CN106378110A - Preparation method of solid amino carbon dioxide capture material - Google Patents

Preparation method of solid amino carbon dioxide capture material Download PDF

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Publication number
CN106378110A
CN106378110A CN201610958740.5A CN201610958740A CN106378110A CN 106378110 A CN106378110 A CN 106378110A CN 201610958740 A CN201610958740 A CN 201610958740A CN 106378110 A CN106378110 A CN 106378110A
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hollow ball
adsorbent
ethanol
silica hollow
amine
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肖福魁
薛光信
赵宁
李磊
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • 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

Abstract

The invention relates to a preparation method of a solid amino carbon dioxide capture material. The method comprises the following steps: carrying out hydrothermal reaction on a glucose solution to prepare carbon spheres, dissolving the carbon spheres, cetyl trimethylammonium bromide and tetraethyl orthosilicate in a methanol-ethanol mixed solution, adding stronger ammonia water to react, filtering, roasting to prepare silicon oxide hollow spheres, adding the silicon oxide hollow spheres into an organic amine-ethanol mixed solution or a surfactant-organic amine-ethanol mixed solution, and drying to obtain the silicon-oxide-hollow-sphere-carried amine-type adsorbent. The method has the advantages of accessible raw materials, low price, mild preparation conditions, simple steps and high efficiency, and can implement large-scale production.

Description

A kind of preparation method of solid amine base carbon dioxide capture material
Technical field
The invention belongs to a kind of preparation method of solid amine base carbon dioxide capture material
Background technology
Since the industrial revolution, a large amount of combustion of fossil fuels of mankind's activity leads to carbon dioxide content in air persistently to rise High.As a kind of " greenhouse gases ", it is to the contribution rate of greenhouse effects more than 70% for carbon dioxide.Greenhouse effects cause the whole world Climate warming, EI Nino phenomenon takes place frequently, and threatens human survival, and the content therefore reducing carbon dioxide in air becomes people's day Beneficial focus of attention.Collecting carbonic anhydride, seal up for safekeeping and utilize technology, can directly, effectively reduce carbon dioxide in flue gas, It is predicted that contribution more and more higher that can be within coming few decades to carbon dioxide discharge-reduction, it has also become the emphasis of current various countries research. At present the capture technique of comparative maturity is liquid amine absorption process, but its major defect to be regeneration energy consumption big, amine substance easily loses Live, and serious to equipment corrosion.And solid amine absorption agent adsorption capacity is high, selectivity is good and can overcome lacking of liquid amine absorption process Point.Shubin Yang etc. is prepared for Sanming City with graphene oxide/mesopore silicon oxide stratiform material for carrier loaded polyethyleneimine Control type carbon dioxide absorber.This type sorbing material has good thermal conductance, and polyethyleneimine load capacity is high, and flake structure has Help carbon dioxide in material surface diffusion, absorption, be conducive to heat transfer.75 DEG C, under 100kPa carbon dioxide partial pressure conditions, should Adsorbent maximum adsorption capacity is 3.9mmol-CO2/ g- adsorbent, and show higher stability.(Yang,S.；Zhan, L.；Xu,X.；Wang,Y.；Ling,L.；Feng, X., advanced material 2013,25 (15), 2130-2134.) Sanz, Ra ú l etc. adopts With the difunctional method of grafting-dipping, it is prepared for amine modification reaming SBA-15 adsorbent.Due to grafting-type ammonia functional group and dipping class amine Synergy between material, 45 DEG C, under 0.15bar carbon dioxide bias condition, difunctional amine absorber carbon dioxide loaded Amount is up to 5.34mmol-CO2/ g- adsorbent.(Sanz,R.；Calleja,G.；Arencibia,A.；Sanz-Pérez,E.S., Materials chemistry A 2013,1 (6), 1956.) but solid-state amine sorbent circulation stability is poor, and adsorbent preparation process is complicated Or needing expensive raw material and template agent, loaded amine utilization rate is low, adsorbent carbon dioxide adsorption capacity, adsorption dynamics adsorption kinetics speed Need to be improved further.
