50-70℃ for 1-3 hours to obtain double modified 3- (diethoxymethylsilyl) propylamine.

[0022] By adopting the above technical solution, the first step reaction is carried out at 40-60℃ under nitrogen protection, and the appropriate temperature and protective atmosphere can ensure that the reaction proceeds smoothly and avoids side reactions, so that the aminopropyl silane group is effectively introduced, and toluene sulfonic acid as a catalyst is conducive to improving the reaction rate of introducing the aminopropyl silane group; the second step is reacted at 50-70℃, and this temperature range is conducive to the full reaction of polyethylene glycol diglycidyl ether and the preliminary modified product to form a stable polyethylene glycol segment coating layer. By accurately controlling the reaction conditions, the performance of the double modified product is stable, so as to better achieve the effects of improving high temperature stability, increasing adsorption capacity and improving adsorption rate.

[0023] Optionally, in step A, the mass concentration of the γ-aminopropyl triethoxysilane solution is 5%-10%; the mass ratio of 3- (diethoxymethylsilyl) propylamine to γ-aminopropyl triethoxysilane solution is 1: (0.4-0.6).

[0024] Optionally, in step A, the amount of toluene sulfonic acid added is 1.5%-2.5% of the total mass of 3- (diethoxymethylsilyl) propylamine and γ-aminopropyl triethoxysilane solution.

[0025] By adopting the above technical solution, toluene sulfonic acid as a catalyst, appropriate addition can speed up the first step modification reaction rate and improve production efficiency. At the same time, the appropriate amount of catalyst can ensure that the reaction proceeds fully, so that the aminopropyl silane group is effectively introduced, laying a foundation for the subsequent formation of a stable double modified structure, which is conducive to improving the high temperature stability and adsorption performance of the decarburizer.

[0026] Optionally, in step B, the mass concentration of the polyethylene glycol diglycidyl ether solution is 3%-8%; the mass ratio of the preliminary modified product to the polyethylene glycol diglycidyl ether solution is 1: (0.4-0.8).

[0027] Optionally, the active component comprises 20%-40% metal organic framework material and 60%-80% N-vinyl pyrrolidone.

[0028] The above-mentioned proportion of the activated component can make the high specific surface area and strong adsorption capacity of the metal organic framework material and the dispersion effect of N-vinylpyrrolidone fully play a synergistic effect. Both sufficient adsorption sites for adsorbing carbon dioxide and uniform dispersion of the metal organic framework material in the decarburizer system can be ensured, thereby improving the adsorption efficiency and increasing the adsorption capacity and adsorption rate of the decarburizer.

[0029] Optionally, the metal organic framework material is any one of UiO-66-NH2 and MIL-125-NH2.

[0030] Optionally, the stabilizer comprises 2-mercaptobenzothiazole, dilauryl thiodipropionate and tris (2, 4-di-tert-butylphenyl) phosphite in a mass ratio of 1: (1-2): (0.5-1.5).

[0031] The above-mentioned stabilizer system in the above-mentioned ratio can effectively enhance the synergistic mechanism of the stabilizer system of the present application through “chelation-decomposition-trapping”, fundamentally inhibit the high-temperature hydrolysis and oxidative degradation of silicon-based amines, and solve the problem of dramatic increase in viscosity and decrease in mass transfer efficiency of the traditional decarburizer due to hydrolysis and condensation. The above-mentioned stabilizer system effectively improves the high-temperature stability of the decarburizer, which is conducive to maintaining a better adsorption capacity and adsorption rate of the decarburizer under high-temperature working conditions.

[0032] Optionally, the antioxidant is any one of DBPC and BHT.

[0033] The present application also provides a preparation method of the high-efficiency decarburizer.

[0034] The preparation method of the high-efficiency decarburizer comprises the following steps:

[0035] S1, after the piperazine is melted by heating, N-methyl monoethanolamine is added to form a base liquid A, and then sulfolane and double-modified 3- (diethoxymethylsilyl) are mixed and stirred to form a base liquid B;

[0036] S2, the base liquid A and the base liquid B are added to a blending kettle, deionized water is added, and stirring and mixing are performed for 30-40 min, and then the activated component, the stabilizer and the antioxidant are added and stirred for 30-45 min to obtain the high-efficiency decarburizer.

