CN115382513A - Adapt to medium-low concentration CO 2 Method and process for efficient capture - Google Patents

Adapt to medium-low concentration CO 2 Method and process for efficient capture Download PDF

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CN115382513A
CN115382513A CN202210933769.3A CN202210933769A CN115382513A CN 115382513 A CN115382513 A CN 115382513A CN 202210933769 A CN202210933769 A CN 202210933769A CN 115382513 A CN115382513 A CN 115382513A
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lithium aluminum
aluminum hydrotalcite
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ionic liquid
adsorbent
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王瀚翔
王志章
樊燕芳
曾荣佳
韩云
陈文浩
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Beijing Shida Youyuan Technology Development Co ltd
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Abstract

The invention discloses a method for adapting to medium-low concentration CO 2 The method designs a novel amino modified solid adsorbent, selects natural clay mineral lithium aluminum hydrotalcite as a matrix for research and development of the adsorbent, and simultaneously selects amino carboxylic acid type ionic liquid as an amino load material in addition to the traditional organic amine polyethyleneimine as an amino load compound. The method adopts the synergistic effect of physical impregnation and chemical grafting to modify amino, improves the surface amino active sites of the matrix, and realizes medium and low concentration CO 2 High efficiency of trapping.

Description

Adapt to medium-low concentration CO 2 Method and process for efficient capture
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to a method for adapting to medium-low concentration CO 2 A method and a flow path for high-efficiency trapping. The modification of the amino groups in the first step by chemical grafting enablesThe dispersion of the amine molecule polymer on the surface of the support material increases the amount of available amines, while, on the other hand, for the amine molecules introduced in the second step by physical impregnation, the increase in adsorption temperature is effective in most cases for increasing the CO content of the adsorbent by reordering the amine molecule polymer on the surface of the support material 2 And (4) adsorption performance.
Background
With the gradual increase of the use of fossil fuels such as coal, petroleum and natural gas by human beings, CO 2 Emissions have caused a range of environmental problems and climate change. Since 1951, the global temperature has increased by at least 0.8 ℃, and this increase has continued for as long as the 21 st century. At the same time, the amount of greenhouse gas emissions has increased significantly over the past 20 years. As global warming continues to increase, a number of more serious problems have arisen. Including the reduction of the ice coverage area of the arctic sea, the reduction of the volume of glaciers, the rise of the sea level and the like. For these reasons, efforts to reduce the environmental impact have been increased in recent years, and preventive and remedial measures have been taken. Preventive strategies are associated with promoting renewable energy and energy efficiency programs, while remedial approaches are associated with the current generation of large quantities of CO 2 The implementation method in the industrial facility is relevant.
In which carbon capture and sequestration technology is proposed as an effective CO reduction 2 An emerging technology for emissions. Therefore, new and cost-effective technical solutions have been developed and implemented to reduce greenhouse gases (i.e., CO) 2 ) Is an important step towards sustainable energy based on fossil fuels. At present, for high concentration of CO 2 Conventional CO of large-scale point sources 2 The capture method is already mature. However, low concentrations of CO are involved 2 The exploration of direct capture techniques, including direct capture from air or enclosed spaces, is still ongoing. In typical manned enclosed spaces (e.g. naval submarines, spacecraft, space stations and shelters), CO is present in excess of the human body tolerance (2%) 2 The concentration may be a serious threat to the health and life safety of the cabin personnel. For low concentration CO 2 Capture technology of CO in closed space and atmosphere 2 Is caused by the emission aspectThere is an increasing interest. In addition, CO 2 The core of trapping is based on the development of green adsorbents and trapping processes.
In recent years, CO capture by adsorption 2 Is one of the most widely discussed technologies, has low potential cost and convenient application, and simultaneously avoids the absorption of CO by an amine aqueous solution 2 A series of disadvantages of (a). In CO 2 In adsorption technology, the adsorbent is the cornerstone of all adsorption processes, and many porous solid adsorbents have been developed for post-combustion CO 2 The trapping process of (1). However, on the one hand, these solid adsorbents have CO 2 The adsorption capacity is not ideal enough; on the other hand, the solid adsorbents have harsh requirements on the operating environment; more importantly, because of their higher concentration of CO 2 The trapping capacity rapidly decreases. It is therefore critical for the adsorption process to develop a solid adsorbent with high adsorption and selectivity.
