A new type of non-aqueous glyceryl fatty amine absorbent for capturing carbon dioxide in mixed gas and application

Abstract

The application discloses a new type of non-water glyceryl fatty amine absorbent for capturing carbon dioxide in mixed gas and application thereof, and belongs to the technical field of carbon neutralization. The absorption system of the application does not need solvent water, and can realize complete desorption of carbon dioxide within 30 minutes under the condition of heating at 80 DEG C, greatly reducing the desorption energy consumption; by introducing a glyceryl ether group with low toxicity and biodegradability into the molecular structure of the absorbent, the flowability of the non-water absorbent in the carbon dioxide capture process is improved, thereby the internal mass transfer of the system is strengthened, and the capture capacity is increased; meanwhile, the amine group in the structure of the absorbent is alkylated, the hydrogen bond interaction between molecules is inhibited, the system viscosity is reduced, and the reaction heat of the absorbent and carbon dioxide is controlled, thereby the desorption efficiency is improved, and the desorption energy consumption is reduced. The application is processed by targeted low-viscosity functionalization at the molecular level, and the carbon dioxide capture capacity of the absorbent is increased, and the desorption efficiency is improved, and the desorption energy consumption is reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of carbon neutralization, and relates to a new type of non-aqueous glyceryl fatty amine absorbent for capturing carbon dioxide in mixed gas and application. BACKGROUND

[0002] Carbon dioxide is a major greenhouse gas, and its excessive emission leads to natural disasters represented by climate change. Human civilization relies on industrial production based on energy engineering mainly based on fossil fuel combustion, which produces a large amount of carbon dioxide emissions every year. Therefore, how to reduce industrial carbon dioxide emissions and then inhibit the increase of atmospheric carbon dioxide concentration has become a common concern of the global society. As an important participant and leader in global climate governance, China has included "carbon neutralization" and "carbon peak" into the overall development strategy planning to lead the international community to work together to address environmental problems caused by the greenhouse effect. Under the current "double carbon" target background, the academic and industrial circles are accelerating the development of new energy to replace traditional fossil energy while actively developing efficient and low-cost decarbonization technology to meet the huge demand for carbon dioxide emission reduction. On the other hand, carbon dioxide is a cheap and renewable carbon resource, which can be used as a C1 building block to construct chemical raw materials and energy products such as urea, carbonate, polycarbonate, methanol, formamide, carboxylic acid and olefin. Therefore, considering environmental protection, national policy guidance and economic benefits, developing, improving and applying carbon dioxide capture technology has very important strategic significance, which is not only an effective way to solve environmental problems, but also provides a material basis for resource utilization.

[0003] Industrial flue gas with carbon dioxide content of about 5-20% is the primary application scenario of carbon capture technology. The current industry mainly uses chemical absorption method based on alcohol amine (ethanol amine, diethanol amine, methyldiethanol amine, hydroxyethyl ethylenediamine and piperazine, etc.) solution. The alcohol amine molecule in the aqueous solution reacts reversibly with carbon dioxide to generate ammonium carbamate or ammonium bicarbonate, and then the carbon dioxide is separated from the flue gas by heating to desorb carbon dioxide and regenerate the absorbent (reaction formula 1). The capture capacity of 30wt% ethanol amine solution under stable circulation is 6-10wt%, the desorption temperature is above 120℃, and the desorption enthalpy is 70-90kJ / mol. The alcohol amine is cheap and has good reactivity. The water-based chemical absorption method based on alcohol amine solution has little effect on the existing process and is easy to operate. It is a mature strategy for decarburization of flue gas at present, and there are many industrial demonstration projects in operation. However, due to the limitations of the structure of alcohol amine solution absorbent, it has the following three insurmountable shortcomings: 1) water needs to be added as a solvent to dilute alcohol amine to reduce its working viscosity, but the addition of a large amount of solvent water not only reduces the system mass capture capacity, but also causes a sharp increase in energy consumption in the carbon dioxide thermal desorption process; 2) the aqueous solution is rich in hydrogen bond donors, which is conducive to the stability of ammonium carbamate and ammonium bicarbonate, thereby increasing the difficulty of carbon dioxide thermal desorption; 3) the alcohol amine solution has strong corrosiveness to metal equipment and pipelines.