[0037] By adopting the technical scheme, the piperazine is first heated and melted to be mixed with N-methyl monoethanolamine to form a base liquid A, then the sulfolane and the double modified 3-(diethoxymethylsilyl) propylamine are mixed to form a base liquid B, then the base liquid A and the base liquid B are added into a blending kettle, and deionized water, an activating component, a stabilizer and an antioxidant are sequentially added and stirred and mixed. The preparation method of the step-by-step mixing is beneficial to fully mixing and uniformly mixing the raw materials, ensures that the components can fully play their roles, so that the high-efficiency decarbonizing agent with excellent performance is prepared, and the high-temperature stability, the adsorption capacity and the adsorption rate of the decarbonizing agent are improved.

[0038] In summary, the present application has the following beneficial effects:

[0039] 1. The present application utilizes γ-aminopropyl triethoxysilane and polyethylene glycol diglycidyl ether to modify 3-(diethoxymethylsilyl) propylamine. In the first step, the aminopropyl silane group is introduced to change the electron cloud distribution and spatial structure, laying the foundation for preventing hydrolysis at high temperature; in the second step, the polyethylene glycol segment coating layer is formed, which effectively prevents water molecules from approaching the silicon-based amine core structure by steric hindrance effect, avoiding the formation of long-chain polymers or network macromolecules by hydrolysis-condensation at high temperature, solving the problem of traditional decarbonizing agents that the concentration of active ingredients decreases, the solution viscosity increases, and the mass transfer efficiency decreases due to hydrolysis at high temperature. At the same time, 2-mercaptobenzothiazole, dilauryl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite in the stabilizer synergistically act in a specific ratio through the "chelation-decomposition-capture" mechanism, fundamentally inhibiting the high-temperature hydrolysis and oxidative degradation of silicon-based amine, further enhancing the high-temperature stability of the decarbonizing agent, and ensuring that it can still stably play a decarbonizing role under high-temperature conditions.

[0040] 2. The polyethylene glycol segment of the double modified 3-(diethoxymethylsilyl) propylamine in the present application has hydrophilicity, can produce dipole-dipole interaction with carbon dioxide molecules, etc., increasing the adsorption and binding capacity of carbon dioxide. The metal-organic framework material in the activating component has a high specific surface area and a regular pore structure, which can provide a large number of adsorption sites and has strong adsorption capacity for carbon dioxide molecules; N-vinyl pyrrolidone can improve the dispersibility of the metal-organic framework material in the decarbonizing agent system, making it better play the adsorption role. The two synergistically act, fully exerting the high adsorption capacity of the metal-organic framework material and the dispersing effect of N-vinyl pyrrolidone, which can not only ensure sufficient adsorption sites, but also make the metal-organic framework material uniformly dispersed, improving the adsorption efficiency. In addition, the amino groups in N-methyl monoethanolamine and piperazine as basic groups can also react with carbon dioxide, further increasing the adsorption capacity of the decarbonizing agent for carbon dioxide.

[0041] 3、The amino groups contained in N-methyl monoethanolamine and piperazine in the decarburization agent of the present application can rapidly undergo acid-base neutralization or salt formation reaction with carbon dioxide, accelerating the process of carbon dioxide transferring from gas phase to liquid phase and being adsorbed, thereby providing a basis for improving the adsorption rate. Sulfolane as an organic solvent has good solubility and suitable viscosity, which can adjust the viscosity of the decarburization agent system, improve the mass transfer efficiency of carbon dioxide therein, promote the contact reaction between carbon dioxide and the adsorption components, and thus effectively enhance the adsorption rate of the decarburization agent. DETAILED DESCRIPTION

[0042] The present application will be further described in detail below in combination with examples.

