CN103894160A - Carbon dioxide solid absorbent as well as preparation method thereof - Google Patents
Carbon dioxide solid absorbent as well as preparation method thereof Download PDFInfo
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- CN103894160A CN103894160A CN201410153964.XA CN201410153964A CN103894160A CN 103894160 A CN103894160 A CN 103894160A CN 201410153964 A CN201410153964 A CN 201410153964A CN 103894160 A CN103894160 A CN 103894160A
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- 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
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a carbon dioxide solid absorbent. The carbon dioxide solid absorbent comprises a composite carrier consisting of activated carbon and zirconium dioxide; the surface of the composite carrier is loaded with an ion liquid polymer, and the surface of the activated carbon is loaded with zirconium dioxide. The preparation method of the carbon dioxide solid absorbent comprises the following steps: preparing zirconium dioxide gel by taking zirconium oxychloride as a precursor and taking H2O2 as a hydrolysis promotion agent, adding activated carbon in the reaction process to prepare a composite carrier; dissolving an ionic liquid polymer by absolute ethyl alcohol so as to prepare an ionic liquid polymer solution; immersing the composite carrier into the ion liquid polymer solution, immersing at room temperature, filtering, drying the obtained solid to obtain solid particles, and crushing the particles. The carbon dioxide solid absorbent provided by the invention has the advantages of low regeneration temperature, high regeneration rate, no pollution, good cycle performance, low equipment corrosion, high absorption capacity and economic cost reduction, is used for capturing carbon dioxide in various fields, and is especially used for capturing coal combusted flue gas carbon dioxide.
Description
Technical field
The present invention relates to a kind of carbon dioxide solid absorbent and preparation method thereof, belong to environmental pollution prevention and control and Filter Tuber For Clean Coal field of combustion technology.
Background technology
The greenhouse effects that CO2 emission causes cause serious climatic effect to our earth.World's majority state including China has all been signed Kyoto Protocol at present, and the discharge capacity of controlling carbon dioxide is described, has become the problem that countries in the world are extremely paid close attention to.Carbon dioxide as a kind of carbon resource of preciousness, is widely used in the multiple fields such as chemical industry, food, medicine simultaneously, if effectively developed, just can be continuously for we provide carbon resource.The source of China's carbon dioxide is very abundant, but unfavorable owing to reclaiming the measure of carbon dioxide, the carbon dioxide of annual recycling also not enough total release 1%, therefore, the emission problem that effectively solves carbon dioxide is extremely urgent.
The method of collecting carbonic anhydride mainly contains: solvent absorption, physisorphtion, membrane separation process, O
2production by Catalytic Combustion Process etc.Wherein chemical solvent method absorbing carbon dioxide technology is widely used in the discharge sources of the gas such as natural gas, refinery gas, synthesis gas, flue gas.At present, hydramine is the conventional absorbent of chemical solvent method absorbing carbon dioxide in industrial production.The method using hydramine if the aqueous solution of monoethanolamine (MEA), diethanol amine (DEA), diisopropanolamine (DIPA) (DIPA), N methyldiethanol amine (MDEA) etc. is as absorbent.For further improve absorbent absorbability, reduce corrosivity, energy consumption while reducing the loss that causes because of volatilization and regeneration, people are devoted to develop efficient chemical solution absorbent always, through years of researches, develop into the absorbent of present compounding ingredients low energy consumption from the absorbent of one pack system high energy consumption starting, but still exist at present, process energy consumption is high, equipment corrosion serious, absorbent rate of deterioration is fast, high volatility causes the problems such as absorbent loss.Therefore, developing absorbent efficient, eco-friendly capturing carbon dioxide is current problem demanding prompt solution.
Utilize dry method absorbent by the focus that the technology of gas-solid reaction carbon dioxide removal has that energy consumption of reaction is low, cyclic utilization rate is high, the advantage such as, non-secondary pollution corrosion-free to equipment has become current research.
More the having lithium salts absorbent, calcium-base absorbing agent and amino be grafted to the absorbent on porous carrier of research at present, but the expensive reactivity of the material price of lithium salts is lower, is difficult to obtain popularization; In calcium-base absorbing agent easily there is product layer blockage of the micro orifice, CO in CaO carbonation
2be difficult to be diffused into granule interior and react, the easy sintered surface of the higher CaO particle of regeneration temperature is long-pending to be reduced with porosity, and absorption efficiency declines; Amino is grafted to the absorbent on porous carrier, due to amino and CO
2the materials such as reaction Formed hydrochlorate, bicarbonate cause adsorbent could regenerate the energy consumption of adsorption separation process is increased at higher temperature.