At present, the difficult point of absorption method popularization and application is that the selection of high-performance adsorbent is prepared with extensive.Therefore, study Develop new and effective carbon dioxide absorber, significant.
Content of the invention
The purpose of the present invention is that a kind of raw material is easy to get, and price is low, and preparation condition is gentle, and step is simple, can be mass-produced, The preparation method of efficient solid amine carbon dioxide absorber.
The present invention uses the cheap raw materials such as glucose, using masterplate method, is prepared for meso-porous nano oxidation in a mild condition Silicon hollow ball.Then adopt simple infusion process, by the amine substances such as TEPA, pentaethylene hexamine, polyethyleneimine and ten Six alkyl trimethyl ammonium bromides (CTAB), PEO-PPOX-PEO triblock copolymer (P123), The surfactant load such as polyethylene glycol (PEG), on oxide hollow sphere, are prepared for carbon dioxide absorber.Prepare this absorption Agent is easy to get using raw material, and price is low, and preparation condition is gentle, and step is simple, and therefore this invention has stronger novelty and big rule Mould prepares feasibility.
The specific preparation method of the present invention, comprises the steps:
(1) configuration concentration is the glucose solution of 1～4M, moves in reactor containing teflon-lined, 150～ Hydro-thermal reaction 10～20h under the conditions of 180 DEG C, prepares carbon ball；
(2) by carbon ball, cetyl trimethylammonium bromide, it is molten with the mixing of ethanol that tetraethyl orthosilicate priority is dissolved in methyl alcohol Liquid (methyl alcohol:Ethanol volume ratio is 1:1～3), in, add concentrated ammonia liquor, stirring reaction 12～24h, filter, 500～600 DEG C of roastings Burn 3～6h, prepare silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 10～20:1～2:1～4:400:10～20；
(3) in the mixed solution adding organic amine to form with ethanol silica hollow ball, stirring 1～2h, 80～100 DEG C Dry 24～48h, prepared silica hollow ball loads amine type adsorbent, is named as SX-AYType adsorbent, wherein silica are hollow Ball:Organic amine:Ethanol mass ratio is 10:10～50:100；
Or silica hollow ball is added to surfactant, in organic amine and the mixed solution of ethanol composition, stirring 1～ 2h, 80～100 DEG C of drying 24～48h, prepared silica hollow ball loads amine type adsorbent, wherein silica hollow ball:Surface Activating agent:Organic amine:The mass ratio of ethanol is 10:1～6:10～50:100, it is named as SX-AY-BZType adsorbent.
Organic amine as above is TEPA (TEPA), pentaethylene hexamine (PEHA) or polyethyleneimine (PEI).
Surfactant as above is cetyl trimethylammonium bromide (CTAB), PEO-polycyclic oxygen third Alkane-PEO triblock copolymer (P123) or polyethylene glycol (PEG).
Adsorbent composition is as follows:
SX-AYType adsorbent, wherein SXFor silica hollow ball, A is organic amine, and Y is quality in adsorbent for the organic amine Percentage, Y:50～83wt.%.
SX-AY-BZType adsorbent, wherein SXFor silica hollow ball, A is organic amine, and Y is organic amine in adsorbent Mass percent, B be surfactant, Z be mass percent in adsorbent for the surfactant, Y:70～78wt.%, Z:2～10wt.%.
Silica hollow ball nature parameters:Specific surface area 800～1400m2g-1, mesoporous pore size 2～3nm, particle diameter 400～ 900nm, thickness of the shell is 20～90nm.
The application of the adsorbent of present invention preparation, comprises the steps:
Adsorbent is first in normal pressure, air speed 5000～6000mL g-1h-1, under the conditions of T=80～120 DEG C, it is desorbed 2 with nitrogen ～3h；Again in normal pressure, air speed 3000～4000mL g-1h-1, to CO under the conditions of T=30～100 DEG C2Volume content be 14～ 16% flue gas carries out adsorbing 2～3h.