[0004] Reaction formula 1

[0005]

[0006] In summary, although the conventional alcohol amine chemical absorbent is mature in technology, due to the limitations of its structure, the capture capacity cannot be further improved, and its desorption temperature is high and the energy consumption is huge, and it also has strong corrosion to the equipment. Therefore, the academic and industrial circles have invested a lot of resources in the research and development of new carbon dioxide capture systems, and have proposed the concept of non-aqueous absorbent to avoid the performance defects caused by aqueous conditions from the source. However, as the research and application of non-aqueous chemical absorption technology continue to deepen, some problems that need to be solved have become increasingly prominent, especially the sudden increase in the viscosity of the absorbent during the absorption process, which causes the deterioration of the internal mass transfer of the system and the difficulty of pipeline transmission, thereby limiting the efficiency of the absorption and desorption process. Therefore, in order to achieve the goal of "carbon neutralization" of the country, it is still urgent to develop non-aqueous absorbents with higher capture capacity, lower working viscosity and lower desorption energy consumption. SUMMARY

[0007] The purpose of the present application is to provide a new type of non-aqueous glycerol-based fatty amine absorbent with high efficiency and low energy consumption for capturing carbon dioxide in mixed gas and its application, in order to solve the problems of low capture capacity, high desorption energy consumption and strong corrosion of the existing alcohol amine solution absorption system.

[0008] The technical solutions of the present application are as follows:

[0009] A kind of high-efficiency energy-saving new type non-water glyceryl fatty amine absorbent for capturing carbon dioxide in mixed gas, the structural skeleton of the absorbent is 1,3-glycerol ether, and 2-aminoethoxy, 2-(2-aminoethoxy) ethoxy or 2-(2-(2-aminoethoxy) ethoxy)-ethoxy is linked to its 2-position, the amine group contained in the absorbent is functionalized as a secondary amine;

[0010] The glyceryl fatty amine absorbent is one or more of compounds shown in formula (I), formula (II) and formula (III);

[0011]

[0012] Wherein, R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0013] R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0014] R 3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0015] R 4 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0016] R 5 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0017] R 6 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0018] R 7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0019] R 8 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl;

[0020] R 9 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl or 2-hydroxyethyl.

[0021] The novel non-aqueous glycerol-based fatty amine absorbent has a water content of less than 1 wt%.

[0022] This invention features a targeted design of the absorbent structure at the molecular level: 1) The absorbent structure contains glycerol ether groups with low toxicity and biodegradability, which can improve the fluidity of the non-aqueous absorbent during carbon dioxide capture, thereby enhancing the internal mass transfer of the system and increasing its capture capacity; 2) The amine groups in the absorbent structure are alkylated, that is, the primary amine is converted into a secondary amine, which inhibits the hydrogen bonding between molecules, thereby reducing the viscosity of the system and controlling the heat of reaction between the absorbent and carbon dioxide, thus improving the desorption efficiency and reducing the desorption energy consumption.

[0023] This invention also provides a method for preparing the novel non-aqueous glycerol-based fatty amine absorbent, comprising the following steps:

[0024] S1. Chloroalkoxy-1,3-glycerol diether containing the corresponding function, denoted as component 1, and amine or amine solution containing the corresponding function, denoted as component 2, are added sequentially to a high-pressure reactor and reacted at 70-80°C for 12 hours to obtain a reaction mixture; the molar ratio of component 1 to component 2 is 1:5-30.

[0025] After S2 is immersed in an ice-water bath in an autoclave, the reaction mixture is transferred to a beaker cooled in an ice-water bath. NaOH is added in batches with stirring. The molar ratio of NaOH to component 1 is 10-6:1. After stirring the solution for 20-40 minutes, it is transferred to a separatory funnel and allowed to stand. The white NaOH-containing emulsion (lower layer) and the brownish-yellow water-containing organic phase (upper layer) gradually separate.

