CN111514857A - CO (carbon monoxide)2Preparation method and application of adsorbent - Google Patents

CO (carbon monoxide)2Preparation method and application of adsorbent Download PDF

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CN111514857A
CN111514857A CN202010292627.4A CN202010292627A CN111514857A CN 111514857 A CN111514857 A CN 111514857A CN 202010292627 A CN202010292627 A CN 202010292627A CN 111514857 A CN111514857 A CN 111514857A
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clay
adsorbent
mixture
ion intercalation
reaction product
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宋永臣
凌铮
张毅
石常瑞
李冠初
陈明坤
柴丰圆
赵佳飞
杨磊
李洋辉
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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Abstract

CO (carbon monoxide)2The preparation method and application of the adsorbent are characterized in that the two-dimensional nanosheet composite material is obtained by taking clay with a layered structure as a raw material and carrying out ion intercalation, liquid phase stripping, centrifugal screening and amine loading on the clay for CO2High-efficiency adsorption. Because the ultrathin nano flaky clay used as the carrier has an exposed surface with negative charges and is easier to approach, the surface of the solid carrier is accurately and uniformly modified by using amine; the two-dimensional nano-sheet composite material is used for CO2The adsorption has a series of advantages of large adsorption capacity, high cycle stability, wide temperature range and the like. In the preparation method, no organic solvent, initiator and surfactant are used in the preparation process of the two-dimensional nano-sheet composite material, so that the preparation method has the advantages of environmental friendliness, safety, easiness in operation and the like, and in addition, the clay serving as a carrier raw material is self-containedBut the reserves in the world are abundant, the price is low, thereby being beneficial to reducing the production cost.

Description

CO (carbon monoxide)2Preparation method and application of adsorbent
Technical Field
The invention belongs to the technical field of preparation and improvement of adsorbents, and relates to a method for preparing CO2A preparation method and application of an efficient adsorbent for adsorption.
Background
In recent years, the use of fossil fuels in large quantities has resulted in atmospheric CO2The concentration is rising continuously, and the problems of sea level rising, land desertification, increase of plant diseases and insect pests and the like caused by the greenhouse effect are more and more severe. A very effective solution to this problem is to develop CO2Capture and containment technology (CCS).
At present, various methods such as an alcohol amine solution absorption method, a metal compound absorption method, low-temperature storage, a membrane separation method and the like are applied to CO2Trapping and sealing, however, the chemical reagents and equipment used are expensive, and the increase of production cost due to high regeneration energy limits the large-scale application of the method. The solid amine absorption method has the advantages of stronger adsorption capacity, lower regeneration energy consumption, excellent cycle stability and the like, and becomes ideal CO2Trapping and sealing techniques.
As the solid amine absorption method takes a solid porous material as a carrier, the amine is loaded on the surface of the solid to increase the number of alkaline sites, thereby improving CO2Adsorption capacity, therefore, the pore structure and surface properties of the solid porous material will be towards CO2The adsorption performance has a significant impact. Hu Xiao et al in "a CO2The adsorbent and its preparation method "(CN 110548486A) introduce a CO loaded with ammonium chloride by using metal organic skeleton, inorganic substance and forming assistant as carrier2An adsorbent for CO at normal pressure and 80 deg.C2Is the most important ofThe large adsorption capacity can reach 190mg g-1. Chuai Wei Ye et al in' amino modified mesoporous composite oxide CO2The preparation method of the adsorbent (CN104148020B) introduces CO which takes an alumina-based mesoporous composite oxide as a carrier to load tetraethylenepentamine2An adsorbent for CO at room temperature and normal pressure2The maximum adsorption capacity of the adsorbent can reach 2.02mmol g-1. Yangxianghua et al in 'an organic amine-loaded silicon-based aerogel and a preparation method and application thereof' (CN110551317A) introduce a method for preparing organic amine-loaded silicon-based aerogel CO by adopting a sol-gel method through a copolycondensation reaction2Adsorbent for CO at normal pressure and 40 deg.C2The maximum adsorption capacity of the adsorbent can reach 24mg g-1. However, the supports used in the reported methods are all three-dimensional porous structures, which are disadvantageous for precise and uniform modification using amines, and the high cost of the porous supports limits the large-scale application of the solid amine absorption method. Therefore, there is a need for a low cost solid amine absorption process with a support material having a pore structure and a surface that is more easily modified by amines for CO2The trapping and the sealing have great significance.