The present invention compared with prior art has the advantage that:
1) this sorbent preparation method is simple, and raw material is cheap and easy to get, and and performance reproducibility is good it is easy to operation, easily real Existing industry is amplified.
2) hollow ball cavity has larger volume, can improve amine load capacity, and mesoporous material is worked in coordination with amine substance and made With improving CO2Adsorption capacity.
3) hollow mesoporous material has suitable particle diameter size and thickness of the shell, both can ensure that the structural stability of material, and Be conducive to CO2Diffusion, improve adsorption dynamics adsorption kinetics.
4) add a small amount of surfactant in adsorbent, not only improve CO2Diffusion, the CO of sorbing material can be improved again2 Load capacity.
Specific embodiment
Embodiment 1. configuration concentration is the glucose solution of 1M, moves in reactor containing teflon-lined, 150 DEG C Under the conditions of hydro-thermal reaction 10h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:1), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 500 DEG C Roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S1.By silica hollow ball add TEPA with In the mixed solution of ethanol composition, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball loads amine type adsorbent, wherein Silica hollow ball:TEPA:Ethanol mass ratio is 10:10:100, it is named as S1-TEPA50Type adsorbent.
S1-TEPA50In type adsorbent, the mass percent of organic amine TEPA is 50wt.%.Silica hollow ball S1Property Parameter：Specific surface area 800m2g-1, mesoporous pore size 2nm, particle diameter 400nm, thickness of the shell is 20nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 100 DEG C, air speed 5000mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 14%, other are N2), T=80 DEG C, flow velocity 4000mL g-1h-1, adsorb 2h, carbon dioxide infrared spectrum analyser on-line checking tail Gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 2. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 160 DEG C Under the conditions of hydro-thermal reaction 12h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:2), in, add concentrated ammonia liquor, stirring reaction 12h, filter, 520 DEG C Roasting 3h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 12:1.2:1:400:12, it is named as S2.Silica hollow ball is added TEPA In the mixed solution of ethanol composition, stir 1h, 80 DEG C of drying 28h, prepared silica hollow ball loads amine type adsorbent, wherein Silica hollow ball:TEPA:Ethanol mass ratio is 10:10:100, it is named as S2-TEPA50Type adsorbent.
S2-TEPA50In type adsorbent, the mass percent of organic amine TEPA is 50wt.%.Silica hollow ball S2Property Parameter：Specific surface area 860m2g-1, mesoporous pore size 2.5nm, particle diameter 400nm, thickness of the shell is 40nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 80 DEG C, air speed 5300mL g-1h-1 Lower desorption 2.4h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=30 DEG C, flow velocity 3300mL g-1h-1, adsorb 3h, carbon dioxide infrared spectrum analyser on-line checking tail Gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 3. configuration concentration is the glucose solution of 3M, moves in reactor containing teflon-lined, 170 DEG C Under the conditions of hydro-thermal reaction 15h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:1.5), in, add concentrated ammonia liquor, stirring reaction 16h, filter, 550 DEG C roasting 4h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methyl alcohol/second Mixed alkoxide solution:Concentrated ammonia liquor mass ratio is 14:1.4:1:400:14, it is named as S3.Silica hollow ball is added four ethene five In the mixed solution that amine is formed with ethanol, stir 1.4h, 85 DEG C of drying 32h, prepared silica hollow ball loads amine type adsorbent, Wherein silica hollow ball:TEPA:Ethanol mass ratio is 10:10:100, it is named as S3-TEPA50Type adsorbent.