[0026] S3 collects the brownish-yellow aqueous organic phase and transfers it to a beaker cooled in an ice-water bath. NaOH is added in batches with stirring, and the molar ratio of NaOH to component 1 is 1-3:1. After stirring at room temperature for 20-40 minutes, the mixed solution is transferred to a separatory funnel and allowed to stand for separation. After the lower aqueous phase is released, the upper brownish-yellow aqueous organic phase is extracted with dichloromethane. The dichloromethane phases are combined and dried overnight with anhydrous Na2SO4. After removing the dichloromethane solvent using a rotary evaporator, one or more of the compounds shown in formula (I), formula (II), and formula (III) are obtained by vacuum distillation.

[0027] The amount of dichloromethane added in step S3 is 100 mL × 3.

[0028] The novel non-aqueous glycerol-based fatty amine absorbent is applied to the decarbonization treatment of industrial waste gases containing carbon dioxide, such as flue gas from power plants, tail gas from oil refineries, tail gas from steel mills, tail gas from cement plants, tail gas from chemical plants, water gas, biogas, natural gas, and decomposition gas from carbonate ores.

[0029] Furthermore, the operating conditions of the novel non-aqueous glycerol-based fatty amine absorbent are as follows: mixed gas pressure of 0.05–0.50 MPa, absorption temperature of 20.0–50.0 °C, absorption time of 0.1–1.0 h, desorption temperature of 60–90 °C, and desorption time of 0.1–1.0 h.

[0030] The beneficial effects of this invention are:

[0031] Compared with the traditional amine solution absorption method, this invention adopts a novel non-aqueous absorbent structural design concept, which has the following superior performance: 1) The absorption system does not require the addition of solvent water, and carbon dioxide can be completely desorbed within 30 minutes under heating conditions of 80℃, significantly reducing desorption energy consumption and inhibiting the corrosive effect of the absorbent on the equipment to a certain extent; 2) Introducing glycerol ether groups with low toxicity and biodegradability at the molecular level can improve the fluidity of the non-aqueous absorbent in the carbon dioxide capture process, thereby strengthening the internal mass transfer of the system and significantly increasing the capture capacity, which can reach up to 17wt% at 25℃ and up to 16wt% at 40℃; 3) The amino groups in the absorbent structure are alkylated, that is, the primary amine is converted into a secondary amine, which inhibits the hydrogen bonding between molecules, thereby reducing the viscosity of the system and controlling the heat of reaction between the absorbent and carbon dioxide, thereby improving the desorption efficiency and reducing the desorption energy consumption. The viscosity of each absorbent structure at 25℃ and under absorption saturation is 79-110 cP, and at 40℃ and under absorption saturation is 25-39 cP, with a desorption enthalpy of 41-67 kJ / mol.

[0032] Taking 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether as an example, its advantages include:

[0033] (1) The carbon dioxide mass absorption capacity of 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether is 17 wt% at 25℃ and 0.1 MPa for 30 min, and 16 wt% at 40℃ and 0.1 MPa for 30 min.

[0034] (2) The dynamic viscosity of 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether in the absorption saturation state at 25°C is 79 cP, and the dynamic viscosity in the absorption saturation state at 40°C is 29 cP.

[0035] (3) 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether can completely desorb carbon dioxide within 30 min at 80℃, and its desorption enthalpy is 67 kJ / mol. Detailed Implementation

[0036] The present invention will be further described in detail below with reference to the appendix and specific examples.

[0037] Example 1

[0038] Synthesis of 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether

[0039]