Disclosure of Invention
The invention aims to provide a method for CO aiming at the defects of the prior art2A preparation method and application of an efficient adsorbent for adsorption. The invention takes clay with a layered structure as a raw material, and the two-dimensional nano-sheet composite material for CO is obtained by ion intercalation, liquid phase stripping, centrifugal screening and amine loading2High-efficiency adsorption.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
firstly, carrying out sodium ion intercalation through a hydrothermal reaction;
mixing clay and saturated sodium chloride solution according to the mass volume ratio of 3g/1L, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 12-48 hours, naturally cooling the mixture to room temperature after the constant temperature is finished, filtering a reaction product, washing the reaction product with deionized water, and washing the reaction product with absolute ethyl alcohol to obtain the clay subjected to sodium ion intercalation.
Secondly, carrying out lithium ion intercalation through hydrothermal reaction;
mixing the clay subjected to sodium ion intercalation and a lithium chloride solution with the concentration of 0.5-2.5mol/L according to the mass volume ratio of 3g/1L, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 12-48 hours, naturally cooling the mixture to room temperature after constant temperature, filtering a reaction product, washing the reaction product with deionized water, and washing the reaction product with absolute ethyl alcohol to obtain the clay subjected to sodium ion intercalation and lithium ion intercalation.
Thirdly, ultrasonically assisting liquid phase stripping;
mixing the sodium ions and the clay subjected to lithium ion intercalation obtained in the second step with deionized water, wherein the volume ratio of the deionized water to the lithium chloride solution in the second step is 4: 5; the clay nanoplatelets are then exfoliated using a tip sonicator at an amplitude of 40% for 0.5-2 hours in an ice bath to obtain a mixture of clay nanoplatelet dispersion with unexfoliated clay particles and impurities.
Fourthly, centrifugal screening;
and centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove the unexfoliated clay particles and impurities to obtain the stable dispersion liquid of the clay nanosheets.
Fifthly, dipping and freeze-drying to load amine;
adding amine into the stable dispersion liquid obtained in the fourth step, then violently stirring for 0.5-1.5 hours to fully mix the clay nano-sheets and the amine, freezing by using liquid nitrogen after stirring is finished, and freeze-drying for 48 hours to obtain the two-dimensional nano-sheet composite material used for CO2High-efficiency adsorbent for adsorption.
The clay is one or more of vermiculite, montmorillonite, kaolin and illite.
In the fifth step, the amine is one or more than two of tetraethylenepentamine, triethylenetetramine, diethanolamine, polyethyleneimine, tripropylamine, triisopropanolamine, formamide, p-phenylenediamine and phthalimide.
The mass of the load amine is 0.2-50% of that of the clay nano-sheets in the stable dispersion liquid.
CO as described above2Use of an adsorbent for adsorbing said CO2Placing the adsorbent in a fixed bed reactor, vacuum degassing at 150 deg.C for 12 hr, and performing CO treatment at 25-75 deg.C under 0-50bar2And (4) adsorbing.
The absolute pressure of the vacuum degassing was 0.013 bar.