[0043] Preparation example of double-modified 3-(diethoxymethylsilyl)propylamine

[0044] Preparation example 1

[0045] Double-modified 3-(diethoxymethylsilyl)propylamine is prepared by the following method:

[0046] A. 10 kg of 3-(diethoxymethylsilyl)propylamine is mixed with 4 kg of γ-aminopropyl triethoxysilane solution with a mass concentration of 5%, and then 0.21 kg of toluenesulfonic acid is added. Under nitrogen protection, stirring reaction is carried out at 40℃ for 4 hours to obtain a preliminary modified product;

[0047] B. 10 kg of the preliminary modified product is stirred with 4 kg of polyethylene glycol diglycidyl ether solution with a mass concentration of 3% at 50℃ for 3 hours to obtain double-modified 3-(diethoxymethylsilyl)propylamine.

[0048] Preparation example 2

[0049] Double-modified 3-(diethoxymethylsilyl)propylamine is prepared by the following method:

[0050] A. 10 kg of 3-(diethoxymethylsilyl)propylamine is mixed with 5 kg of γ-aminopropyl triethoxysilane solution with a mass concentration of 8%, and then 0.3 kg of toluenesulfonic acid is added. Under nitrogen protection, stirring reaction is carried out at 50℃ for 3 hours to obtain a preliminary modified product;

[0051] B. 10 kg of the preliminary modified product is stirred with 6 kg of polyethylene glycol diglycidyl ether solution with a mass concentration of 5% at 60℃ for 2 hours to obtain double-modified 3-(diethoxymethylsilyl)propylamine.

[0052] Preparation example 3

[0053] Double-modified 3-(diethoxymethylsilyl)propylamine is prepared by the following method:

[0054] A, 10 kg of 3- (diethoxymethylsilyl) propylamine is mixed with 6 kg of γ-aminopropyl triethoxysilane solution with a mass concentration of 10%, then 0.4 kg of toluenesulfonic acid is added, and the reaction is stirred at 60°C for 2 hours under nitrogen protection to obtain a preliminary modified product;

[0055] B, 10 kg of the preliminary modified product is stirred with 8 kg of polyethylene glycol diglycidyl ether solution with a mass concentration of 8% at 70°C for 1 hour to obtain a double modified 3- (diethoxymethylsilyl) propylamine.

[0056] Preparation Example 4

[0057] The modified 3- (diethoxymethylsilyl) propylamine is prepared by the following method:

[0058] 10 kg of 3- (diethoxymethylsilyl) propylamine is mixed with 6 kg of γ-aminopropyl triethoxysilane solution with a mass concentration of 10%, then 0.4 kg of toluenesulfonic acid is added, and the reaction is stirred at 60°C for 2 hours under nitrogen protection to obtain a preliminary modified product;

[0059] Preparation Example 5

[0060] The modified 3- (diethoxymethylsilyl) propylamine is prepared by the following method:

[0061] 10 kg of 3- (diethoxymethylsilyl) propylamine is mixed with 6 kg of γ-aminopropyl triethoxysilane solution with a mass concentration of 10%, then 0.4 kg of toluenesulfonic acid is added, and the reaction is stirred at 60°C for 2 hours under nitrogen protection to obtain a preliminary modified product;

[0062] Example

[0063] Example 1

[0064] A high-efficiency decarburizing agent, the raw material components and amounts are shown in Table 1, wherein the double modified 3- (diethoxymethylsilyl) propylamine is selected from the double modified 3- (diethoxymethylsilyl) propylamine prepared in Preparation Example 1; the ratio of the activation component is 20% UiO-66-NH2 and 80% N-vinylpyrrolidone; the stabilizer is 2-mercaptobenzothiazole, dilauryl thiodipropionate and tris (2, 4-di-tert-butylphenyl) phosphite with a mass ratio of 1:1:0.5; and the antioxidant is DBPC.

[0065] A preparation method of a high-efficiency decarburizing agent, comprising the following steps:

[0066] S1, after the piperazine is melted, N-methyl monoethanolamine is added to form a base liquid A, then sulfolane and double modified 3- (diethoxymethylsilyl) are mixed to form a base liquid B;

[0067] S2, add base liquid A and base liquid B to the blending kettle, then add deionized water, stir and mix for 30 min, then add the activating component, stabilizer and antioxidant and stir for 30 min to obtain the high-efficiency decarburizer.