Researcher is take materials such as active carbon (AC), titanium dioxide, alchlor, magnesia, silica as carrier is by K both at home and abroad
2cO
2, the absorbent load such as organic amine thereon, and carried out experimental study.The CN101862666 patent of the Chen Xiao equality application of Southeast China University is take aluminium oxide as carrier take potash as active component, using one or more in arsenic trioxide, vanadic anhydride and amion acetic acid as catalyst, prepared a kind of this absorbent of drikold absorbent have high to carbon dioxide absorption efficiency, infiltration rate is fast, cyclic utilization rate is high and to advantages such as equipment corrosion are little.
Poly ion liquid is the polymer being synthesized by ionic liquid monomer, CO absorption for ionic liquid at room temperature monomer
2ability is stronger, and has absorption-desorption rate faster.This polymer, we are referred to as poly ion liquid.Anion, cation and the skeleton of poly ion liquid are to CO
2the impact of adsorption capacity, also totally different with ionic liquid at room temperature.For example,, at CO
2in adsorption process, the cation in poly ion liquid plays a major role, and in ionic liquid at room temperature, anion is decisive parameter.Simultaneously poly ion liquid also have non-volatile, ionic structure can design, liquid state exists that temperature range is wide, good stability, advantages of environment protection, have broad application prospects at aspects such as extract and separate, catalytic reaction, GAS ABSORPTION.Poly ion liquid, as the absorbent of sour gas, can make up the volatile shortcoming of traditional hydramine absorbent, can not pollute and need Purge gas and environment, can not cause because of volatilization the loss of absorbent.In addition, poly ion liquid is to CO
2absorption-desorption is completely reversibility.
Summary of the invention
The technical problem to be solved in the present invention is: provide that a kind of regeneration temperature is low, regeneration rate is high, pollution-free, good cycle, little to equipment corrosion, absorptive capacity is high, reduce carbon dioxide solid absorbent of financial cost and preparation method thereof, solve with absorbent cyclic utilization rate in solution prior art low, regeneration energy consumption is high, secondary pollution is serious, and equipment corrosion is serious, absorbent rate of deterioration is fast, high volatility causes the problems such as absorbent loss.
In order to solve the problems of the technologies described above, technical scheme of the present invention has been to provide a kind of carbon dioxide solid absorbent, it is characterized in that, comprises the complex carrier with active carbon and zirconium dioxide composition, at the area load ion liquid polymer of complex carrier, activated carbon surface is Zirconium dioxide loaded.
Preferably, described ion liquid polymer is chloroethylenes base butyl imidazole ion liquid polymer or bromoethylene base butyl imidazole ion liquid polymer.
Preferably, the ion liquid polymer preparation process of described chloroethylenes base butyl imidazole is as follows:
The first step: taking molar ratio is 1: 2-1: 6 1-vinyl imidazole and 1-chloro-butane are in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 65-90 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make chloroethylenes base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven chloroethylenes base butyl imidazole ionic liquid; taking mass ratio is 175: 1-100: 1 chloroethylenes base butyl imidazole ionic liquid and initiator A IBN; add chloroform; be prepared into the solution that mass concentration is 5%-15%; under nitrogen protection, fully react 10-16 hour, add ether until there is solid; by solid filtering, the solid obtaining is chloroethylenes base butyl imidazole ion liquid polymer.
Preferably, the ion liquid polymer preparation process of described bromoethylene base butyl imidazole is as follows:
The first step: taking molar ratio is 1: 2-1: 6 1-vinyl imidazole and 1-bromic ether are in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 65-90 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make bromoethylene base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven bromoethylene base butyl imidazole ionic liquid; taking mass ratio is 175: 1-100: 1 bromoethylene base butyl imidazole ionic liquid and initiator A IBN; add chloroform; be prepared into the solution that mass concentration is 5%-15%; be prepared into the solution that mass concentration is 5%-15%; under nitrogen protection; fully reaction 10-16 hour; add ether until there is solid; by solid filtering, the solid obtaining is bromoethylene base butyl imidazole ion liquid polymer.