To increase the concentration of CO in medium and low concentration 2 The performance of the efficient trapping adsorbent breaks through the traditional mode that inorganic materials are combined with organic amine, a novel amino-modified solid adsorbent is designed, a natural clay mineral lithium aluminum hydrotalcite is selected as a matrix for research and development of the adsorbent, meanwhile, besides traditional organic amine polyethyleneimine is selected as an amino load compound, aminocarboxylic acid type ionic liquid is also selected as an amino load material, the polyethyleneimine and the aminocarboxylic acid type ionic liquid have a synergistic effect, the content of silanol groups indicated by the material can be improved, impurity ions and free water molecules in the material are removed, and low-concentration CO is realized 2 High efficiency of trapping.
Therefore, the present invention is directed to CO lift 2 The adsorption capacity of the adsorbent has very important significance for environmental protection.
Disclosure of Invention
Global warming is mainly caused by greenhouse gases emitted from human activities, among which CO 2 The contribution is close to 60 percent, and as a large carbon emission country, china faces huge CO 2 Pressure for emission reduction. To realize CO 2 Sustainable emission reduction of CO 2 Capture,The use of the storage and containment (CCUS) technique is the most realistic approach. In CO 2 In the trapping technology, the research of the amino modified solid adsorbent has been greatly advanced, but deeper problems such as the bias of adsorption capacity and cycle stability, the nature of amino compound, the stability of carrier material and the utilization cost of the carrier material influence the adsorbent to CO at medium and low concentrations 2 The trapping ability of (a).
To improve the medium-low concentration CO 2 The invention provides a method and a process for efficient trapping, and provides the following technical scheme:
s1, synthesis of a lithium aluminum hydrotalcite matrix: collecting LiCl 3-8g and AlCl 4-9g 3 ·6H 2 Dissolving O in 200ml of deionized water, then adding 5-10g of urea into 200ml of deionized water, simultaneously adding the two mixed solutions into a three-neck flask, stirring for 8-12 hours, washing the precipitate with deionized water for filtration until the pH of the precipitate is neutral, placing the precipitate under 378K, drying for 24-36 hours, and finally placing the precipitate into a resistance furnace to be roasted at 573K for 12-16 hours to obtain a lithium aluminum hydrotalcite matrix;
s2, activating anion exchange resin: firstly, soaking anion exchange resin in saturated NaCl solution for 16-24 hours, then soaking in 5% HCl solution for 12-15 hours, washing with deionized water until the pH value is neutral, finally soaking in 4% NaOH solution for 10-13 hours, pouring out the solution, washing with deionized water until the pH value is neutral, and filling the obtained activated anion exchange resin into an ion exchange column for later use;
s3, preparing an amino carboxylic acid type ionic liquid: dissolving 2-6g of tributyl ethyl phosphine bromide in 100ml of deionized water, carrying out ion exchange through activated anion exchange resin, collecting eluate in an ion exchange column, adding a corresponding amount of iminodiacetic acid solid into the solution, stirring the mixture at room temperature for 12-16 hours, and finally carrying out vacuum drying on the mixture at 353K for 42-48 hours to obtain the required ionic liquid;
s4, preparing a polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent: adopting lithium aluminum hydrotalcite as a carrier, modifying the lithium aluminum hydrotalcite by using polyethyleneimine, adding 1-4g of lithium aluminum hydrotalcite powder into 180-200ml of p-xylene solvent, stirring at room temperature for 1-3 hours, adding 0.1-0.4g of polyethyleneimine into the mixed solution, filtering and washing the obtained precipitate until the pH value is neutral, and finally drying the precipitate at the temperature of 353K for 8-12 hours to obtain the polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent;
s5, preparing an amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent: and (3) further modifying the adsorbent obtained in S4 by using an amino carboxylic acid type ionic liquid, dissolving 0.1-0.4g of the ionic liquid in 15-20mL of absolute ethyl alcohol, stirring at room temperature for 20 minutes, adding 1.0-4.0g of polyethyleneimine functionalized lithium aluminum hydrotalcite into the mixed solution, stirring for 30 minutes, ultrasonically dissolving for 30 minutes to ensure that the solid phase and the liquid phase are completely contacted, drying the slurry at 380K for half a day, and finally grinding the adsorbent to 100 meshes to obtain the amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent.