Compared with the prior art, the invention has the advantages and beneficial effects that: the invention takes clay with a layered structure as a raw material, and the two-dimensional nano-sheet composite material for CO is obtained by ion intercalation, liquid phase stripping, centrifugal screening and amine loading2High-efficiency adsorption. Because the ultrathin nano flaky clay used as the carrier has an exposed surface with negative charges and is easier to approach, the surface of the solid carrier is accurately and uniformly modified by using amine; the two-dimensional nano-sheet composite material is used for CO2The adsorption has a series of advantages of large adsorption capacity, high cycle stability, wide temperature range and the like. In the preparation method, no organic solvent, initiator and surfactant are used in the preparation process of the two-dimensional nanosheet composite material, the preparation method has the advantages of environmental friendliness, safety, easiness in operation and the like, and in addition, the clay serving as a carrier raw material is abundant in storage amount and low in price in nature, so that the production cost is favorably reduced. CO processing Using the two-dimensional nanoplate composites of the invention2The adsorption, the adsorption capacity is large, the cycle stability is high, the method is simple and applicable, green and environment-friendly, and is global CO2The emission reduction work provides new technical support.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples.
In the embodiment of the present invention, the clay is one or more than two of vermiculite, montmorillonite, kaolin and illite, and vermiculite is preferred as an example, but not limited thereto. The supported amine is one or more of tetraethylenepentamine, triethylenetetramine, diethanolamine, polyethyleneimine, tripropylamine, triisopropanolamine, formamide, p-phenylenediamine, and phthalimide, and tetraethylenepentamine is preferable, but not limited thereto.
Example 1:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1, carrying out sodium ion intercalation by hydrothermal reaction
Mixing 0.3 g of vermiculite with 100 ml of saturated sodium chloride solution, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 24 hours, naturally cooling the mixture to room temperature after constant temperature is finished, filtering the reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation.
S2, carrying out lithium ion intercalation through hydrothermal reaction
Mixing the vermiculite subjected to sodium ion intercalation with a lithium chloride solution with the concentration of 2mol/L and the volume of 100 ml, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 24 hours, naturally cooling the mixture to room temperature after constant temperature is over, filtering a reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation and lithium ion intercalation.
S3 ultrasonic-assisted liquid phase stripping
Mixing the vermiculite subjected to intercalation of the sodium ions and the lithium ions obtained in the step S2 with deionized water with the volume of 80 ml, and then carrying out ultrasonic treatment on the mixture for 1 hour by using a tip ultrasonic instrument at the amplitude of 40% in an ice bath to peel off the vermiculite nanosheets, so as to obtain a mixture of vermiculite nanosheet dispersion liquid, non-peeled vermiculite particles and impurities.
S4 centrifugal screening
And centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove the non-stripped vermiculite particles and impurities to obtain the stable dispersion liquid of the clay nanosheets.
S5 amine loading by impregnation and freeze drying
Adding tetraethylenepentamine with the mass being 0.2 percent of that of the vermiculite nanosheets into the stable dispersion liquid obtained in the step S4, then violently stirring for 1 hour to fully mix the vermiculite nanosheets and the tetraethylenepentamine, and after stirring is finished, freezing and freeze-drying for 48 hours by using liquid nitrogen to obtain a two-dimensional nanosheet composite material used for CO2High efficiency of adsorptionAn adsorbent.
CO as described above2Application of the adsorbent: placing the two-dimensional nano-sheet composite material into a fixed bed reactor, vacuum degassing at 150 ℃ for 12 hours, and then respectively carrying out CO at 25 ℃, 50 ℃, 75 ℃ and within the pressure range of 0-50bar2And (4) adsorbing. The results showed that the maximum adsorption amount of the adsorbent was 23.3 mmoleg at 25 ℃, 50 ℃ and 75 ℃ respectively-1、19.6mmol g-1、18.9mmol g-1。
Example 2:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1, carrying out sodium ion intercalation by hydrothermal reaction
Mixing 0.3 g of vermiculite with 100 ml of saturated sodium chloride solution, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 24 hours, naturally cooling the mixture to room temperature after constant temperature is finished, filtering the reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation.
S2, carrying out lithium ion intercalation through hydrothermal reaction
Mixing the vermiculite subjected to sodium ion intercalation with a lithium chloride solution with the concentration of 2mol/L and the volume of 100 ml, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 24 hours, naturally cooling the mixture to room temperature after constant temperature is over, filtering a reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation and lithium ion intercalation.
