CN108704627B - Adsorb CO2Preparation and modification method of solid material TSCD-Zr - Google Patents

Adsorb CO2Preparation and modification method of solid material TSCD-Zr Download PDF

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CN108704627B
CN108704627B CN201810487387.6A CN201810487387A CN108704627B CN 108704627 B CN108704627 B CN 108704627B CN 201810487387 A CN201810487387 A CN 201810487387A CN 108704627 B CN108704627 B CN 108704627B
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CN108704627A (en
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杨泛明
王超林
龙长华
韩凌峰
符健斌
阳开艺
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Hunan City University
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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
    • B01J20/22—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
    • 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
    • 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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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Abstract

The invention provides a method for adsorbing CO2The preparation method of the TSCD-Zr solid material comprises the following steps: dissolving sodium citrate in deionized water, adding metal salt, performing ultrasonic treatment for 1-2 h, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 80-100 ℃ for 12-24 h to obtain the CO adsorption product2TSCD-Zr. The invention also provides a method for modifying the prepared solid material TSCD-Zr by utilizing organic amine. The organic amine modified solid material TSCD-Zr-NH provided by the invention2At lower concentrations of CO2The environment has larger adsorption capacity.

Description

Adsorb CO2Preparation and modification method of solid material TSCD-Zr
[ technical field ] A method for producing a semiconductor device
The invention relates to a method for preparing low-CO at lower temperature2High efficiency of CO in concentration environment2A method for preparing and modifying a solid material TSCD-Zr with adsorption performance.
[ background of the invention ]
In recent years, global industrialization has progressed faster, CO2The emission amount is sharply increased, resulting in an increased greenhouse effect. Thus CO2Capture has become a focus of attention in various countries. CO 22In the capture technique, CO2Adsorption is favored because of its advantages of large adsorption capacity, low corrosivity, good cyclic adsorption performance, etc.
The adsorbent is prepared from CO2The core of adsorption technology. CO 22Among the adsorbents, materials such as carbon materials, silicon-based molecular sieves, metal-organic framework (MOFs) materials, super-molecular framework (SOFs) materials and the like have high adsorption rate, low adsorption-desorption temperature and low energy consumption, but the adsorption amount is small, and the selective adsorption performance is poor. In addition, the raw materials used for preparing the MOFs materials and the SOFs materials are expensive, and the synthesis steps are complicated, so that the MOFs materials and the SOFs materials are greatly limited. Thus the utilization is cheapFast preparation of high-efficiency CO from valuable raw materials2Solid adsorbents with adsorptive properties are at hand.
The organic amine is used for modifying the solid material, so that the CO content of the material can be improved2And (4) adsorption performance. The organic amine is Lewis alkali, the molecular structure of the organic amine contains N atoms, and the interaction between the N atoms and metal atoms containing electron holes on the surface of the solid material can be utilized, so that the organic amine is introduced to the surface of the solid material. Therefore, the method for preparing the solid material with Lewis acidity quickly by using the cheap raw materials has important significance. The bimetallic material contains two metal atoms, and the types of metal salts in the raw materials are changed, so that the bimetallic material with different physical and chemical properties can be prepared. Therefore, the solid material meeting the conditions can be prepared by regulating and controlling the metal atom species, and the organic amine is utilized to modify the solid material to prepare the high-efficiency CO2Solid adsorbent with adsorption performance.
[ summary of the invention ]
The invention aims to provide a method for adsorbing CO2The preparation and modification method of the solid material TSCD-Zr.
In order to achieve the above purpose, the invention provides a method for adsorbing CO2The preparation method of the TSCD-Zr solid material comprises the following steps:
dissolving sodium citrate in deionized water, adding metal salt, performing ultrasonic treatment for 1-2 h, filtering, washing a filter cake with deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 80-100 ℃ for 12-24 h to obtain the CO adsorption product2The solid material of (3) TSCD-Zr;
wherein the metal salt is zirconyl chloride octahydrate or zirconyl nitrate.
In the preparation method, the molar ratio of the sodium citrate to the metal salt is 1: 2-1.
The invention also provides a method for adsorbing CO prepared by the method2The method for modifying the TSCD-Zr solid material comprises the following steps:
adding organic amine and 20g of absolute ethyl alcohol into the polytetrafluoroethylene lining, stirring for dissolving, adding adsorbed CO2Of (2) a solidObtaining a turbid liquid A by using TSCD-Zr as a material;
stirring the turbid solution A at room temperature for 2-3 h, performing rotary evaporation at the temperature of 60-80 ℃, removing the solvent, placing the obtained product in a vacuum drying oven at the temperature of 80-100 ℃ for drying for 4-6 h to obtain a modified material TSCD-Zr-NH2；
Wherein the organic amine is ethylenediamine, diethylenetriamine or triethylenetetramine.
In the modification method, the mass ratio of the organic amine to the TSCD-Zr is (0.1-0.4) to 1.
According to the experimental result, the organic amine modified solid material provided by the invention has low CO concentration2In the environment, with CO2The method has the characteristics of large adsorption capacity, low desorption temperature, good cyclic adsorption performance and the like, and solves the problem of common low-concentration CO2CO in the environment2Small adsorption quantity, high desorption temperature and the like.
[ brief description of the drawings ]
FIG. 1 shows the solid material CO obtained in example 1 of the present invention2Graph of the amount of adsorption as a function of time.
Preparation of a solid material TSCD-Zr:
preparation example 1
Dissolving 2.94g of sodium citrate in deionized water, adding 3.22g of zirconium oxychloride octahydrate, carrying out ultrasonic treatment for 1 hour, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 80 ℃ for 24 hours to obtain the CO adsorbed solid2TSCD-Zr.