S3-TEPA50In type adsorbent, the mass percent of organic amine TEPA is 50wt.%.Silica hollow ball S3Property Parameter：Specific surface area 1400m2g-1, mesoporous pore size 3nm, particle diameter 600nm, thickness of the shell is 20nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 120 DEG C, air speed 5600mL g-1 h-1Lower desorption 2.6h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume contains Measure as 16%, other are N2), T=100 DEG C, flow velocity 3600mL g-1h-1, adsorb 2.8h, carbon dioxide infrared spectrum analyser is online Detection tail gas composition (similarly hereinafter).Acquired results are as follows：
Embodiment 4. configuration concentration is the glucose solution of 4M, moves in reactor containing teflon-lined, 180 DEG C Under the conditions of hydro-thermal reaction 20h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:3), in, add concentrated ammonia liquor, stirring reaction 20h, filter, 600 DEG C Roasting 5h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 18:1.8:1:400:18, it is named as S4.Silica hollow ball is added TEPA In the mixed solution of ethanol composition, stir 1.8h, 90 DEG C of drying 36h, prepared silica hollow ball loads amine type adsorbent, its Middle silica hollow ball:TEPA:Ethanol mass ratio is 10:10:100, it is named as S4-TEPA50Type adsorbent.
S4-TEPA50In type adsorbent, the mass percent of organic amine TEPA is 50wt.%.Silica hollow ball S4Property Parameter：Specific surface area 1000m2g-1, mesoporous pore size 2.6nm, particle diameter 900nm, thickness of the shell is 30nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 90 DEG C, air speed 6000mL g-1h-1 Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content is 15.5%, other are N2), T=40 DEG C, flow velocity 4000mL g-1h-1, adsorb 2.5h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 5. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 150 DEG C Under the conditions of hydro-thermal reaction 10h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:3), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 600 DEG C Roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 10:1:2:400:10, it is named as S5.By silica hollow ball add pentaethylene hexamine with In the mixed solution of ethanol composition, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball loads amine type adsorbent, wherein Silica hollow ball:Pentaethylene hexamine:Ethanol mass ratio is 10:30:100, it is named as S5-PEHA75Type adsorbent.
S5-PEHA75In type adsorbent, the mass percent of organic amine PEHA is 75wt.%.Silica hollow ball S5Property Parameter：Specific surface area 900m2g-1, mesoporous pore size 2.3nm, particle diameter 600nm, thickness of the shell is 80nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 100 DEG C, air speed 5500mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=75 DEG C, flow velocity 3500mL g-1h-1, adsorb 2.9h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 6. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 150 DEG C Under the conditions of hydro-thermal reaction 10h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:2), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 550 DEG C Roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 10:1:3:400:10, it is named as S6.By silica hollow ball add pentaethylene hexamine with In the mixed solution of ethanol composition, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball loads amine type adsorbent, wherein Silica hollow ball:Pentaethylene hexamine:Ethanol mass ratio is 10:30:100, it is named as S6-PEHA75Type adsorbent.
S6-PEHA75In type adsorbent, the mass percent of organic amine PEHA is 75wt.%.Silica hollow ball S6Property Parameter：Specific surface area 1100m2g-1, mesoporous pore size 3nm, particle diameter 600nm, thickness of the shell is 90nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 105 DEG C, air speed 5100mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 14%, other are N2), T=85 DEG C, flow velocity 3900mL g-1h-1, adsorb 2.1h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 7. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 150 DEG C Under the conditions of hydro-thermal reaction 10h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:2.5), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 550 DEG C roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methyl alcohol/second Mixed alkoxide solution:Concentrated ammonia liquor mass ratio is 10:1:4:400:10, it is named as S7.Silica hollow ball is added pentaethylene hexamine In the mixed solution of ethanol composition, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball loads amine type adsorbent, its Middle silica hollow ball:Pentaethylene hexamine:Ethanol mass ratio is 10:30:100, it is named as S7-PEHA75Type adsorbent.