S3 ultrasonic-assisted liquid phase stripping
Mixing the vermiculite subjected to intercalation of the sodium ions and the lithium ions obtained in the step S2 with deionized water with the volume of 80 ml, and then carrying out ultrasonic treatment on the mixture for 1 hour by using a tip ultrasonic instrument at the amplitude of 40% in an ice bath to peel off the vermiculite nanosheets, so as to obtain a mixture of vermiculite nanosheet dispersion liquid, non-peeled vermiculite particles and impurities.
S4 centrifugal screening
And centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove the non-stripped vermiculite particles and impurities to obtain the stable dispersion liquid of the clay nanosheets.
S5 amine loading by impregnation and freeze drying
Adding tetraethylenepentamine with the mass being 1% of that of the vermiculite nanosheets into the stable dispersion liquid obtained in the step S4, then violently stirring for 1 hour to fully mix the vermiculite nanosheets and the tetraethylenepentamine, and after stirring is finished, freezing and freeze-drying for 48 hours by using liquid nitrogen to obtain a two-dimensional nanosheet composite material used for CO2High-efficiency adsorbent for adsorption.
CO as described above2Application of the adsorbent: placing the two-dimensional nano-sheet composite material into a fixed bed reactor, vacuum degassing at 150 ℃ for 12 hours, and then respectively carrying out CO at 25 ℃, 50 ℃, 75 ℃ and within the pressure range of 0-50bar2And (4) adsorbing. The results showed that the maximum adsorption amount of the adsorbent was 29.5mmolg at 25 ℃, 50 ℃ and 75 ℃ respectively-1、26.0mmol g-1、22.4mmol g-1. In addition, after undergoing six cycles of adsorption-desorption, the maximum adsorption capacity retention rates of the adsorbents were 96.7% and 96.4% respectively when the adsorption temperatures were 25 ℃ and 50 ℃.
Example 3:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1, carrying out sodium ion intercalation by hydrothermal reaction
Mixing 0.3 g of vermiculite with 100 ml of saturated sodium chloride solution, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 24 hours, naturally cooling the mixture to room temperature after constant temperature is finished, filtering the reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation.
S2, carrying out lithium ion intercalation through hydrothermal reaction
Mixing the vermiculite subjected to sodium ion intercalation with a lithium chloride solution with the concentration of 2mol/L and the volume of 100 ml, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 24 hours, naturally cooling the mixture to room temperature after constant temperature is over, filtering a reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation and lithium ion intercalation.
S3 ultrasonic-assisted liquid phase stripping
Mixing the vermiculite subjected to intercalation of the sodium ions and the lithium ions obtained in the step S2 with deionized water with the volume of 80 ml, and then carrying out ultrasonic treatment on the mixture for 1 hour by using a tip ultrasonic instrument at the amplitude of 40% in an ice bath to peel off the vermiculite nanosheets, so as to obtain a mixture of vermiculite nanosheet dispersion liquid, non-peeled vermiculite particles and impurities.
S4 centrifugal screening
And centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove the non-stripped vermiculite particles and impurities to obtain the stable dispersion liquid of the clay nanosheets.
S5 amine loading by impregnation and freeze drying
Adding tetraethylenepentamine with the mass being 2 percent of that of the vermiculite nanosheets into the stable dispersion liquid obtained in the step S4, then violently stirring for 1 hour to fully mix the vermiculite nanosheets and the tetraethylenepentamine, and after stirring is finished, freezing and freeze-drying for 48 hours by using liquid nitrogen to obtain a two-dimensional nanosheet composite material used for CO2High-efficiency adsorbent for adsorption.