Preparation example 2
Dissolving 2.94g of sodium citrate in deionized water, adding 3.22g of zirconium oxychloride octahydrate, carrying out ultrasonic treatment for 2 hours, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 100 ℃ for 12 hours to obtain the CO adsorbed solid2TSCD-Zr.
Preparation example 3
2.94g of sodium citrate was dissolved in deionized water and 6.44g of chloride octahydrate was added to oxidizeZirconium is filtered after being subjected to ultrasonic treatment for 1 hour, a filter cake is washed by deionized water until the filtrate is neutral, and the obtained solid is placed in a drying oven at 80 ℃ for drying for 24 hours to obtain the adsorbed CO2TSCD-Zr.
Preparation example 4
Dissolving 2.94g of sodium citrate in deionized water, adding 6.44g of zirconium oxychloride octahydrate, carrying out ultrasonic treatment for 2 hours, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 100 ℃ for 12 hours to obtain the CO adsorbed solid2TSCD-Zr.
Preparation example 5
Dissolving 2.94g of sodium citrate in deionized water, adding 2.31g of zirconyl nitrate, carrying out ultrasonic treatment for 1h, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 80 ℃ for 24h to obtain the CO adsorbed solid2TSCD-Zr.
Preparation example 6
Dissolving 2.94g of sodium citrate in deionized water, adding 2.31g of zirconyl nitrate, carrying out ultrasonic treatment for 2 hours, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 100 ℃ for 12 hours to obtain the CO adsorbed solid2TSCD-Zr.
Preparation example 7
Dissolving 2.94g of sodium citrate in deionized water, adding 4.62g of zirconyl nitrate, carrying out ultrasonic treatment for 1h, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 80 ℃ for 24h to obtain the CO adsorbed solid2TSCD-Zr.
Preparation example 8
Dissolving 2.94g of sodium citrate in deionized water, adding 4.62g of zirconyl nitrate, carrying out ultrasonic treatment for 2 hours, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 100 ℃ for 12 hours to obtain the CO adsorbed solid2TSCD-Zr.
Organic aminePreparation of modified solid material:
preparation example 9
a. Adding ethylene diamine and 20g of absolute ethyl alcohol into a polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared in preparation example 12The solid material TSCD-Zr to obtain turbid liquid A. The above operations were repeated to obtain 5 parts of turbid solutions having different mass ratios of ethylenediamine to TSCD-Zr. Wherein, the mass ratio of the ethylenediamine to the TSCD-Zr is respectively 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1;
b. stirring the turbid liquid A obtained in the step a at room temperature for 2 hours, performing rotary evaporation at 60 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 100 ℃ for 4 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 10
a. Adding ethylene diamine and 20g of anhydrous ethanol into the polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared in preparation example 22The solid material TSCD-Zr to obtain turbid liquid A. The above operations were repeated to obtain 5 parts of turbid solutions having different mass ratios of ethylenediamine to TSCD-Zr. Wherein, the mass ratio of the ethylenediamine to the TSCD-Zr is respectively 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1;
b. stirring the turbid solution A obtained in the step a at room temperature for 3 hours, performing rotary evaporation at 80 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 100 ℃ for 4 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 11
a. Adding ethylene diamine and 20g of absolute ethyl alcohol into a polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared in preparation example 32The solid material TSCD-Zr to obtain turbid liquid A. The above operations were repeated to obtain 5 parts of turbid solutions having different mass ratios of ethylenediamine to TSCD-Zr. Wherein, the mass ratio of the ethylenediamine to the TSCD-Zr is respectively 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1;
b. stirring the turbid solution A obtained in the step a at room temperature for 3 hours, performing rotary evaporation at 80 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 100 ℃ for 4 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 12
a. Adding diethylenetriamine and 20g absolute ethyl alcohol into a polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared in the preparation example 42The solid material TSCD-Zr to obtain turbid liquid A. And repeating the operation to obtain 5 parts of turbid liquid with different mass ratios of diethylenetriamine and TSCD-Zr. Wherein the mass ratio of diethylenetriamine to TSCD-Zr is 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1 respectively;
b. stirring the turbid liquid A obtained in the step a at room temperature for 2 hours, performing rotary evaporation at 60 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 100 ℃ for 4 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 13
a. Adding diethylenetriamine and 20g absolute ethyl alcohol into a polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared in the preparation example 52The solid material TSCD-Zr to obtain turbid liquid A. And repeating the operation to obtain 5 parts of turbid liquid with different mass ratios of diethylenetriamine and TSCD-Zr. Wherein the mass ratio of diethylenetriamine to TSCD-Zr is 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1 respectively;
b. stirring the turbid liquid A obtained in the step a at room temperature for 3 hours, performing rotary evaporation at 80 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 80 ℃ for 6 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 14
a. Adding diethylenetriamine and 20g absolute ethyl alcohol into a polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared in the preparation example 62The solid material TSCD-Zr to obtain turbid liquid A. And repeating the operation to obtain 5 parts of turbid liquid with different mass ratios of diethylenetriamine and TSCD-Zr. Wherein the mass ratio of diethylenetriamine to TSCD-Zr is 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1 respectively;
b. stirring the turbid liquid A obtained in the step a at room temperature for 3 hours, performing rotary evaporation at 80 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 80 ℃ for 6 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 15
a. Adding triethylene tetramine and 20g of absolute ethyl alcohol into the polytetrafluoroethylene lining, stirring to dissolve, and adding the adsorbed CO prepared in preparation example 72The solid material TSCD-Zr to obtain turbid liquid A. And repeating the operation to obtain 5 parts of turbid liquid with different mass ratios of triethylene tetramine and TSCD-Zr. Wherein the mass ratio of triethylene tetramine to TSCD-Zr is 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1 respectively;