[0068] Example 2

[0069] A high-efficiency decarburizer, the raw material components and amounts of which are shown in Table 1, wherein the double-modified 3-(diethoxymethylsilyl) propylamine is the double-modified 3-(diethoxymethylsilyl) propylamine prepared in Preparation Example 2; the ratio of the activating component is 30% of UiO-66-NH2 and 70% of N-vinylpyrrolidone; the stabilizer is 2-mercaptobenzothiazole, dilauryl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite at a mass ratio of 1:1.5:1; and the antioxidant is DBPC.

[0070] A preparation method of a high-efficiency decarburizer, comprising the following steps:

[0071] S1, melt piperazine and then mix and stir with N-methyl monoethanolamine to form base liquid A, and then mix and stir sulfolane and double-modified 3-(diethoxymethylsilyl) to form base liquid B;

[0072] S2, add base liquid A and base liquid B to the blending kettle, then add deionized water, stir and mix for 35 min, then add the activating component, stabilizer and antioxidant and stir for 38 min to obtain the high-efficiency decarburizer.

[0073] Example 3

[0074] A high-efficiency decarburizer, the raw material components and amounts of which are shown in Table 1, wherein the double-modified 3-(diethoxymethylsilyl) propylamine is the double-modified 3-(diethoxymethylsilyl) propylamine prepared in Preparation Example 3; the ratio of the activating component is 40% of UiO-66-NH2 and 60% of N-vinylpyrrolidone; the stabilizer is 2-mercaptobenzothiazole, dilauryl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite at a mass ratio of 1:2:1.5; and the antioxidant is DBPC.

[0075] A preparation method of a high-efficiency decarburizer, comprising the following steps:

[0076] S1, melt piperazine and then mix and stir with N-methyl monoethanolamine to form base liquid A, and then mix and stir sulfolane and double-modified 3-(diethoxymethylsilyl) to form base liquid B;

[0077] S2, add base liquid A and base liquid B to the blending kettle, then add deionized water, stir and mix for 40 min, then add the activating component, stabilizer and antioxidant and stir for 45 min to obtain the high-efficiency decarburizer.

[0078] Table 1 Raw material components and amounts (kg) of decarburization agent in Examples 1-3

[0079]

[0080] Example 4

[0081] A high-efficiency decarburization agent, which differs from Example 1 in that MIL-125-NH2 is used instead of UiO-66-NH2 as the metal-organic framework material in the raw material activation component.

[0082] Example 5

[0083] A high-efficiency decarburization agent, which differs from Example 1 in that BHT is selected as the antioxidant in this example.

[0084] Example 6

[0085] A high-efficiency decarburization agent, which differs from Example 1 in that an equal amount of dilauryl thiodipropionate is selected as the stabilizer instead of in the raw material in this example.

[0086] Comparative Example

[0087] Comparative Example 1

[0088] A decarburization agent, in which 30 kg of N-aminoethyl-3-aminopropyl methyl dimethoxy silane and 70 kg of diethylene glycol dimethyl ether are mixed uniformly to obtain the decarburization agent.

[0089] Comparative Example 2

[0090] A high-efficiency decarburization agent, which differs from Example 1 in that an equal amount of the modified 3-(diethoxymethylsilyl)propylamine prepared in Preparation Example 4 is used instead of the double-modified 3-(diethoxymethylsilyl)propylamine in the raw material in this comparative example.

[0091] Comparative Example 3

[0092] A high-efficiency decarburization agent, which differs from Example 1 in that an equal amount of the modified 3-(diethoxymethylsilyl)propylamine prepared in Preparation Example 5 is used instead of the double-modified 3-(diethoxymethylsilyl)propylamine in the raw material in this comparative example.

[0093] Comparative Example 4

[0094] A high-efficiency decarburization agent, which differs from Example 1 in that no activation component is added in the raw material in this comparative example, and the difference is made up with deionized water.