In the invention, S4 adopts a chemical grafting method to obtain the polyethyleneimine functionalized lithium aluminum hydrotalcite solid adsorbent, and an amino active site is loaded on the carrier through a chemical reaction between an effective silanol group and a silanol group on the surface of the carrier.
Preferably: the natural clay mineral selected in the invention is lithium aluminum hydrotalcite.
Preferably: aluminum chloride hexahydrate (AlCl) selected in the invention 3 ·6H 2 O) and lithium chloride (LiCl) are reagents having a purity of 99% or more.
Preferably: the method disclosed by the invention is double modification of a physical impregnation method and a chemical grafting method.
Drawings
FIG. 1 is a schematic diagram of the structure of lithium aluminum hydrotalcite in example 1 of the present invention.
FIG. 2 is a graph showing pore size distributions of adsorbents prepared in example 2 of the present invention and comparative examples 4 and 5.
Fig. 3 is XRD patterns of the adsorbents prepared in example 2 and comparative example 6 of the present invention.
FIG. 4 is a graph showing pore size distributions of adsorbents prepared in example 3 of the present invention and comparative examples 7 and 8.
Fig. 5 is XRD patterns of the adsorbents prepared in example 3 and comparative example 9 of the present invention.
FIG. 6 is a thermal stability analysis chart of lithium aluminum hydrotalcite according to example 3 of the present invention.
FIG. 7 is an SEM image of lithium aluminum hydrotalcite according to example 4 of the present invention.
FIG. 8 is an SEM image of an aminocarboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent in example 4 of the invention.
FIG. 9 shows CO in example 1 of the present invention and comparative examples 1, 2 and 3 2 The selectivity percentage histogram.
FIG. 10 shows CO in example 2 of the present invention and comparative examples 4, 5 and 6 2 The selectivity percentage histogram.
FIG. 11 shows CO in example 3 and comparative examples 7, 8 and 9 of the present invention 2 Percent selectivity histogram.
Detailed Description
In CO 2 In the capture technology, CO is captured by adsorption 2 Is one of the most widely discussed technologies, has low potential cost and convenient application, and simultaneously avoids the absorption of CO by an amine aqueous solution 2 A series of disadvantages of (a). Compared with a single solid material adsorbent, the amino modified solid adsorbent is a type of adsorbent with higher CO 2 Novel CO having adsorption capacity, thermal stability and excellent cyclic regeneration performance 2 An adsorbent. The solid adsorbent introduces amino functional groups into a solid material, and simultaneously utilizes the pore channel structure of the porous solid material and the affinity of an amino compound in acid gas. The amino functional groups uniformly dispersed on the porous solid material provide abundant basic sites for adsorbing acid gases. To CO 2 Screening of porous solid materials to improve adsorbent CO for adsorption capacity and organic amine loading 2 The main factor of the adsorption performance.