b. stirring the turbid liquid A obtained in the step a at room temperature for 2 hours, performing rotary evaporation at 100 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 100 ℃ for 4 hours to obtain a modified material TSCD-Zr-NH2。
Preparation example 16
a. Adding triethylene tetramine and 20g of absolute ethyl alcohol into the polytetrafluoroethylene lining, stirring to dissolve, and adding the adsorbed CO prepared in the preparation example 82The solid material TSCD-Zr to obtain turbid liquid A. And repeating the operation to obtain 5 parts of turbid liquid with different mass ratios of triethylene tetramine and TSCD-Zr. Wherein the mass ratio of triethylene tetramine to TSCD-Zr is 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1 and 0.4: 1 respectively;
b. stirring the turbid liquid A obtained in the step a at room temperature for 3 hours, performing rotary evaporation at 80 ℃, removing the solvent, and drying the obtained product in a vacuum drying oven at 80 ℃ for 6 hours to obtain a modified material TSCD-Zr-NH2。
2CO adsorption determination of TSCD-Zr solid material and modified material thereof
Example 1
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 1 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The time-dependent change curve of the adsorption amount is shown in FIG. 1.
Example 2
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 1 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 3
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 3 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 4
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 4 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, He volume percent is95％；
Introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 5
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 5 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 6
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 6 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 7
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 7 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 8
Placing a proper amount of TSCD-Zr which is a solid material prepared in preparation example 8 in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of the solid material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60min to obtain CO of TSCD-Zr2The adsorption capacity curve with time is similar to that of FIG. 1.
Example 9
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 9 was taken in an appropriate amount2Placing the mixture in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of a material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in preparation example 1, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 10
Taking an appropriate amount of TSCD-Zr-NH, the organic amine modified solid material prepared in preparation example 102Placing in U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep surface of material, heating to 100 deg.C, maintaining for 60min, and cooling75℃；
Introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in the preparation example 2, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 11
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 11 was taken in an appropriate amount2Placing the mixture in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of a material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in preparation example 3, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 12
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 12 is taken in an appropriate amount2Placing the mixture in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of a material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in preparation example 4, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 13
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 13 was taken in an appropriate amount2Placing the mixture in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of a material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in preparation example 5, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 14
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 14 is taken in an appropriate amount2Placing the mixture in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of a material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in preparation example 6, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 15
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 15 is taken in an appropriate amount2Is arranged in a U-shaped pipe of an AutoChem II 2920 and is led inPurging the surface of the material by using high-purity Ar, simultaneously heating to 100 ℃, keeping for 60min, and then cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in preparation example 7, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
Example 16
The organic amine modified solid material TSCD-Zr-NH prepared in preparation example 16 was taken in an appropriate amount2Placing the mixture in a U-shaped tube of AutoChem II 2920, introducing high-purity Ar to sweep the surface of a material, simultaneously heating to 100 ℃, keeping for 60min, and cooling to 75 ℃;
introducing 5% CO2-He gas at a gas pressure of 0.2MPa and a gas flow rate of 10 ml/min-1Keeping for 10min, 5% CO2CO in-He gas2Volume percent is 5%, volume percent He is 95%;
introducing high-purity Ar, simultaneously heating to 100 ℃, and keeping for 60 min;
compared with the material TSCD-Zr in the preparation example 8, the modified material TSCD-Zr-NH2CO of2The adsorption capacity is obviously increased and is between 3 and 5mmol g-1In the meantime.
To further illustrate the superiority of the organic amine modified solid material of the present invention, the following adsorbents were selected as comparative examples.
At 40 ℃, 80.2g P123 is dissolved in 2000ml deionized water and 400ml concentrated hydrochloric acid, 170g tetraethyl orthosilicate is added, stirring is carried out for 16h, then the temperature is raised to 92 ℃, and the reaction is maintained for 18h, thus obtaining white solid. And washing and drying the obtained solid. And (3) roasting the dried solid in a muffle furnace at 550 ℃ for 6h to obtain the molecular sieve SBA-15.
10g of the prepared SBA-15 was dissolved in a mixed solution of 150ml of toluene and 3.2ml of deionized water, and stirred for 1 hour. 10ml of ethylenediamine was added, the temperature was raised and the mixture was refluxed for 4 hours, and methanol and deionized water were added to conduct distillation. And after distillation, cooling the mixed solution to room temperature, filtering, washing the obtained solid with isopropanol, and drying to obtain the ethylenediamine modified molecular sieve material for later use.
CO of molecular sieve material modified by ethylenediamine2The results of the adsorption experiments show that CO is present at room temperature2At a concentration of 15%, the amount of adsorbed substance was 0.46 mmol/g-1. Pure CO2In the environment, CO2The pressure is 1atm, and the adsorption capacity is about 2 mmol. multidot.g-1。