Preferably, described complex carrier is take zirconium oxychloride as presoma is with H
2o
2prepare after adding active carbon in the course of reaction of zirconia sol and make for short hydrolytic reagent.
Preferably, the mass ratio of described ion liquid polymer and complex carrier is 1: 9-1: 1.
Preferably, in described complex carrier, the mass ratio of active carbon and zirconium dioxide is 15: 1-3: 1.
A preparation method for carbon dioxide solid absorbent, is characterized in that, comprises the steps:
Step (1): add the ethanolic solution of zirconium oxychloride in reactor, then drip H under the condition stirring
2o
2ethanolic solution, and add active carbon fully to react, by aging obtained solution left standstill, remove supernatant liquor, obtain zirconium dioxide-active carbon colloidal sol, the colloidal sol of gained is transferred in crucible, put into the fully dry zirconium dioxide-activated carbon granule that obtains of baking oven;
Step (2): zirconium dioxide-activated carbon granule that step (1) is made is put into the Muffle furnace of 450-600 ℃ of nitrogen atmosphere and calcined 1-3 hour, obtains zirconium dioxide-activated carbon composite carrier;
Step (3): be mixed with the ion liquid polymer solution that mass concentration is 10-60% with anhydrous alcohol solution ion liquid polymer;
Step (4): the complex carrier that step (2) is made is immersed in the ion liquid polymer solution that step (3) makes, floods under room temperature after 1.5-3 hour and filters, and gained solid is fully dried and obtained solid particle.
Step (5): the solid particle that step (4) is made is broken into the particle that particle diameter is less than 0.6mm.
Preferably, in described step (1), the particle size range of activated carbon granule is 0.3-5mm.
Preferably, the nitrogen in described step (2) is that purity is greater than 99.9% high pure nitrogen.
Carbon dioxide solid absorbent of the present invention has advantages of that regeneration temperature is low, regeneration rate is high, pollution-free, good cycle, little to equipment corrosion, absorptive capacity is high, reduce financial cost, be used for the trapping of the carbon dioxide in various fields, especially for the trapping of coal-fired flue-gas carbon dioxide.
In carbon dioxide solid absorbent of the present invention, complex carrier is that activated carbon surface is Zirconium dioxide loaded.This complex carrier is take zirconium oxychloride as presoma is with H
2o
2prepare zirconia sol for short hydrolytic reagent, in course of reaction, add active carbon, make complex carrier, complex carrier obtained by this method has good pore structure, be more suitable for as absorbent carrier, and the cost of zirconium oxychloride is lower, is conducive to reduce use cost.Ion liquid polymer be chlorine (bromine) for vinyl butyl imidazoles plasma liquid by the prepared ion liquid polymer of polymerization.This polymer has the performance of better absorbing carbon dioxide than ionic liquid monomer, carbon dioxide is had to higher absorptive capacity, and its absorption-desorb to carbon dioxide is completely reversibility.
Compared with the chemical absorption method that is absorbent with existing organic amine, solid absorbent absorption and desorption speed of the present invention is high, absorptive capacity is large, energy consumption of reaction is low, cyclic utilization rate is high, because be solid absorbent, corrosion-free to equipment, to product non-secondary pollution.
Compared with simple load potash solid absorbent, the pore structure of complex carrier of the present invention is good, specific area increases and has the larger absorbed dose of radiation that carries, thereby total use amount that can reduce complex carrier reduces costs.
The preparation method of carbon dioxide solid absorbent of the present invention is simple, and easily operation, utilizes conventional instrument and equipment to implement.
The specific embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
The present invention is a kind of carbon dioxide solid absorbent, and it comprises that at the area load ion liquid polymer (poly ion liquid) of complex carrier, activated carbon surface is Zirconium dioxide loaded with the complex carrier of active carbon and zirconium dioxide composition.Ion liquid polymer is chloroethylenes base butyl imidazole ion liquid polymer.Complex carrier is take zirconium oxychloride as presoma is with H
2o
2prepare after adding active carbon in the course of reaction of zirconia sol and make for short hydrolytic reagent.Complex carrier obtained by this method has good pore structure, be more suitable for as absorbent carrier, and the cost of zirconium oxychloride is lower, is conducive to reduce use cost.