CO as described above2Application of the adsorbent: placing the two-dimensional nano-sheet composite material into a fixed bed reactor, vacuum degassing at 150 ℃ for 12 hours, and then respectively carrying out CO at 25 ℃, 50 ℃, 75 ℃ and within the pressure range of 0-50bar2And (4) adsorbing. The results showed that the maximum adsorption amount of the adsorbent was 29.5mmolg at 25 ℃, 50 ℃ and 75 ℃ respectively-1、26.0mmol g-1、22.4mmol g-1. In addition, after undergoing six cycles of adsorption-desorption, the maximum adsorption capacity retention rates of the adsorbents were 96.7% and 96.4% respectively when the adsorption temperatures were 25 ℃ and 50 ℃.
Example 4:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1, carrying out sodium ion intercalation by hydrothermal reaction
Mixing 0.3 g of vermiculite with 100 ml of saturated sodium chloride solution, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 12 hours, naturally cooling the mixture to room temperature after constant temperature is finished, filtering the reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation.
S2, carrying out lithium ion intercalation through hydrothermal reaction
Mixing the vermiculite subjected to sodium ion intercalation with a lithium chloride solution with the concentration of 2.5mol/L and the volume of 100 ml, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 12 hours, naturally cooling the mixture to room temperature after constant temperature is over, filtering a reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation and lithium ion intercalation.
S3 ultrasonic-assisted liquid phase stripping
Mixing the vermiculite subjected to intercalation of the sodium ions and the lithium ions obtained in the step S2 with deionized water with the volume of 80 ml, and then carrying out ultrasonic treatment for 2 hours in an ice bath by using a tip ultrasonic instrument at the amplitude of 40% to peel off the vermiculite nanosheets, so as to obtain a mixture of vermiculite nanosheet dispersion liquid, non-peeled vermiculite particles and impurities.
S4 centrifugal screening
And centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove the non-stripped vermiculite particles and impurities to obtain the stable dispersion liquid of the clay nanosheets.
S5 amine loading by impregnation and freeze drying
Adding tetraethylenepentamine with the mass being 10% of that of the vermiculite nanosheets into the stable dispersion liquid obtained in the step S4, then violently stirring for 0.5 hour to fully mix the vermiculite nanosheets and the tetraethylenepentamine, and after stirring is finished, freezing and freeze-drying for 48 hours by using liquid nitrogen to obtain a two-dimensional nanosheet composite material used for CO2High-efficiency adsorbent for adsorption.
Example 5:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1, carrying out sodium ion intercalation by hydrothermal reaction
Mixing 0.3 g of vermiculite with 100 ml of saturated sodium chloride solution, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 48 hours, naturally cooling the mixture to room temperature after constant temperature is finished, filtering the reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation.
S2, carrying out lithium ion intercalation through hydrothermal reaction
Mixing the vermiculite subjected to sodium ion intercalation with a lithium chloride solution with the concentration of 0.5mol/L and the volume of 100 ml, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 48 hours, naturally cooling the mixture to room temperature after constant temperature is over, filtering a reaction product, washing the reaction product with deionized water for a plurality of times, and washing the reaction product with absolute ethyl alcohol to obtain the vermiculite subjected to sodium ion intercalation and lithium ion intercalation.
S3 ultrasonic-assisted liquid phase stripping
Mixing the vermiculite subjected to intercalation of the sodium ions and the lithium ions obtained in the step S2 with deionized water with the volume of 80 ml, and then carrying out ultrasonic treatment for 0.5 hour at 40% of amplitude in an ice bath by using a tip ultrasonic instrument to peel off the vermiculite nanosheets, so as to obtain a mixture of the vermiculite nanosheet dispersion liquid, the non-peeled vermiculite particles and impurities.
S4 centrifugal screening
And centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove the non-stripped vermiculite particles and impurities to obtain the stable dispersion liquid of the clay nanosheets.