Claims (3)

1. Adsorb CO2The preparation method of the TSCD-Zr solid material comprises the following steps:
dissolving sodium citrate in deionized water, adding metal salt, performing ultrasonic treatment for 1-2 h, filtering, washing a filter cake by using the deionized water until the filtrate is neutral, and drying the obtained solid in a drying oven at 80-100 ℃ for 12-24 h to obtain the CO adsorption product2The solid material of (3) TSCD-Zr; the molar ratio of the sodium citrate to the metal salt is 1: 2-1]；
Wherein the metal salt is zirconyl chloride octahydrate or zirconyl nitrate.
2. Adsorb CO2The modification method of the TSCD-Zr solid material comprises the following steps:
adding organic amine and 20g of absolute ethyl alcohol into a polytetrafluoroethylene lining, stirring and dissolving, and adding the adsorbed CO prepared by the preparation method of claim 12The TSCD-Zr solid material is adopted to obtain turbid liquid A;
stirring the turbid solution A at room temperature for 2-3 h, performing rotary evaporation at 60-80 ℃, removing the solvent, placing the obtained product in a vacuum drying oven at 80-100 ℃ for drying for 4-6 h to obtain the modified material TSCD-Zr-NH2；
Wherein the organic amine is ethylenediamine, diethylenetriamine or triethylenetetramine.
3. The modification method as claimed in claim 2, wherein the mass ratio of the organic amine to the TSCD-Zr is [ 0.2-0.4 ] to 1.
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CN103418336A (en) * 2013-08-20 2013-12-04 昆明理工大学 Preparation method of high-temperature calcium-based CO2 absorbing material
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