Example 1
S1, synthesizing a lithium aluminum hydrotalcite matrix: taking 8g LiCl and 9g AlCl 3 ·6H 2 Dissolving O in 200ml deionized water, adding 10g urea into 200ml deionized water, and adding the above two mixed solutions simultaneouslyStirring in a three-neck flask for 12 hours, washing the precipitate with deionized water until the pH value of the precipitate is neutral, placing the precipitate in a 378K oven, drying for 36 hours, and finally placing the precipitate in a resistance furnace, and roasting at the high temperature of 573K for 16 hours to obtain a lithium-aluminum hydrotalcite matrix;
s2, activating anion exchange resin: firstly, soaking anion exchange resin in saturated NaCl solution for 24 hours, then soaking in 5% HCl solution for 15 hours, washing with deionized water until the pH value is neutral, finally soaking in 4% NaOH solution for 13 hours, pouring out the solution, washing with deionized water until the pH value is neutral, and filling the obtained activated anion exchange resin into an ion exchange column for later use;
s3, preparing an amino carboxylic acid type ionic liquid: dissolving 6g of tributyl ethyl phosphine bromide in 100ml of deionized water, carrying out ion exchange through activated anion exchange resin, collecting eluate in an ion exchange column, adding a corresponding amount of iminodiacetic acid solid into the solution, stirring the mixture at room temperature for 16 hours, and finally carrying out vacuum drying on the mixture at the temperature of 353K for 48 hours to obtain the required ionic liquid;
s4, preparing a polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent: adopting lithium aluminum hydrotalcite as a carrier, modifying the lithium aluminum hydrotalcite by using polyethyleneimine, adding 4g of lithium aluminum hydrotalcite powder into 200ml of p-xylene solvent, stirring at room temperature for 3 hours, adding 0.4g of polyethyleneimine into the mixed solution, filtering and washing the obtained precipitate until the pH value is neutral, and finally drying the precipitate at the temperature of 353K for 12 hours to obtain the polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent;
s5, preparing an amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent: and (3) further modifying the adsorbent obtained in S4 by using an amino carboxylic acid type ionic liquid, dissolving 0.4g of the ionic liquid in 20mL of absolute ethyl alcohol, stirring at room temperature for 20 minutes, adding 4.0g of polyethyleneimine functionalized lithium aluminum hydrotalcite into the mixed solution, stirring for 30 minutes, ultrasonically dissolving for 30 minutes to ensure that the solid phase and the liquid phase are completely contacted, drying the slurry at 380K for half a day, and finally grinding the adsorbent to 100 meshes to obtain the amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent.
Comparative example 1 AlCl in step S1 was removed 3 ·6H 2 Conversion of O to Al (NO) 3 ) 3 ·6H 2 Conversion of urea/Cl-to urea/NO in addition to O 3 The procedure was as in example 1.
Comparative example 2 AlCl in step S1 was removed 3 ·6H 2 Conversion of O to Al (CH) 3 COO) 3 4H2O, urea/Cl-to Urea/CH 3 COO-the steps are the same as in example 1.
Comparative example 3 AlCl in step S1 was removed 3 ·6H 2 Conversion of O to Al 2 (SO 4 ) 3 ·9H 2 O, urea/Cl - Modified to urea/SO 4 2- The steps are the same as in example 1.
TABLE 1
Detecting items Comparative example 1 Comparative example 2 Comparative example 3 Example 1
CO 2 Selectivity (%) 60.3±0.03 70.2±0.02 49.8±0.03 79.6±0.02
FIG. 1 is a drawing illustrating the practice of the present inventionSchematic structure of lithium aluminum hydrotalcite in example 1. FIG. 9 shows CO obtained in example 1 of the present invention and comparative examples 1, 2 and 3 2 The selectivity percentage histogram. Table 1 shows examples 1 of the present invention and comparative examples 1, 2 and 3CO 2 Statistical table of percent mean of selectivity. From FIG. 9 and Table 1, it can be seen that CO is contained in example 1 2 The percentage of selectivity is higher than that of comparative examples 1, 2 and 3. The results show that AlCl is used 3 ·6H 2 The lithium aluminum hydrotalcite prepared by O has extremely high anion exchange capacity, and therefore greatly strengthens CO thereof 2 Adsorption capacity. According to FIG. 1, with Cl - The lithium aluminum hydrotalcite has extremely special microstructure and maximum interlayer charge density, improves the porosity of the material and the silanol group content on the surface of the material, thereby improving the CO content under medium and low concentration 2 High trapping capacity.