S5 amine loading by impregnation and freeze drying
Adding tetraethylenepentamine with the mass being 50% of that of the vermiculite nanosheets into the stable dispersion liquid obtained in the step S4, then violently stirring for 1.5 hours to fully mix the vermiculite nanosheets and the tetraethylenepentamine, and after stirring is finished, freezing and freeze-drying for 48 hours by using liquid nitrogen to obtain a two-dimensional nanosheet composite material used for CO2High-efficiency adsorbent for adsorption.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (7)

1. CO (carbon monoxide)2The preparation method of the adsorbent is characterized by comprising the following steps:
firstly, carrying out sodium ion intercalation through a hydrothermal reaction;
mixing clay and saturated sodium chloride solution according to the mass-volume ratio of 3g/1L, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 12-48 hours, naturally cooling the mixture to room temperature after constant temperature is finished, filtering a reaction product, washing the reaction product with deionized water, and washing the reaction product with absolute ethyl alcohol to obtain clay subjected to sodium ion intercalation;
secondly, carrying out lithium ion intercalation through hydrothermal reaction;
mixing the clay subjected to sodium ion intercalation with a lithium chloride solution with the concentration of 0.5-2.5mol/L according to the mass-volume ratio of 3g/1L, placing the mixture in a hydrothermal reactor, heating the mixture at 110 ℃ for 12-48 hours, naturally cooling the mixture to room temperature after constant temperature, filtering a reaction product, washing the reaction product with deionized water, and washing the reaction product with absolute ethyl alcohol to obtain the clay subjected to sodium ion intercalation and lithium ion intercalation;
thirdly, ultrasonically assisting liquid phase stripping;
mixing the sodium ions and the clay subjected to lithium ion intercalation obtained in the second step with deionized water, wherein the volume ratio of the deionized water to the lithium chloride solution in the second step is 4: 5; then carrying out ultrasonic treatment in ice bath for 0.5-2 hours to enable the clay nano-sheets to be peeled off, and obtaining a mixture of clay nano-sheet dispersion liquid, un-peeled clay particles and impurities;
fourthly, centrifugal screening;
centrifuging the mixture obtained after ultrasonic stripping at the rotating speed of 500rpm for 1 hour to remove un-stripped clay particles and impurities to obtain stable dispersion liquid of clay nanosheets;
fifthly, dipping and freeze-drying to load amine;
adding amine into the stable dispersion liquid obtained in the fourth step, then violently stirring for 0.5-1.5 hours to fully mix the clay nano-sheets and the amine, freezing by using liquid nitrogen after stirring is finished, and freeze-drying for 48 hours to obtain the two-dimensional nano-sheet composite material used for CO2AdsorptionThe high-efficiency adsorbent of (1).
2. CO according to claim 12The preparation method of the adsorbent is characterized in that the clay is one or more than two of vermiculite, montmorillonite, kaolin and illite.
3. CO according to claim 12The preparation method of the adsorbent is characterized in that in the fifth step, the amine is one or more of tetraethylenepentamine, triethylenetetramine, diethanolamine, polyethyleneimine, tripropylamine, triisopropanolamine, formamide, p-phenylenediamine and phthalimide.
4. CO according to claim 12The preparation method of the adsorbent is characterized in that the mass of the loaded amine is 0.2-50% of the mass of the clay nanosheet in the stable dispersion liquid.
5. CO produced by the process according to claims 1 to 42An adsorbent.
6. CO according to claim 52Use of an adsorbent, characterized in that the CO is introduced2Placing the adsorbent in a fixed bed reactor, vacuum degassing at 150 deg.C for 12 hr, and performing CO treatment at 25-75 deg.C under 0-50bar2And (4) adsorbing.
7. CO according to claim 62Use of an adsorbent, characterized in that the vacuum degassing absolute pressure is 0.013 bar.
CN202010292627.4A 2020-04-15 2020-04-15 CO (carbon monoxide)2Preparation method and application of adsorbent Withdrawn CN111514857A (en)

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CN112791707A (en) * 2021-04-01 2021-05-14 北京锦绣新技术发展有限公司 Preparation method and application of nano carbon dioxide capture agent
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