S7-PEHA75In type adsorbent, the mass percent of organic amine PEHA is 75wt.%.Silica hollow ball S7Property Parameter：Specific surface area 1300m2g-1, mesoporous pore size 2nm, particle diameter 900nm, thickness of the shell is 90nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 105 DEG C, air speed 5200mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 14.5%, other are N2), T=77 DEG C, flow velocity 3950mL g-1h-1, adsorb 2h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 8. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 160 DEG C Under the conditions of hydro-thermal reaction 16h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:3), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 550 DEG C Roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S8.By silica hollow ball add polyethyleneimine with In the mixed solution of ethanol composition, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball loads amine type adsorbent, wherein Silica hollow ball:Polyethyleneimine:Ethanol mass ratio is 10:20:100, it is named as S8-PEI66Type adsorbent.
S8-PEI66In type adsorbent, the mass percent of organic amine PEI is 66wt.%.Silica hollow ball S8Property is joined Number：Specific surface area 1200m2g-1, mesoporous pore size 2.7nm, particle diameter 700nm, thickness of the shell is 30nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 110 DEG C, air speed 6000mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=60 DEG C, flow velocity 4000mL g-1h-1, adsorb 3h, carbon dioxide infrared spectrum analyser on-line checking tail Gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 9. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 160 DEG C Under the conditions of hydro-thermal reaction 12h, prepare carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in first Mixed solution (the methyl alcohol of alcohol/ethanol:Ethanol volume ratio is 1:3), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 550 DEG C Roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol Mixed solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S9.By silica hollow ball add polyethyleneimine with In the mixed solution of ethanol composition, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball loads amine type adsorbent, wherein Silica hollow ball:Polyethyleneimine:Ethanol mass ratio is 10:40:100, it is named as S9-PEI80Type adsorbent.
S9-PEI80In type adsorbent, the mass percent of organic amine PEI is 80wt.%.Silica hollow ball S9Property is joined Number：Specific surface area 1300m2g-1, mesoporous pore size 2.2nm, particle diameter 700nm, thickness of the shell is 60nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 120 DEG C, air speed 5900mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15.5%, other are N2), T=75 DEG C, flow velocity 4000mL g-1h-1, adsorb 2.3h, carbon dioxide infrared spectrum analyser is examined online Survey tail gas composition (similarly hereinafter).Acquired results are as follows：
Embodiment 10. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 180 Hydro-thermal reaction 10h under the conditions of DEG C, prepares Nano carbon balls.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate is successively It is dissolved in the mixed solution (methyl alcohol of methanol/ethanol:Ethanol volume ratio is 1:3), in, concentrated ammonia liquor, stirring reaction 24h, mistake are added Filter, 580 DEG C of roasting 6h, prepare silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:First Alcohol/alcohol mixed solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S10.Silica hollow ball is added polyethylene In the mixed solution that imines is formed with ethanol, stir 2h, 100 DEG C of drying 24h, prepared silica hollow ball load amine type absorption Agent, wherein silica hollow ball:Polyethyleneimine:Ethanol mass ratio is 10:50:100, it is named as S10-PEI83Type adsorbent.
S10-PEI83In type adsorbent, the mass percent of organic amine PEI is 83wt.%.Silica hollow ball S10Property Parameter：Specific surface area 1230m2g-1, mesoporous pore size 2.7nm, particle diameter 900nm, thickness of the shell is 80nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 105 DEG C, air speed 5800mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=74 DEG C, flow velocity 3700mL g-1h-1, adsorb 2.4h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 11. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 180 Hydro-thermal reaction 10h under the conditions of DEG C, prepares Nano carbon balls.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate is successively It is dissolved in the mixed solution (methyl alcohol of methanol/ethanol:Ethanol volume ratio is 1:3), in, concentrated ammonia liquor, stirring reaction 24h, mistake are added Filter, 580 DEG C of roasting 6h, prepare silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:First Alcohol/alcohol mixed solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S10.Silica hollow ball is added hexadecane Base trimethylammonium bromide, in the mixed solution that pentaethylene hexamine is formed with ethanol, stirs 2h, 100 DEG C of drying 24h, oxidation is obtained Silicon hollow ball loads amine type adsorbent, wherein silica hollow ball:Cetyl trimethylammonium bromide:Pentaethylene hexamine:Ethanol Mass ratio is 10:1:39:100, it is named as S10-PEHA78-CTAB2Type adsorbent.