[0040] A 500 mL high-pressure reaction kettle was sequentially charged with 2-(2-chloroethoxy)-1,3-glycerol dimethyl ether (240 mmol, 43.83 g) and aqueous methylamine solution (40 wt%, 240 mL), and after sealing, the reaction was carried out in an 80°C oil bath for 12 h with magnetic stirring at 800 r / min. After the reaction was completed, the high-pressure kettle was immersed in an ice water bath for 1 h, and then the reaction solution was transferred to a 1 L beaker cooled in an ice water bath, and NaOH (80 g) was added portionwise with magnetic stirring (1000 r / min). After the solution was stirred for 30 min, it was all transferred to a 500 mL separatory funnel and allowed to stand, and the white NaOH-containing aqueous phase (lower layer) and the brownish yellow water-containing organic phase (upper layer) were gradually separated. The brownish yellow water-containing organic phase was collected and transferred to a beaker cooled in an ice water bath, and NaOH (20 g) was added portionwise with stirring, and after the mixture was stirred at room temperature for 30 min, it was transferred to a separatory funnel and allowed to stand. The lower aqueous phase was discharged, and the upper brownish yellow water-containing organic phase was extracted with dichloromethane (100 mL x 3), and the dichloromethane phases were combined and dried overnight using anhydrous Na2SO4. After the solvent dichloromethane was removed using a rotary evaporator, 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether was obtained by distillation under reduced pressure (60°C, 0.5 mm Hg), with a yield of 90%. NMR characterization data: 1 H NMR (400 MHz, CDCl3) δ = 4.05 (dd, J = 14.6, 9.3 Hz, 2H), 3.99 (dd, J = 10.4, 5.0 Hz, 1H), 3.93-3.76 (m, 4H), 3.74 (s, 6H), 3.11-3.00 (m, 2H), 2.77 (d, J = 22.6 Hz, 3H), 1.89 (s, 1H). 13 C NMR (100 MHz, CDCl3) δ = 78.3, 73.3, 69.9, 58.9, 52.3, 36.5.

[0041] Example 2

[0042] Synthesis of 2-(2-methylaminoethoxy)-1,3-glycerol diethyl ether

[0043]

[0044] A 500 mL high-pressure reaction kettle was sequentially charged with 2-(2- chloroethoxy)-1,3-glycerol diethyl ether (240 mmol, 50.57 g) and aqueous methylamine solution (40 wt%, 240 mL), sealed and reacted in an 80 °C oil bath for 12 h with magnetic stirring at 800 r / min. After the reaction was completed, the high-pressure kettle was immersed in an ice water bath for 1 h, and the reaction solution was transferred to a 1 L beaker cooled in an ice water bath, and NaOH (80 g) was added portionwise with magnetic stirring (1000 r / min). After the solution was stirred for 30 min, it was all transferred to a 500 mL separatory funnel and allowed to stand, and the white NaOH-containing aqueous phase (lower layer) and the brownish yellow water-containing organic phase (upper layer) were gradually separated. The brownish yellow water-containing organic phase was collected and transferred to a beaker cooled in an ice water bath, and NaOH (20 g) was added portionwise with stirring, and after the mixture was stirred at room temperature for 30 min, it was transferred to a separatory funnel and allowed to stand. The lower aqueous phase was discharged, and the upper brownish yellow water-containing organic phase was extracted with dichloromethane (100 mL x 3), and the dichloromethane phases were combined and dried overnight with anhydrous Na2SO4. After the solvent dichloromethane was removed using a rotary evaporator, 2-(2-methylaminoethoxy)-1,3-glycerol diethyl ether was obtained by distillation under reduced pressure (63-65 °C, 0.5 mmHg), with a yield of 88%. NMR characterization data: 1 H NMR (400 MHz, CDCl3) δ = 3.68-3.63 (m, 2H), 3.54 (dd, J = 10.3, 5.0 Hz, 1H), 3.46-3.39 (m, 8H), 2.71-2.61 (m, 2H), 2.36 (s, 3H), 1.12 (t, J = 7.0 Hz, 6H). 13 C NMR (100 MHz, CDCl3) δ = 78.2, 70.7, 69.6, 66.9, 51.7, 36.4, 15.3.

[0045] Example 3

[0046] Synthesis of 2-(2-methylaminoethoxy)-1,3-glycerol di(2-methoxyethyl) ether

[0047]