Ion liquid polymer (poly ion liquid) is 1 with the mass ratio of complex carrier: 9-1: 1, and its most preferred mass ratio is 1: 6-1: 1.5.In complex carrier, the mass ratio of active carbon and zirconium dioxide is 15: 1-3: 1, and its most preferred mass ratio is 7: 1-5: 1.
Chlorine (bromine) for vinyl butyl imidazoles poly ion liquid preparation method as shown in the formula:
The ion liquid polymer preparation process of chloroethylenes base butyl imidazole is as follows:
The first step: take molar ratio and be the 1-vinyl imidazole of 1mol and the 1-chloro-butane of 2mol in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 65 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make chloroethylenes base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven chloroethylenes base butyl imidazole ionic liquid; taking quality is chloroethylenes base butyl imidazole ionic liquid and the 0.2g initiator A IBN of 35g; 156ml adds chloroform; be prepared into mass concentration and be 15% solution; under nitrogen protection, fully react 10 hours, add ether until there is solid; by solid filtering, the solid obtaining is chloroethylenes base butyl imidazole ion liquid polymer.
The preparation method of above-mentioned carbon dioxide solid absorbent comprises the steps:
Step (1): add the ethanolic solution of the 0.5mol/L zirconium oxychloride of 250ml in reactor, then slowly drip the 0.45mol/L H of 500ml under the condition stirring
2o
2ethanolic solution, and add the active carbon of 50g fully to react 6 hours, will within aging obtain solution left standstill 3 days, obtain zirconium dioxide-active carbon colloidal sol sample.After the aging sample obtaining is removed to supernatant liquor, transfer in crucible, put into after 90 ℃, baking oven is dried and obtain zirconium dioxide-activated charcoal solid particle;
Step (2): zirconium dioxide-activated charcoal solid particle that step (1) is made is put into the Muffle furnace of the nitrogen atmosphere that the purity of 500 ℃ is 99.9% and calcined 2 hours, makes zirconium dioxide-activated carbon composite carrier;
Step (3): take 36g absolute ethyl alcohol with beaker, 4g chloroethylenes base butyl imidazole ion liquid polymer is poured into wherein, stir it is dissolved completely with glass bar, be configured to mass concentration and be 10% solution;
Step (4): the complex carrier that step (2) is made is got 36g and is immersed in the solution that step (3) makes, floods under room temperature after 2 hours and filters, and gained solid is dried 4 hours at 110 ℃, obtains solid particle;
Step (5): the solid particle that step (4) is made is broken into the particle that particle diameter is less than 0.6mm.
Embodiment 2
The present invention is a kind of carbon dioxide solid absorbent, and it comprises that at the area load ion liquid polymer (poly ion liquid) of complex carrier, activated carbon surface is Zirconium dioxide loaded with the complex carrier of active carbon and zirconium dioxide composition.Ion liquid polymer is bromoethylene base butyl imidazole ion liquid polymer.Complex carrier is to make add active carbon in the course of reaction of preparing zirconia sol take zirconium oxychloride as presoma take H2O2 as short hydrolytic reagent after.Complex carrier obtained by this method has good pore structure, be more suitable for as absorbent carrier, and the cost of zirconium oxychloride is lower, is conducive to reduce use cost.
Chlorine (bromine) for vinyl butyl imidazoles poly ion liquid preparation method as shown in the formula:
The ion liquid polymer preparation process of bromoethylene base butyl imidazole is as follows:
The first step: take the 1-vinyl imidazole of 1mol and the 1-butyl bromide of 4mol in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 80 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make bromoethylene base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven bromoethylene base butyl imidazole ionic liquid; taking quality is bromoethylene base butyl imidazole ionic liquid and the initiator A IBN0.2g of 30g; be dissolved in 200ml chloroform; under nitrogen protection; fully react 16 hours in 60 ℃; add ether until there is solid, by solid filtering, the solid obtaining is the ion liquid polymer of bromoethylene base butyl imidazole.