S10-PEHA78-CTAB2In type adsorbent, the mass percent 78wt.% of organic amine PEHA, the percent mass of CTAB Number is 2wt.%.Silica hollow ball S10Nature parameters：Specific surface area 1050m2g-1, mesoporous pore size 3nm, particle diameter 900nm, shell Thickness is 65nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 100 DEG C, air speed 5000mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=75 DEG C, flow velocity 4000mL g-1h-1, adsorb 2.4h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 12. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 180 Hydro-thermal reaction 10h under the conditions of DEG C, prepares carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in Mixed solution (the methyl alcohol of methanol/ethanol:Ethanol volume ratio is 1:3), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 600 DEG C roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methyl alcohol/second Mixed alkoxide solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S11.By silica hollow ball add PEO- PPOX-PEO triblock copolymer, in the mixed solution that pentaethylene hexamine is formed with ethanol, stirs 1.2h, 85 DEG C of drying 48h, prepared silica hollow ball loads amine type adsorbent, wherein silica hollow ball:PEO-polycyclic oxygen Propane-PEO triblock copolymer:Pentaethylene hexamine:Ethanol mass ratio is 10:2:38:100, it is named as S11- PEHA76-P1234Type adsorbent.
S11-PEHA76-P1234In type adsorbent, the mass percent of PEHA is 76wt.%, the matter of surfactant P123 Amount percentage is 4wt.%.Silica hollow ball S11Nature parameters：Specific surface area 1100m2g-1, mesoporous pore size 2.4nm, particle diameter 700nm, thickness of the shell is 40nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 104 DEG C, air speed 6000mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 16%, other are N2), T=85 DEG C, flow velocity 4000mL g-1h-1, adsorb 2.5h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 13. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 180 Hydro-thermal reaction 10h under the conditions of DEG C, prepares carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in Mixed solution (the methyl alcohol of methanol/ethanol:Ethanol volume ratio is 1:3), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 600 DEG C roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methyl alcohol/second Mixed alkoxide solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S11.By silica hollow ball add polyethylene glycol, five In the mixed solution that hexamine is formed with ethanol, stir 1.6h, 90 DEG C of drying 36h, prepared silica hollow ball loads amine type Adsorbent, wherein silica hollow ball:Polyethylene glycol:Pentaethylene hexamine:Ethanol mass ratio is 10:4:36:100, it is named as S11- PEHA72-PEG8Type adsorbent.
S11-PEHA72-PEG8In type adsorbent, the mass percent of organic amine PEHA is 72wt.%, Surfactant PEG Mass percent be 8wt.%.Silica hollow ball S11Nature parameters：Specific surface area 1100m2g-1, mesoporous pore size 2.4nm, Particle diameter 700nm, thickness of the shell is 40nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 115 DEG C, air speed 5900mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=70 DEG C, flow velocity 3800mL g-1h-1, adsorb 2.5h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
Embodiment 14. configuration concentration is the glucose solution of 2M, moves in reactor containing teflon-lined, 180 Hydro-thermal reaction 10h under the conditions of DEG C, prepares carbon ball.By carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in Mixed solution (the methyl alcohol of methanol/ethanol:Ethanol volume ratio is 1:2), in, add concentrated ammonia liquor, stirring reaction 24h, filter, 600 DEG C roasting 6h, prepares silica hollow ball, wherein carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methyl alcohol/second Mixed alkoxide solution:Concentrated ammonia liquor mass ratio is 10:1:1:400:10, it is named as S11.By silica hollow ball add polyethylene glycol, five In the mixed solution that hexamine is formed with ethanol, stir 1.7h, 95 DEG C of drying 40h, prepared silica hollow ball loads amine type Adsorbent, wherein silica hollow ball:Polyethylene glycol:Pentaethylene hexamine:Ethanol mass ratio is 10:5:35:100, it is named as S11- PEHA70-PEG10Type adsorbent.