[0048] A 500 mL high-pressure reaction kettle was sequentially charged with 2-(2- chloroethoxy)-1,3-glycerol di(2-methoxyethyl) ether (240 mmol, 64.98 g) and aqueous methylamine solution (40 wt%, 240 mL), sealed and reacted in an 80 °C oil bath for 12 h with magnetic stirring at 800 r / min. After the reaction was completed, the high-pressure kettle was immersed in an ice water bath for 1 h, and the reaction solution was transferred to a 1 L beaker cooled in an ice water bath, and NaOH (80 g) was added portionwise with magnetic stirring (1000 r / min). After the solution was stirred for 30 min, it was all transferred to a 500 mL separatory funnel and allowed to stand, and the white NaOH-containing aqueous phase (lower layer) and the brownish yellow water-containing organic phase (upper layer) were gradually separated. The brownish yellow water-containing organic phase was collected and transferred to a beaker cooled in an ice water bath, and NaOH (20 g) was added portionwise with stirring, and after the mixture was stirred at room temperature for 30 min, it was transferred to a separatory funnel and allowed to stand. The lower aqueous phase was discharged, and the upper brownish yellow water-containing organic phase was extracted with dichloromethane (100 mL x 3), and the dichloromethane phases were combined and dried overnight with anhydrous Na2SO4. After the solvent dichloromethane was removed using a rotary evaporator, 2-(2-methylaminoethoxy)-1,3-glycerol di(2-methoxyethyl) ether was obtained by distillation under reduced pressure (130 °C, 0.5 mm Hg), with a yield of 86%. NMR characterization data: 1 H NMR (400 MHz, CDCl3) δ = 3.67-3.44 (m, 16H), 3.31 (s, 6H), 2.66 (t, J = 5.0 Hz, 2H), 2.36 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ = 78.1, 72.0, 71.4, 70.9, 69.6, 59.2, 51.7, 36.4.

[0049] Example 4

[0050] Synthesis of 2-[2-(2-methylaminoethoxy)]-ethoxy]-1,3-glycerol dimethyl ether

[0051]

[0052] A 500 mL high-pressure reactor was charged with 2-[2-(2- chloroethoxy)]-ethoxy]-1,3-glyceroldimethyl ether (240 mmol, 54.41 g) and aqueous methylamine solution (40 wt%, 240 mL) sequentially, sealed and reacted in an 80 °C oil bath for 12 h with magnetic stirring at 800 r / min. After the reaction was completed, the high-pressure reactor was immersed in an ice-water bath for 1 h, and the reaction solution was transferred to a 1 L beaker cooled in an ice-water bath, and NaOH (80 g) was added portionwise with magnetic stirring (1000 r / min). After the solution was stirred for 30 min, it was transferred to a 500 mL separatory funnel and allowed to stand, and the white NaOH-containing aqueous phase (lower layer) and the brownish yellow water-containing organic phase (upper layer) were gradually separated. The brownish yellow water-containing organic phase was collected and transferred to a beaker cooled in an ice-water bath, and NaOH (20 g) was added portionwise with stirring, and the mixture was stirred at room temperature for 30 min and then transferred to a separatory funnel and allowed to stand. The lower aqueous phase was discharged, and the upper brownish yellow water-containing organic phase was extracted with dichloromethane (100 mL x 3), and the dichloromethane phases were combined and dried overnight with anhydrous Na2SO4. The solvent dichloromethane was removed using a rotary evaporator, and 2-[2-(2-methylaminoethoxy)]-ethoxy]-1,3- glyceroldimethyl ether was obtained by distillation under reduced pressure (95 °C, 0.5 mm Hg), with a yield of 83%. NMR characterization data: 1 H NMR (400 MHz, CDCl3) δ = 3.69 (dd, J = 5.8, 4.2 Hz, 2H), 3.59-3.50 (m, 5H), 3.44-3.38 (m, 4H), 3.33-3.27 (m, 6H), 2.71-2.63 (m, 2H), 2.37 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ = 77.2, 71.7, 69.6, 69.4, 68.6, 58.2, 50.4, 35.4.

[0053] Example 5

[0054] Synthesis of 2-(2-(2-(2-methylaminoethoxy)-ethoxy)-ethoxy)-1,3- glyceroldimethyl ether

[0055]