Example 2
S1, synthesizing a lithium aluminum hydrotalcite matrix: taking 3g of LiCl and 4g of AlCl 3 ·6H 2 Dissolving O in 200ml of deionized water, then adding 5g of urea into 200ml of deionized water, simultaneously adding the two mixed solutions into a three-neck flask, stirring for 8 hours, washing the precipitate with deionized water for filtration until the pH of the precipitate is neutral, placing the precipitate under 378K, drying for 24 hours, and finally placing the precipitate into a resistance furnace, and roasting for 12 hours at the high temperature of 573K to obtain the lithium-aluminum hydrotalcite matrix;
s2, activating anion exchange resin: firstly, soaking anion exchange resin in saturated NaCl solution for 16 hours, then soaking in 5% HCl solution for 12 hours, washing with deionized water until the pH value is neutral, finally soaking in 4% NaOH solution for 10 hours, pouring out the solution, washing with deionized water until the pH value is neutral, and filling the obtained activated anion exchange resin into an ion exchange column for later use;
s3, preparing an amino carboxylic acid type ionic liquid: dissolving 2-6g of tributyl ethyl phosphine bromide in 100ml of deionized water, carrying out ion exchange through activated anion exchange resin, collecting eluate in an ion exchange column, adding a corresponding amount of iminodiacetic acid solid into the solution, stirring the mixture at room temperature for 12 hours, and finally carrying out vacuum drying on the mixture at the temperature of 353K for 42 hours to obtain the required ionic liquid;
s4, preparing a polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent: adopting lithium aluminum hydrotalcite as a carrier, modifying the lithium aluminum hydrotalcite by using polyethyleneimine, adding 1g of lithium aluminum hydrotalcite powder into 180ml of paraxylene solvent, stirring at room temperature for 1 hour, adding 0.1g of polyethyleneimine into the mixed solution, filtering and washing the obtained precipitate until the pH value is neutral, and finally drying the precipitate at the temperature of 353K for 8 hours to obtain the polyethyleneimine-functionalized lithium aluminum hydrotalcite adsorbent;
s5, preparing an amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent: and (3) further modifying the adsorbent obtained in S4 by using an amino carboxylic acid type ionic liquid, dissolving 0.1g of the ionic liquid in 15mL of absolute ethyl alcohol, stirring at room temperature for 20 minutes, adding 1.0g of polyethyleneimine functionalized lithium aluminum hydrotalcite into the mixed solution, stirring for 30 minutes, ultrasonically dissolving for 30 minutes to ensure that the solid phase and the liquid phase are completely contacted, drying the slurry at 380K for half a day, and finally grinding the adsorbent to 100 meshes to obtain the amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent.
Comparative example 4 the procedure was the same as in example 2 except that no polyethyleneimine was added in step S4.
Comparative example 5 the same procedures as in example 2 were carried out except that no aminocarboxylic acid type ionic liquid was added in step S5.
Comparative example 6 the same procedures as in example 2 were carried out except that polyethyleneimine was not added in step S4 and aminocarboxylic acid type ionic liquid was not added in step S5.
TABLE 2
Test itemEyes of a user Comparative example 4 Comparative example 5 Comparative example 6 Example 2
CO 2 Selectivity (%) 30.2±0.03 20.1±0.02 40.3±0.03 69.8±0.02
FIG. 2 is a plot of the pore size distribution of the adsorbents prepared in example 2 of the present invention and comparative examples 4 and 5. Fig. 3 is XRD patterns of the adsorbents prepared in example 2 and comparative example 6 of the present invention. FIG. 10 shows CO in example 2 of the present invention and comparative examples 4, 5 and 6 2 The selectivity percentage histogram. Table 2 shows inventive example 2 and comparative examples 4, 5 and 6CO 2 Percent selectivity.
The result shows that the aminocarboxylic acid type ionic liquid obtained by neutralizing the tributyl ethyl hydrogen phosphine oxide solution with iminodiacetic acid overcomes the thermal instability of the traditional organic amine load material, improves the porosity of the material, and has less pore distribution, which proves that the polyethyleneimine and aminocarboxylic acid type ionic liquid molecules are successfully loaded on the lithium aluminum hydrotalcite matrix by a physical impregnation method and fill partial pore channels of the matrix. In the synthesis process, electron-withdrawing substituent acetate is introduced to amino acid anions to activate carboxylate radicals in the amino acids, so that the negative induction effect of amino groups in the amino acid anions is reduced, and the carboxylate radicals and CO are remarkably improved 2 The interaction of the amino group and the carboxylate radical in the amino carboxylic acid type ionic liquid is realized to generate CO 2 The multi-point absorption of the CO greatly improves the CO 2 Capacity of absorption.