S11-PEHA70-PEG10In type adsorbent, the mass percent of organic amine PEHA is 70wt.%, surfactant The mass percent of PEG is 10wt.%.Silica hollow ball S11Nature parameters：Specific surface area 1100m2g-1, mesoporous pore size 2.4nm, particle diameter 700nm, thickness of the shell is 40nm.
Carry out CO in fixed bed reactors2Absorption, before reaction adsorbent with nitrogen at 100 DEG C, air speed 6000mL g-1 h-1Lower desorption 2h, switches to CO2/N2Gaseous mixture adsorbed, adsorption conditionses are：Simulated flue gas (wherein CO2Volume content For 15%, other are N2), T=75 DEG C, flow velocity 4000mL g-1h-1, adsorb 2.5h, carbon dioxide infrared spectrum analyser on-line checking Tail gas forms (similarly hereinafter).Acquired results are as follows：
In sum, oxide hollow sphere mesoporous material load amine type adsorbent has preferable selectivity to carbon dioxide And higher adsorption capacity, by the regulation to preparation condition, the more excellent adsorbent of performance can be prepared.Hollow-core construction Presence can improve the load capacity of amine substance, relatively thin wall thickness can improve CO2Adsorption desorption dynamics, surfactant Adding the then raising to adsorption capacity and adsorption dynamics adsorption kinetics speed has facilitation.It is experimentally confirmed, this sorbent systems Generally there is to carbon dioxide higher selection performance, its adsorption capacity can reach about 5.40mmol/g.By literature search, Do not meet similar sorbent systems report, belong to innovative works.

Claims (8)

1. a kind of preparation method of solid amine base carbon dioxide capture material is it is characterised in that comprise the steps：
(1) configuration concentration is the glucose solution of 1～4M, moves in reactor containing teflon-lined, 150～180 DEG C Under the conditions of hydro-thermal reaction 10～20h, prepare carbon ball；
(2) by carbon ball, cetyl trimethylammonium bromide, tetraethyl orthosilicate priority is dissolved in the mixed solution of methyl alcohol and ethanol In, add concentrated ammonia liquor, stirring reaction 12～24h, filter, 500～600 DEG C of roasting 3～6h, prepare silica hollow ball, its Middle carbon ball:Cetyl trimethylammonium bromide:Tetraethyl orthosilicate:Methanol/ethanol mixed solution:Concentrated ammonia liquor mass ratio be 10～ 20:1～2:1～4:400:10～20；
(3), in the mixed solution adding organic amine to form with ethanol silica hollow ball, 1～2h, 80～100 DEG C of drying are stirred 24～48h, prepared silica hollow ball loads amine type adsorbent, is named as SX-AYType adsorbent, wherein silica hollow ball:Have Machine amine:Ethanol mass ratio is 10:10～50:100；
Or silica hollow ball is added to surfactant, in the mixed solution that organic amine is formed with ethanol, stir 1～2h, 80～100 DEG C of drying 24～48h, prepared silica hollow ball loads amine type adsorbent, wherein silica hollow ball:Surface-active Agent:Organic amine:The mass ratio of ethanol is 10:1～6:10～50:100, it is named as SX-AY-BZType adsorbent.
2. as claimed in claim 1 a kind of preparation method of solid amine base carbon dioxide capture material it is characterised in that described Organic amine be TEPA, pentaethylene hexamine or polyethyleneimine.
3. as claimed in claim 1 a kind of preparation method of solid amine base carbon dioxide capture material it is characterised in that described Surfactant be cetyl trimethylammonium bromide, PEO-PPOX-PEO triblock copolymer Thing or polyethylene glycol (.