[0095] Performance detection test

[0096] 1. Static adsorption capacity test

[0097] Test method: 50 g of decarburization agent was placed in a constant temperature sealed reaction kettle (volume 500 mL, pressure 3 MPa), high-purity N2 (99.99%) was blown for 30 min to remove air, then CO2 gas was introduced into the reaction kettle, the pressure was maintained at 1.5 MPa, constant temperature stirring (300 r / min) for 4 h. After adsorption equilibrium, the pressure was reduced to normal pressure, and the remaining CO2 concentration was analyzed by gas chromatography. The mass of CO2 adsorbed by unit mass of decarburization agent (mg / g) was calculated by mass conservation. Two groups of samples were set for each decarburization agent obtained in Examples 1-6 and Comparative Example 4, and the adsorption test was carried out in a constant temperature sealed reaction kettle at temperatures of 25°C and 70°C, respectively. The results are shown in Table 2.

[0098] 2. Adsorption rate test

[0099] Test method: 50 g of decarburization agent was placed in a 500 mL high-pressure reaction kettle, CO2 was introduced to a pressure of 2.0 MPa, and constant temperature stirring (500 r / min) was carried out at 25°C and 70°C. The CO2 partial pressure drop rate per unit time was recorded to indirectly represent the adsorption rate. The results are shown in Table 2.

[0100] Table 2 test results

[0101]

[0102] As can be seen from Table 2, the adsorption capacity of Example 1 decreased from 195 mg / g to 186 mg / g at 70°C, with a decrease of about 4.6%. The adsorption rate decreased from 8.8 kPa / min to 7.9 kPa / min, with a decrease of about 10.2%. The adsorption capacity of Example 2 decreased by about 4.6%, and the adsorption rate decreased by about 12.4%. The adsorption capacity of Example 3 decreased by about 7.0%, and the adsorption rate decreased by about 14.4%. The adsorption capacity of Example 4 decreased by about 3.6%, and the adsorption rate decreased by about 10.2%. In contrast, the adsorption capacity of the traditional decarburization agent of Comparative Example 1 decreased by about 38.4%, and the adsorption rate decreased by about 57.9%. Therefore, the decarburization agent provided by the present application has better high temperature resistance, and the attenuation loss of adsorption capacity and adsorption rate under high temperature conditions is significantly smaller than that of traditional decarburization agents. The double-modified 3- (diethoxymethylsilyl) propylamine used in the present application forms a steric hindrance layer with its polyethylene glycol segment, inhibits the hydrolysis of the silicon-based amine, and reduces the viscosity increase; the activated component (UiO-66-NH2 and N-vinyl pyrrolidone) cooperatively provides adsorption sites and improves dispersibility, thereby enhancing the adsorption stability of the decarburization agent at high temperatures.

[0103] The adsorption capacity of Example 5 decreased by about 5.1%, and the adsorption rate decreased by about 9.4%. It is shown that replacing the antioxidant with BHT has an antioxidant effect similar to that of DBPC, which can inhibit the oxidative degradation of the silicon-based amine; the double modifier and the activated component act stably, and the attenuation amplitude of the adsorption performance under high temperature is close to that of Example 1.

[0104] The adsorption capacity of Example 6 decreased by about 10.7%, and the adsorption rate decreased by about 17.2%. Since the stabilizer only uses dilauryl thiodipropionate, it lacks the chelation of 2-mercaptobenzothiazole and the free radical capture ability of phosphite, and cannot effectively inhibit the high-temperature hydrolysis and oxidation of silicon-based amines, resulting in a decrease in active ingredient concentration, an increase in solution viscosity, a decrease in mass transfer efficiency, and a significant decrease in adsorption performance.

[0105] The adsorption capacity of Comparative Example 2 decreased by about 35.6%, and the adsorption rate decreased by about 42.3%. 3-(diethoxymethylsilyl) propylamine only introduces an aminopropyl silane group, and lacks the steric hindrance protection of the polyethylene glycol segment, so water molecules can still contact the silicon-based amine core structure at high temperatures, resulting in hydrolysis-condensation reactions, an increase in viscosity, and a decrease in mass transfer efficiency.

[0106] The adsorption capacity of Comparative Example 3 decreased by about 33.5%, and the adsorption rate decreased by about 49.4%. 3-(diethoxymethylsilyl) propylamine is only wrapped with polyethylene glycol and does not introduce an aminopropyl silane group to change the molecular structure, so the stability of the silicon-based amine core structure is insufficient, and hydrolysis still occurs at high temperatures. In addition, the polyethylene glycol segment itself may be oxidized and degraded at high temperatures, resulting in the failure of the wrapping layer.