Example 3
S1, combination of lithium aluminum hydrotalcite matrixThe composition is as follows: 4g LiCl and 5g AlCl 3 ·6H 2 Dissolving O in 200ml of deionized water, then adding 7g of urea into 200ml of deionized water, simultaneously adding the two mixed solutions into a three-neck flask, stirring for 9 hours, washing the precipitate with deionized water for filtration until the pH of the precipitate is neutral, placing the precipitate in a 378K oven, drying for 28 hours, and finally placing the precipitate in a resistance furnace, and roasting for 13 hours at the high temperature of 573K to obtain the lithium-aluminum hydrotalcite matrix;
s2, activating anion exchange resin: firstly, soaking anion exchange resin in saturated NaCl solution for 18 hours, then soaking in 5% HCl solution for 13 hours, washing with deionized water until the pH value is neutral, finally soaking in 4% NaOH solution for 11 hours, pouring out the solution, washing with deionized water until the pH value is neutral, and filling the obtained activated anion exchange resin into an ion exchange column for later use;
s3, preparing an amino carboxylic acid type ionic liquid: dissolving 3g of tributyl ethyl phosphine bromide in 100ml of deionized water, carrying out ion exchange by using activated anion exchange resin, collecting eluate in an ion exchange column, adding a corresponding amount of iminodiacetic acid solid into the solution, stirring the mixture at room temperature for 13 hours, and finally carrying out vacuum drying on the mixture at the temperature of 353K for 44 hours to obtain the required ionic liquid;
s4, preparing a polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent: adopting lithium aluminum hydrotalcite as a carrier, modifying the lithium aluminum hydrotalcite by using polyethyleneimine, adding 2g of lithium aluminum hydrotalcite powder into 190ml of p-xylene solvent, stirring at room temperature for 2 hours, adding 0.2g of polyethyleneimine into the mixed solution, filtering and washing the obtained precipitate until the pH value is neutral, and finally drying the precipitate at the temperature of 353K for 9 hours to obtain the polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent;
s5, preparing an amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent: and (3) further modifying the adsorbent obtained in S4 by using an amino carboxylic acid type ionic liquid, dissolving 0.2g of the ionic liquid in 16mL of absolute ethyl alcohol, stirring at room temperature for 20 minutes, adding 2.0g of polyethyleneimine functionalized lithium aluminum hydrotalcite into the mixed solution, stirring for 30 minutes, ultrasonically dissolving for 30 minutes to ensure that the solid phase and the liquid phase are completely contacted, drying the slurry at 380K for half a day, and finally grinding the adsorbent to 100 meshes to obtain the amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent.
Comparative example 7 Each procedure was the same as in example 3 except that the HT treatment at a high temperature of 573K in step S1 was changed to the HT treatment at a high temperature of 500K.
Comparative example 8 Each procedure was the same as in example 3 except that the HT treatment at a high temperature of 573K in step S1 was changed to the HT treatment at a high temperature of 550K.
Comparative example 9 Each of the steps was the same as in example 3 except that the HT heat-treatment at a high temperature of 573K in step S1 was changed to the heat-treatment at a high temperature of 600K.
TABLE 3
Detecting items Comparative example 7 Comparative example 8 Comparative example 9 Example 3
CO 2 Selectivity (%) 40.2±0.02 30.1.±0.03 50.2±0.02 60.3±0.02
FIG. 4 is a graph showing pore size distributions of adsorbents prepared in example 3 of the present invention and comparative examples 7 and 8A wire. Fig. 5 is XRD patterns of the adsorbents prepared in example 3 and comparative example 9 of the present invention. FIG. 10 shows CO in example 2 of the present invention and comparative examples 7, 8 and 9 2 The selectivity percentage histogram. Table 2 shows inventive example 3 and comparative examples 7, 8 and 9CO 2 Percent selectivity. FIG. 6 is a thermal stability analysis chart of lithium aluminum hydrotalcite according to example 3 of the present invention. The results show that in the range of 423K to 503K, CO is responsible 3 2- And OH - The polymeric dehydration in the layer causes the weight loss of the lithium aluminum hydrotalcite, and the removal of the hetero-ions is the main reason for the phenomenon. However, when the temperature is higher than 623K, the crystal form of the lithium aluminum hydrotalcite is transformed and the structure of the slab layer begins to collapse, and the metal oxide occurs. The lithium aluminum hydrotalcite is put under 573K high temperature for heat treatment, so that the crystal form collapse can be effectively avoided, the crystal form degree of the carrier is improved, and the better loading of amino is facilitated.