The preparation method of above-mentioned carbon dioxide solid absorbent comprises the steps:
Step (1): add the ethanolic solution of the 0.5mol/L zirconium oxychloride of 300ml in reactor, then slowly drip the 0.45mol/L H of 600ml under the condition stirring
2o
2ethanolic solution, and add the active carbon of 50g fully to react 6 hours, will within aging obtain solution left standstill 3 days, obtain zirconium dioxide-active carbon colloidal sol sample.After the aging sample obtaining is removed to supernatant liquor, transfer in crucible, put into after 90 ℃, baking oven is dried and obtain zirconium dioxide-activated charcoal solid particle;
Step (2): zirconium dioxide-activated charcoal solid particle that step (1) is made is put into the Muffle furnace of the nitrogen atmosphere that the purity of 550 ℃ is 99.9% and calcined 3 hours, makes zirconium dioxide-activated carbon composite carrier;
Step (3): take 10.3g absolute ethyl alcohol with beaker, 4.4g bromoethylene base butyl imidazole ion liquid polymer is poured into wherein, stir it is dissolved completely with glass bar, be configured to mass concentration and be 30% solution;
Step (4): the complex carrier that step (2) is made is got 20g and is immersed in the solution that step (3) makes, floods under room temperature after 2 hours and filters, and gained solid is dried 4 hours at 110 ℃, obtains solid particle;
Step (5): the solid particle that step (4) is made is broken into the particle that particle diameter is less than 0.6mm.
Embodiment 3
The present invention is a kind of carbon dioxide solid absorbent, and it comprises that at the area load ion liquid polymer (poly ion liquid) of complex carrier, activated carbon surface is Zirconium dioxide loaded with the complex carrier of active carbon and zirconium dioxide composition.Ion liquid polymer is chloroethylenes base butyl imidazole ion liquid polymer.Complex carrier is to make add active carbon in the course of reaction of preparing zirconia sol take zirconium oxychloride as presoma take H2O2 as short hydrolytic reagent after.Complex carrier obtained by this method has good pore structure, be more suitable for as absorbent carrier, and the cost of zirconium oxychloride is lower, is conducive to reduce use cost.
Chlorine (bromine) for vinyl butyl imidazoles poly ion liquid preparation method as shown in the formula:
The ion liquid polymer preparation process of chloroethylenes base butyl imidazole is as follows:
The first step: take the 1-vinyl imidazole of lmol and the 1-chloro-butane of 6mol in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 90 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make chloroethylenes base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven chloroethylenes base butyl imidazole ionic liquid; taking quality is chloroethylenes base butyl imidazole ionic liquid and the 0.2g initiator A IBN of 20g; add 76ml chloroform; be prepared into mass concentration and be 15% solution; under nitrogen protection, fully react 16 hours, add ether until there is solid; by solid filtering, the solid obtaining is chloroethylenes base butyl imidazole ion liquid polymer.
The preparation method of above-mentioned carbon dioxide solid absorbent comprises the steps:
Step (1): add the ethanolic solution of the 0.5mol/L zirconium oxychloride of 400ml in reactor, then slowly drip the 0.45mol/L H of 800ml under the condition stirring
2o
2ethanolic solution, and add the active carbon of 50g fully to react 6 hours, will within aging obtain solution left standstill 3 days, obtain zirconium dioxide-active carbon colloidal sol sample.After the aging sample obtaining is removed to supernatant liquor, transfer in crucible, put into after 90 ℃, baking oven is dried and obtain zirconium dioxide-activated charcoal solid particle;
Step (2): the activated carbon granule that step (1) is made is put into the Muffle furnace calcining 2 hours of the nitrogen atmosphere that the purity of 600 ℃ is 99.9%, makes zirconium dioxide-activated carbon composite carrier;
Step (3): take 30g absolute ethyl alcohol with beaker, 20g chloroethylenes base butyl imidazole ion liquid polymer is poured into wherein, stir it is dissolved completely with glass bar, be configured to mass concentration and be 60% solution;
Step (4): the complex carrier that step (2) is made is got 20g and is immersed in the solution that step (3) makes, floods under room temperature after 2 hours and filters, and gained solid is dried 4 hours at 110 ℃, obtains solid particle;
Step (5): the solid particle that step (4) is made is broken into the particle that particle diameter is less than 0.6mm.
The mensuration of solid absorbent absorption/desorption performance
Adopt ℃ O
2steel cylinder and N
2steel cylinder distribution, the main pipeline of device is 8mm by internal diameter, bed height is 40cm copper pipe (preheating section, adsorption column) and Teflon pipe (bypass etc.) composition.Heating temperature control device is self-control, and temperature-controlled precision is scholar l ℃.Contain certain proportion CO
2, N
2mist first form a mass transfer adsorption zone at the initiating terminal of adsorption column by adsorption bed, along with accumulation throughput increases, mass-transfer zone is pushed ahead along airflow direction, and adsorption column tail end air-flow concentration remains unchanged at the beginning, then raises until approach inlet concentration gradually.At set intervals copper pipe is shifted out to system, seal immediately, determine the quality of solid absorbent absorbing carbon dioxide with electronic balance (0.1mg).Again by copper pipe connecting system, repeat aforesaid operations, until copper pipe constant mass.