[0056] A 500 mL high-pressure reactor was sequentially charged with 2-(2-(2-(2- chloroethoxy)-ethoxy)-ethoxy)-1,3-glycerol dimethyl ether (240 mmol, 64.98 g) and aqueous methylamine solution (40 wt%, 240 mL), sealed and reacted in an 80 °C oil bath for 12 h with magnetic stirring at 800 r / min. After the reaction was completed, the high-pressure reactor was immersed in an ice-water bath for 1 h, and the reaction solution was transferred to a 1 L beaker cooled in an ice-water bath. NaOH (80 g) was added portionwise with magnetic stirring (1000 r / min). After the solution was stirred for 30 min, it was transferred to a 500 mL separatory funnel and allowed to stand. The white NaOH-containing aqueous phase (lower layer) and the brownish yellow water-containing organic phase (upper layer) gradually separated. The brownish yellow water-containing organic phase was collected and transferred to a beaker cooled in an ice-water bath. NaOH (20 g) was added portionwise with stirring, and the mixture was transferred to a separatory funnel and allowed to stand after stirring at room temperature for 30 min. The lower aqueous phase was discharged, and the upper brownish yellow water-containing organic phase was extracted with dichloromethane (100 mL x 3). The dichloromethane phases were combined and dried over anhydrous Na2SO4 overnight. The solvent dichloromethane was removed using a rotary evaporator, and 2-(2-(2-(2-methylaminoethoxy)-ethoxy)-ethoxy)-1,3-glycerol dimethyl ether was obtained by distillation under reduced pressure (130-132 °C, 0.5 mm Hg), with a yield of 82%. NMR characterization data: 1 H NMR (400 MHz, CDCl3) δ = 3.70 (t, J = 4.6 Hz, 2H), 3.64-3.47 (m, 10H), 3.44-3.38 (m, 4H), 3.30 (s, 6H), 2.68 (t, J = 4.7 Hz, 2H), 2.37 (s, 3H). 13 C NMR (100 MHz, CDCl3) δ = 78.2, 72.7, 70.8, 70.8, 70.5, 70.4, 69.7, 59.3, 51.4, 36.5.

[0057] Example 6

[0058] A 25 mL round-bottom flask was charged with 2-(2-methylaminoethoxy)-1,3- glycerol dimethyl ether (3 mL), followed by slow carbon dioxide bubbling under magnetic stirring at a flow rate of 100 mL / min and a pressure of 0.1 MPa, with the oil bath temperature controlled at 25 °C or 40 °C. The amount of carbon dioxide absorbed was measured using a precision electronic balance, and the dynamic viscosity under carbon dioxide absorption saturation was measured using a rheometer. The carbon dioxide mass absorption capacity of 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether was 17 wt% at 25 °C for 30 min, and the viscosity was 79 cP. The carbon dioxide mass absorption capacity was 16 wt% at 40 °C for 30 min, and the viscosity was 29 cP.

[0059] Example 7

[0060] In a 25 mL round bottom flask, 3 mL of glyceryl fatty amine absorbent obtained in Example 2-5 was added, followed by slowly bubbling carbon dioxide under magnetic stirring, controlling the carbon dioxide gas flow at 100 mL / min, the pressure at 0.1 MPa, and the oil bath temperature at 25°C or 40°C, measuring the carbon dioxide absorption amount with a precision electronic balance, and measuring the dynamic viscosity under absorption saturation with a rheometer, obtaining the carbon dioxide capture performance of the glyceryl fatty amine absorbent at 25°C or 40°C as shown in the following table (Table 1).

[0061] Table 1 Carbon dioxide capture performance of glyceryl fatty amine absorbent

[0062]

[0063] Example 8

[0064] In a 25 mL round bottom flask, 3 mL of 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether saturated with carbon dioxide absorption in Example 6 was added, and the oil bath temperature was raised to 80°C under magnetic stirring, the carbon dioxide desorption amount was measured with a precision electronic balance, and the carbon dioxide desorption enthalpy was measured with a differential scanning calorimeter. The carbon dioxide desorption ratio of 2-(2-methylaminoethoxy)-1,3-glycerol dimethyl ether at 30 min was 100%, and the desorption enthalpy was 67 kJ / mol.

[0065] Example 9

[0066] In a 25 mL round bottom flask, glyceryl fatty amine absorbent saturated with carbon dioxide absorption in Example 7 was added, and the oil bath temperature was controlled at 80°C, the carbon dioxide desorption amount was measured with a precision electronic balance, and the carbon dioxide desorption enthalpy was measured with a differential scanning calorimeter, obtaining the carbon dioxide desorption performance of the glyceryl fatty amine absorbent at 80°C at 30 min as shown in the following table (Table 2).