Example 4
S1, synthesizing a lithium aluminum hydrotalcite matrix: taking 6g LiCl and 8g AlCl 3 ·6H 2 Dissolving O in 200ml of deionized water, then adding 8g of urea into 200ml of deionized water, simultaneously adding the two mixed solutions into a three-neck flask, stirring for 10 hours, washing the precipitate with deionized water for filtration until the pH value of the precipitate is neutral, placing the precipitate under 378K, drying for 32 hours, and finally placing the precipitate into a resistance furnace, and roasting for 15 hours at the high temperature of 573K to obtain the lithium-aluminum hydrotalcite matrix;
s2, activating anion exchange resin: firstly, soaking anion exchange resin in saturated NaCl solution for 22 hours, then soaking in 5% HCl solution for 14 hours, washing with deionized water until the pH value is neutral, finally soaking in 4% NaOH solution for 12 hours, pouring out the solution, washing with deionized water until the pH value is neutral, and filling the obtained activated anion exchange resin into an ion exchange column for later use;
s3, preparing the amino carboxylic acid type ionic liquid: dissolving 5g of tributyl ethyl phosphine bromide in 100ml of deionized water, carrying out ion exchange by using activated anion exchange resin, collecting eluate in an ion exchange column, adding a corresponding amount of iminodiacetic acid solid into the solution, stirring the mixture at room temperature for 15 hours, and finally carrying out vacuum drying on the mixture at the temperature of 353K for 46 hours to obtain the required ionic liquid;
s4, preparing a polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent: adopting lithium aluminum hydrotalcite as a carrier, modifying the lithium aluminum hydrotalcite by using polyethyleneimine, adding 3g of lithium aluminum hydrotalcite powder into 190ml of p-xylene solvent, stirring at room temperature for 2 hours, adding 0.3g of polyethyleneimine into the mixed solution, filtering and washing the obtained precipitate until the pH value is neutral, and finally drying the precipitate at the temperature of 353K for 11 hours to obtain the polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent;
s5, preparing an amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent: and (3) further modifying the adsorbent obtained in S4 by using an amino carboxylic acid type ionic liquid, dissolving 0.3g of the ionic liquid in 18mL of absolute ethyl alcohol, stirring at room temperature for 20 minutes, adding 3.0g of polyethyleneimine functionalized lithium aluminum hydrotalcite into the mixed solution, stirring for 30 minutes, ultrasonically dissolving for 30 minutes to ensure that the solid phase and the liquid phase are completely contacted, drying the slurry at 380K for half a day, and finally grinding the adsorbent to 100 meshes to obtain the amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent.
FIG. 7 is an SEM photograph of lithium aluminum hydrotalcite according to example 4 of the present invention. FIG. 8 is an SEM image of an aminocarboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent in example 4 of the invention. After hydrochloric acid treatment and high temperature calcination treatment, the lithium aluminum hydrotalcite matrix clearly exhibits a typical regular hexagonal layered structure. The structural morphology of the adsorbent modified by the amino carboxylic acid type ionic liquid becomes coarser, which is mainly caused by removing water molecules and hetero ions. This makes the amino active site more accessible to CO 2 The molecules interact with each other to increase the CO content of the adsorbent 2 The adsorption capacity of (1).