The mensuration of solid absorbent Desorption of Carbon Dioxide ability: by above-mentioned copper pipe connecting system, copper pipe is heated to desorption temperature, at set intervals copper pipe is taken out, pass into air, determine the quality of solid absorbent Desorption of Carbon Dioxide with electronic balance (0.1mg).Again by copper pipe connecting system, repeat aforesaid operations, until copper pipe constant mass.
Absorbability test condition: absorbent consumption 30.0g, absorption pressure 0.1MPa, absorbs temperature and be respectively 0 ℃, 20 ℃, 30 ℃ and 50 ℃, mist flow velocity 100mL/min.
Desorption ability test condition: desorption pressures 0.1MPa, desorption temperature is 75 ℃ and 80 ℃.
Be below the performance measurement of embodiment 1-3 under different condition:
Solid absorbent recycles the mensuration of performance
The solid absorbent powder that above-described embodiment 1,2,3 is made, puts into the vacuum chamber vacuum drying of microbalance and degassed 12 hours, to eliminate moisture or other volatile contaminants, until its weight reached at least 30 minutes constant; Abundant dried carbon dioxide, at 30 ℃, is passed into sample room by carbon dioxide dress under normal pressure, record weight, until within 30 minutes, there is no significant change; Then vacuum chamber is vacuumized, so circulation repeatedly.
Claims (10)
1. a carbon dioxide solid absorbent, is characterized in that, comprises that at the area load ion liquid polymer of complex carrier, activated carbon surface is Zirconium dioxide loaded with the complex carrier of active carbon and zirconium dioxide composition.
2. a kind of carbon dioxide solid absorbent as claimed in claim 1, is characterized in that, described ion liquid polymer is chloroethylenes base butyl imidazole ion liquid polymer or bromoethylene base butyl imidazole ion liquid polymer.
3. a kind of carbon dioxide solid absorbent as claimed in claim 2, is characterized in that, the ion liquid polymer preparation process of described chloroethylenes base butyl imidazole is as follows:
The first step: taking molar ratio is 1: 2-1: 6 1-vinyl imidazole and 1-chloro-butane are in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 65-90 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make chloroethylenes base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven chloroethylenes base butyl imidazole ionic liquid; taking mass ratio is 175: 1-100: 1 chloroethylenes base butyl imidazole ionic liquid and initiator A IBN; add chloroform; be prepared into the solution that mass concentration is 5%-15%; under nitrogen protection, fully react 10-16 hour, add ether until there is solid; by solid filtering, the solid obtaining is chloroethylenes base butyl imidazole ion liquid polymer.
4. a kind of carbon dioxide solid absorbent as claimed in claim 2, is characterized in that, the ion liquid polymer preparation process of described bromoethylene base butyl imidazole is as follows:
The first step: taking molar ratio is 1: 2-1: 6 1-vinyl imidazole and 1-bromic ether are in two mouthfuls of flasks, under nitrogen protection, reflux and add thermal response in 65-90 ℃, until generation thick liquid, after being diluted to completely and dissolving with ethanol, rotary evaporation is removed unreacted material, in triplicate, and be placed in vacuum drying chamber and dry, make bromoethylene base butyl imidazole ionic liquid;
Second step: by fully dry in baking oven bromoethylene base butyl imidazole ionic liquid; taking mass ratio is 175: 1-100: 1 bromoethylene base butyl imidazole ionic liquid and initiator A IBN; add chloroform; be prepared into the solution that mass concentration is 5%-15%; be prepared into the solution that mass concentration is 5%-15%; under nitrogen protection; fully reaction 10-16 hour; add ether until there is solid; by solid filtering, the solid obtaining is bromoethylene base butyl imidazole ion liquid polymer.
5. a kind of carbon dioxide solid absorbent as claimed in claim 1, is characterized in that, described complex carrier is take zirconium oxychloride as presoma is with H
2o
2prepare after adding active carbon in the course of reaction of zirconia sol and make for short hydrolytic reagent.