[0107] The adsorption capacity of Comparative Example 4 decreased by about 10.9%, and the adsorption rate decreased by about 40.2%. Since no active ingredient was added, the decarburizer lacks the high specific surface area adsorption sites of metal-organic framework materials, and the dispersion of N-vinylpyrrolidone also disappears, so the decarburizer mainly relies on the reaction of amines with CO2 at high temperatures, but the adsorption sites are insufficient, and the mass transfer efficiency decreases due to the increase in viscosity, resulting in a more severe decrease in adsorption performance.

[0108] The specific embodiments are merely illustrative of the present application, and are not intended to limit the present application. Those skilled in the art can make modifications to the embodiments without creative contributions after reading the present specification, and the modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A highly efficient decarbonizing agent, characterized in that, Raw materials comprising the following weight components: 40-60 parts of dual-modified 3-(diethoxymethylsilyl)propylamine; 10-25 parts of N-methylmonoethanolamine; Sulfolane 13-30 parts; Piperazine 5-15 parts; 3-10 parts of activating component; 5-10 parts deionized water; Stabilizer 0.5-3 parts; Antioxidant 0.1-1 part; The modified 3-(diethoxymethylsilyl)propylamine was prepared by the following method: A. Mix 3-(diethoxymethylsilyl)propylamine with a solution of γ-aminopropyltriethoxysilane, then add toluenesulfonic acid, and stir the mixture at 40-60°C for 2-4 hours under nitrogen protection to obtain a preliminary modified product; B. The preliminary modified product is reacted with polyethylene glycol diglycidyl ether solution at 50-70℃ for 1-3 hours to obtain bis-modified 3-(diethoxymethylsilyl)propylamine; The activating components include metal-organic framework materials and N-vinylpyrrolidone.

2. The high-efficiency decarbonizing agent according to claim 1, characterized in that: In step A, the mass concentration of the γ-aminopropyltriethoxysilane solution is 5%-10%; the mass ratio of 3-(diethoxymethylsilyl)propylamine to the γ-aminopropyltriethoxysilane solution is 1:(0.4-0.6).

3. The high-efficiency decarbonizing agent according to claim 2, characterized in that: In step A, the amount of toluenesulfonic acid added is 1.5%-2.5% of the total mass of the solutions of 3-(diethoxymethylsilyl)propylamine and γ-aminopropyltriethoxysilane.

4. The high-efficiency decarbonizing agent according to claim 1, characterized in that: In step B, the mass concentration of the polyethylene glycol diglycidyl ether solution is 3%-8%; the mass ratio of the preliminary modified product to the polyethylene glycol diglycidyl ether solution is 1:(0.4-0.8).

5. The high-efficiency decarbonizing agent according to claim 1, characterized in that: The activating components include 20%-40% metal-organic framework material and 60%-80% N-vinylpyrrolidone.

6. The high-efficiency decarbonizing agent according to claim 5, characterized in that: The metal-organic framework material is either UiO-66-NH2 or MIL-125-NH2.

7. The high-efficiency decarbonizing agent according to claim 1, characterized in that: The stabilizer comprises 2-mercaptobenzothiazole, dilauryl thiodipropionate, and tris(2,4-di-tert-butylphenyl) phosphite in a mass ratio of 1:(1-2):(0.5-1.5).

8. The high-efficiency decarbonizing agent according to claim 1, characterized in that: The antioxidant is DBPC.

9. A method for preparing a high-efficiency decarbonizing agent according to any one of claims 1-8, characterized in that, Includes the following steps: S1. After heating and melting piperazine, add N-methyl monoethanolamine and mix and stir to form base solution A. Then mix sulfolane and bis-modified 3-(diethoxymethylsilyl) to form base solution B. S2. Add base solution A and base solution B to the mixing tank, then add deionized water and stir for 30-40 minutes. Then add the activating component, stabilizer and antioxidant and stir for 30-45 minutes to obtain a high-efficiency decarbonizing agent.

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