[0067] The experimental results show that the molecular functionalization strategy of the carbon dioxide non-aqueous absorbent proposed in the present application can effectively improve the desorption efficiency of the absorbent: all the absorbents (taking Nos. 1-5 as examples) can achieve complete desorption of carbon dioxide within 30 min, and the desorption enthalpy is between 41-67 kJ / mol.

[0068] Table 2 Carbon dioxide desorption performance of glyceryl fatty amine absorbent

[0069]

[0070] The above examples are only part of the specific embodiments of the present application. Obviously, there are various variants of the embodiments described in the present application, and all variants directly or indirectly deduced by those skilled in the art from the disclosure of the present application should be considered as falling within the protection scope of the present application.

Claims

1. A new class of non-aqueous glyceryl fatty amine absorbents for capturing carbon dioxide in a mixed gas, characterized by: The structural skeleton of the absorbent is 1,3-glycerol ether, and 2-aminoethoxy, 2-(2-aminoethoxy)ethoxy or 2-(2-(2-aminoethoxy)ethoxy)-ethoxy is linked to the 2-position thereof, so that the amine group in the absorbent is functionalized as a secondary amine; The glyceryl fatty amine absorbent is one or more of the compounds shown in formulas (I), (II) and (III); Among them, R 1 It can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxyethyl, or 2-hydroxyethyl; R 2 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 3 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 4 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 5 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 6 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 7 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 8 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl; R 9 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, methoxyethyl or 2-hydroxyethyl.

2. A process for the preparation of a novel non-aqueous glyceryl fatty amine absorbent according to claim 1, characterized by: The method comprises the following steps: S1: a high-pressure reactor is sequentially filled with a chloroalkoxy-1,3-glycerol diether containing a corresponding functional group, denoted as component 1, and an amine or amine solution containing a corresponding functional group, denoted as component 2, and reacted at 70-80°C for 12 h to obtain a reaction mixture; the molar ratio of the component 1 to the component 2 is 1:5-30; S2: after the high-pressure reactor is immersed in an ice-water bath for 30 min, the reaction mixture is transferred to a beaker cooled in an ice-water bath, and NaOH is added in batches under stirring; the molar ratio of the added NaOH to the component 1 is 10-6:1; after the solution is stirred for 20-40 min, it is all transferred to a separatory funnel and left to stand, and a white NaOH-containing emulsion water phase and a brownish-yellow water-containing organic phase are gradually separated; S3: the brownish-yellow water-containing organic phase is collected and transferred to a beaker cooled in an ice-water bath, NaOH is added in batches under stirring; the molar ratio of the added NaOH to the component 1 is 1-3:1; after the mixture is stirred at room temperature for 20-40 min, it is transferred to a separatory funnel and left to stand; the lower water phase is discharged, the upper brownish-yellow water-containing organic phase is extracted with dichloromethane, the dichloromethane phases are combined and dried with anhydrous Na2SO4 overnight, the solvent dichloromethane is removed by using a rotary evaporator, and one or more of the compounds shown in formulas (I), (II) and (III) is obtained by distillation under reduced pressure.

3. Use of the novel non-aqueous glyceryl fatty amine absorbent according to claim 1 in capturing carbon dioxide in a mixed gas.

4. Use of the novel non-aqueous glyceryl fatty amine absorbent according to claim 3 for capturing carbon dioxide in a mixed gas, characterized by: The novel non-aqueous glyceryl fatty amine absorbent is used in the decarburization treatment of industrial waste gas containing carbon dioxide, such as flue gas from power plants, tail gas from oil refineries, tail gas from steel plants, tail gas from cement plants, tail gas from chemical plants, water gas, biogas, natural gas and decomposition gas of carbonate ores.

5. Use of the novel non-aqueous glyceryl fatty amine absorbent according to claim 4 for capturing carbon dioxide in a mixed gas, characterized by: The use conditions of the novel non-aqueous glyceryl fatty amine absorbent are as follows: the pressure of the mixed gas is 0.05-0.50 MPa, the absorption temperature is 20.0-50.0°C, the absorption time is 0.1-1.0 h, the desorption temperature is 60-90°C, and the desorption time is 0.1-1.0 h.

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