6. a kind of carbon dioxide solid absorbent as claimed in claim 1, is characterized in that, described ion liquid polymer and the mass ratio of complex carrier are 1: 9-1: 1.
7. a kind of carbon dioxide solid absorbent as claimed in claim 1, is characterized in that, in described complex carrier, the mass ratio of active carbon and zirconium dioxide is 15: 1-3: 1.
8. a preparation method for the carbon dioxide solid absorbent as described in claim 1-7 any one, is characterized in that, comprises the steps:
Step (1): add the ethanolic solution of zirconium oxychloride in reactor, then drip H under the condition stirring
2o
2ethanolic solution, and add active carbon fully to react, by aging obtained solution left standstill, remove supernatant liquor, obtain zirconium dioxide-active carbon colloidal sol, the colloidal sol of gained is transferred in crucible, put into the fully dry zirconium dioxide-activated carbon granule that obtains of baking oven;
Step (2): the activated carbon granule that step (1) is made is put into the Muffle furnace of 450-600 ℃ of nitrogen atmosphere and calcined, and obtains zirconium dioxide-activated carbon composite carrier;
Step (3): be mixed with the ion liquid polymer solution that mass concentration is 10-60% with anhydrous alcohol solution ion liquid polymer;
Step (4): the complex carrier that step (2) is made is immersed in the ion liquid polymer solution that step (3) makes, floods under room temperature after 1.5-3 hour and filters, and gained solid is fully dried and obtained solid particle.
Step (5): the solid particle that step (4) is made is broken into the particle that particle diameter is less than 0.6mm.
9. a kind of carbon dioxide solid absorbent as claimed in claim 8, is characterized in that, in described step (1), the particle size range of activated carbon granule is 0.3-5mm.
10. a kind of carbon dioxide solid absorbent as claimed in claim 8, is characterized in that, the nitrogen in described step (2) is that purity is greater than 99.9% high pure nitrogen.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107159132A (en) * | 2017-06-07 | 2017-09-15 | 华中科技大学 | CO2/ CO selective absorbents and preparation method thereof |
| CN108273477A (en) * | 2018-02-07 | 2018-07-13 | 厦门大学 | A kind of porous poly ion liquid adsorbent and its application |
| CN108905501A (en) * | 2018-08-31 | 2018-11-30 | 东南大学 | A kind of fluent material and preparation method thereof with porous structure |
| CN111715031A (en) * | 2020-06-24 | 2020-09-29 | 江西师范大学 | Carbon dioxide absorption medium and optimization process thereof |
| CN115254032A (en) * | 2022-04-15 | 2022-11-01 | 中国辐射防护研究院 | Ionic liquid immobilized activated carbon and preparation method thereof |
| WO2023176583A1 (en) * | 2022-03-15 | 2023-09-21 | 国立大学法人九州大学 | Method and apparatus for producing synthesis gas containing carbon monoxide |
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Cited By (9)
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| CN106268718A (en) * | 2016-08-22 | 2017-01-04 | 昆明理工大学 | A kind of method of modified activated carbon and application thereof |
| CN107159132A (en) * | 2017-06-07 | 2017-09-15 | 华中科技大学 | CO2/ CO selective absorbents and preparation method thereof |
| CN107159132B (en) * | 2017-06-07 | 2019-12-10 | 华中科技大学 | CO 2/CO selective adsorbent and preparation method thereof |
| CN108273477A (en) * | 2018-02-07 | 2018-07-13 | 厦门大学 | A kind of porous poly ion liquid adsorbent and its application |
| CN108905501A (en) * | 2018-08-31 | 2018-11-30 | 东南大学 | A kind of fluent material and preparation method thereof with porous structure |
| CN108905501B (en) * | 2018-08-31 | 2021-03-26 | 东南大学 | Liquid material with porous structure and preparation method thereof |
| CN111715031A (en) * | 2020-06-24 | 2020-09-29 | 江西师范大学 | Carbon dioxide absorption medium and optimization process thereof |
| WO2023176583A1 (en) * | 2022-03-15 | 2023-09-21 | 国立大学法人九州大学 | Method and apparatus for producing synthesis gas containing carbon monoxide |
| CN115254032A (en) * | 2022-04-15 | 2022-11-01 | 中国辐射防护研究院 | Ionic liquid immobilized activated carbon and preparation method thereof |
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