4. as claimed in claim 1 a kind of preparation method of solid amine base carbon dioxide capture material it is characterised in that mixing Methyl alcohol in solution:Ethanol volume ratio is 1:1～3.
5. the S as described in any one of claim 1-4X-AYType adsorbent is it is characterised in that SX-AYS in type adsorbentXFor oxidation Silicon hollow ball, A is organic amine, and Y is mass percent in adsorbent for the organic amine, Y:50～83wt%, silica hollow ball Nature parameters:Specific surface area 800～1400m2g-1, mesoporous pore size 2～3nm, particle diameter 400～900nm, thickness of the shell be 20～ 90nm.
6. the S as described in any one of claim 1-4X-AY-BZType adsorbent is it is characterised in that SX-AY-BZS in type adsorbentXFor Silica hollow ball, A is organic amine, and Y is mass percent in adsorbent for the organic amine, and B is surfactant, and Z is table Mass percent in adsorbent for the face activating agent, Y:70～78wt%, Z:2～10wt%, silica hollow ball nature parameters: Specific surface area 800～1400m2g-1, mesoporous pore size 2～3nm, particle diameter 400～900nm, thickness of the shell is 20～90nm.
7. S as claimed in claim 5X-AYThe application of type adsorbent is it is characterised in that comprise the steps：
Adsorbent is first in normal pressure, air speed 5000～6000mL g-1h-1, under the conditions of T=80～120 DEG C, 2～3h is desorbed with nitrogen；Again In normal pressure, air speed 3000～4000mL g-1h-1, to CO under the conditions of T=30～100 DEG C2Volume content is 14～16% flue Gas carries out adsorbing 2～3h.
8. S as claimed in claim 6X-AY-BZThe application of type adsorbent is it is characterised in that comprise the steps：
Adsorbent is first in normal pressure, air speed 5000～6000mL g-1h-1, under the conditions of T=80～120 DEG C, 2～3h is desorbed with nitrogen；Again In normal pressure, air speed 3000～4000mL g-1h-1, to CO under the conditions of T=30～100 DEG C2Volume content is 14～16% flue Gas carries out adsorbing 2～3h.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106861631A (en) * 2017-02-27 2017-06-20 苏州大学 Hollow mesoporous silicon dioxide nano microballoon of functionalization and preparation method thereof and the application in Adsorption of Heavy Metals ion
CN108636378A (en) * 2018-05-03 2018-10-12 淮北师范大学 A kind of organic amino-functionalization There-dimensional ordered macroporous materials CO2Adsorbent and preparation method thereof
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CN109821517A (en) * 2019-04-09 2019-05-31 乐清市智格电子科技有限公司 A kind of particle nanomicroporous material and preparation method thereof
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CN113000030A (en) * 2021-03-03 2021-06-22 王华兵 Carbon dioxide adsorbent and preparation method thereof
CN113509903A (en) * 2020-04-09 2021-10-19 石河子大学 Photostimulation response type material and preparation method and application thereof
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102500324A (en) * 2011-10-08 2012-06-20 中国科学院山西煤炭化学研究所 Organic-inorganic composite carbon dioxide adsorbing material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102500324A (en) * 2011-10-08 2012-06-20 中国科学院山西煤炭化学研究所 Organic-inorganic composite carbon dioxide adsorbing material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIAGUO YU, ET AL.: "Fabrication and CO2 adsorption performance of bimodal porous silica hollow spheres with amine-modified surfaces", 《RSC ADVANCES》 *
JITONG WANG, ET AL.: "Surfactant promoted solid amines sorbents for CO2 capture", 《ENERGY & ENVIRONMENTAL SCIENCE》 *
RASOUL SAFDARI, ET AL.: "Synthesis of porous silica hollow spheres using sacrificial template for drug delivery applications", 《CURRENT CHEMISTRY LETTERS》 *

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