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. Adapt to medium-low concentration CO 2 The method and the process for efficient trapping specifically select polyethyleneimine and aminocarboxylic acid type ionic liquid as amino load materials, and perform amino modification on lithium aluminum hydrotalcite by utilizing the synergistic effect of a physical impregnation method and a chemical grafting method, and are characterized in that: the method comprises the following steps:
s1, synthesizing a lithium aluminum hydrotalcite matrix: collecting LiCl 3-8g and AlCl 4-9g 3 ·6H 2 Dissolving O in 200ml of deionized water, then adding 5-10g of urea into 200ml of deionized water, simultaneously adding the two mixed solutions into a three-neck flask, stirring for 8-12 hours, washing the precipitate with deionized water for filtration until the pH of the precipitate is neutral, placing the precipitate under 378K, drying for 24-36 hours, and finally placing the precipitate into a resistance furnace to be roasted at 573K for 12-16 hours to obtain a lithium aluminum hydrotalcite matrix;
s2, activating anion exchange resin: firstly, soaking anion exchange resin in saturated NaCl solution for 16-24 hours, then soaking in 5% HCl solution for 12-15 hours, washing with deionized water until the pH value is neutral, finally soaking in 4% NaOH solution for 10-13 hours, pouring out the solution, washing with deionized water until the pH value is neutral, and filling the obtained activated anion exchange resin into an ion exchange column for later use;
s3, preparing the amino carboxylic acid type ionic liquid: dissolving 2-6g of tributyl ethyl phosphine bromide in 100ml of deionized water, carrying out ion exchange through activated anion exchange resin, collecting eluate in an ion exchange column, adding a corresponding amount of iminodiacetic acid solid into the solution, stirring the mixture at room temperature for 12-16 hours, and finally carrying out vacuum drying on the mixture at the temperature of 353K for 42-48 hours to obtain the required ionic liquid;
s4, preparing a polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent: adopting lithium aluminum hydrotalcite as a carrier, modifying the lithium aluminum hydrotalcite by using polyethyleneimine, adding 1-4g of lithium aluminum hydrotalcite powder into 180-200ml of p-xylene solvent, stirring at room temperature for 1-3 hours, adding 0.1-0.4g of polyethyleneimine into the mixed solution, filtering and washing the obtained precipitate until the pH value is neutral, and finally drying the precipitate at the temperature of 353K for 8-12 hours to obtain the polyethyleneimine functionalized lithium aluminum hydrotalcite adsorbent;
s5, preparing an amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent: and (3) further modifying the adsorbent obtained in S4 by using an amino carboxylic acid type ionic liquid, dissolving 0.1-0.4g of the ionic liquid in 15-20mL of absolute ethyl alcohol, stirring at room temperature for 20 minutes, adding 1.0-4.0g of polyethyleneimine functionalized lithium aluminum hydrotalcite into the mixed solution, stirring for 30 minutes, ultrasonically dissolving for 30 minutes to ensure that the solid phase and the liquid phase are completely contacted, drying the slurry at 380K for half a day, and finally grinding the adsorbent to 100 meshes to obtain the amino carboxylic acid type ionic liquid functionalized lithium aluminum hydrotalcite adsorbent.
2. The method of claim 1 for accommodating low and medium CO concentrations 2 The method and the process for high-efficiency trapping are characterized in that: the high-temperature heat treatment temperature selected in the step S1 is 573K.
3. An adaptation to medium to low concentrations of CO according to claim 1 or 2 2 The method and the process for high-efficiency trapping are characterized in that: liCl and AlCl selected in S1 3 ·6H 2 O is a reagent with the purity of 99%.
4. The method of claim 1 for accommodating low and medium CO concentrations 2 The method and the process for high-efficiency trapping are characterized in that: and 5% HCl solution is required to be used for soaking the ion exchange resin in the S2.
5. The method of claim 1 for accommodating low and medium CO concentrations 2 The method and the process for high-efficiency trapping are characterized in that: in the S3, the lithium aluminum hydrotalcite is modified by polyethyleneimine through a chemical grafting method.
6. Root of herbaceous plantAn adaptation to medium to low concentrations of CO according to claim 1 or 3 2 The method and the process for high-efficiency trapping are characterized in that: and in the S3, activated ion exchange resin is selected for ion exchange.
7. The method of claim 1 for accommodating low and medium CO concentrations 2 The method and the process for high-efficiency trapping are characterized in that: in the S3, the mixture needs to be dried in a vacuum drying oven.
8. The method of claim 1 for accommodating low and medium CO concentrations 2 The method and the process for high-efficiency trapping are characterized in that: and the ionic liquid selected in the S5 is an amino carboxylic acid type ionic liquid.
9. The method of claim 1 for accommodating low and medium CO concentrations 2 The method and the process for high-efficiency trapping are characterized in that: the grinding mesh number of the adsorbent in the S5 is 100 meshes.
CN202210933769.3A 2022-08-04 2022-08-04 Adapt to medium-low concentration CO 2 Method and process for efficient capture Withdrawn CN115382513A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116371464A (en) * 2023-02-10 2023-07-04 华东师范大学 Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN S. P.等: ""CO2 adsorption on premodified LiAl hydrotalcite impregnated with polyethylenimine"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, no. 58, pages 1177 - 1189 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116371464A (en) * 2023-02-10 2023-07-04 华东师范大学 Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application
CN116371464B (en) * 2023-02-10 2024-05-17 华东师范大学 Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application

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