CN104258828A - Carbon dioxide adsorbent and preparation method thereof - Google Patents
Carbon dioxide adsorbent and preparation method thereof Download PDFInfo
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- CN104258828A CN104258828A CN201410491323.5A CN201410491323A CN104258828A CN 104258828 A CN104258828 A CN 104258828A CN 201410491323 A CN201410491323 A CN 201410491323A CN 104258828 A CN104258828 A CN 104258828A
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- hollow silica
- silica ball
- carbon dioxide
- carrier
- dioxide absorber
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003463 adsorbent Substances 0.000 title abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 78
- 239000004793 Polystyrene Substances 0.000 claims abstract description 35
- 229920002223 polystyrene Polymers 0.000 claims abstract description 34
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005576 amination reaction Methods 0.000 claims abstract description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 239000006096 absorbing agent Substances 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 239000004475 Arginine Substances 0.000 claims description 34
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 229920002521 macromolecule Polymers 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 21
- 150000001412 amines Chemical class 0.000 abstract description 21
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 229920000724 poly(L-arginine) polymer Polymers 0.000 abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000002336 sorption--desorption measurement Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000003795 desorption Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- -1 compound carbon dioxide Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002627 poly(phosphazenes) Polymers 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Classifications
-
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
-
- 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
-
- 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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention discloses a carbon dioxide solid amine adsorbent and a preparation method thereof. The adsorbent comprises a silicon dioxide hollow ball carrier with a large hole size (50nm-550nm) and linear poly-L-arginine (PLA) which is chemically bonded on the inner and outer surfaces of a hollow ball by an in situ polymerization manner. The specific preparation method comprises the following steps: (1) synthesizing the silicon dioxide hollow ball carrier by using tetraethoxysilane and polystyrene emulsion (PS); (2) carrying out amination on the surface of the hollow ball carrier with 3-aminopropyltrimethoxysilane; and (3) polymerizing PLA on the inner and outer surfaces of the hollow ball in situ by adopting the in situ polymerization manner. The adsorbent has the remarkable advantages of high adsorption-desorption speed, large adsorption capacity, good long-period stability and the like; the problems of corrosion and high energy consumption of a liquid ammonia adsorbent in current industry are solved; and the problems of the solid amine adsorbent that the long-period adsorptivity is poor and the adsorption capacity is low are also solved.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of carbon dioxide absorber and preparation method thereof.
Background technology
In recent decades, due in air with CO
2greenhouse gas concentration for representative continues to raise, CO
2catch to obtain with memory technology and develop fast.Ammonia absorption method carries out the method that large-scale industry GAS ABSORPTION commonly uses the most at present, but this method exists a lot of not enough, and such as: high energy consumption, strong to the corrosivity of equipment, absorptive capacity is low.In order to better improve these problems, scientists starts the research turning to solid absorbent, Small molecular ammonia or macromolecule ammonia is directly embedded in solid carrier (as mesoporous silicon, carbon, organic resin and other macromolecular material).With traditional liquefied ammonia Adsorption Phase ratio, solid amine adsorbent reactivation energy consumption is little, little to the corrosivity of equipment, and at CO
2acquisition procedure in have very high selective.In recent years, mesoporous silicon receives much concern owing to having in the larger heat endurance than table volume and the excellence more than ten years in the past, the multiplex carrier making organic solid ammonia adsorbent.
At present, there are three kinds of modes that ammonia is embedded in solid carrier.The first is traditional dipping method, namely porous silicon carrier is directly dipped in the solution of Small molecular ammonia (as TEPA) or macromolecule amine (polymine).The shortcoming of this mode is the combination of amine and silicon carrier is physical bond, and to live again adsorbent once employing heating, ammonia easily departs from by modes such as volatilizations, thus reduction performance of the adsorbent.As Chinese patent CN 201110147916.6 discloses a kind of mesoporous silica/organic matter compound carbon dioxide absorber, adopt dipping method to be embedded in mesoporous silicon by Small molecular ammonia or macromolecule amine, there is the shortcoming of long-term hidden qualitative difference.The second way is fixed on porous silicon carrier by small molecule amine by chemical mode, this investment fashion is because adopt chemical bond to connect, the stable connection of amine and carrier, but because amine molecule amount is less, adsorbent amine content is low, therefore adsorbance low (Ind.Eng.Chem.Res.2007,46,446-458).The third mode is the in-situ polymerization carrying out macromolecule amine on porous silicon carrier, the shortcoming of this adsorbent is, owing to adopting the hole of silicon carrier less, the branched polymer organic amine that polymerization is formed very easily blocks mesoporous, cause the degradation (Chem.Mater.2008 of adsorption capacity, 20,1126-1133).
For these reasons, find a kind of absorptive capacity large, absorption and desorption speed is fast, the novel C O that stability is high
2adsorbent becomes the problem that solution is needed in this field badly.In the application, by adopting the polystyrene microsphere of macropore yardstick (diameter >50nm) for sacrificing template, prepare (50 ~ 500nm) hollow silica ball carrier of macropore yardstick, can solve and use the susceptible to plugging defect of mesoporous yardstick carrier; Due to the existence of macropore yardstick three-dimensional channel, CO
2the attached speed of absorption and desorption is fast; Owing to adopting mode in-situ polymerization macromolecule amine on carrier of chemical bonding, the stability of gained adsorbent is high, and absorptive capacity is large.
In prior art, carbon dioxide absorber major part adopts physical method to be adsorbed on carrier macromolecule amine, and chemical method is less, and what we adopted is chemical method; Further, what adopt chemical method is generally be fixed on the carrier of mesoporous yardstick by macromolecule amine, and easy like this duct of causing blocks, and adsorption dynamics adsorption kinetics declines, and macromolecular material is fixed on the carrier of macropore yardstick by we; Further, and in the past the spongiform porous SiO of macropore yardstick is adopted
2carrier is different, eliminates the use of nitric acid in present invention process, thus the hollow ball carrier needed for preparation.
Described PLA is linear macromolecule, and by chemical bond and hollow silica ball carrier phase bonding, this macromolecule has no at CO
2use in adsorbent; PR is linear macromolecule, the abscess blocking that the right Gao Shiyi of branching type polyphosphazene polymer can be avoided to cause, the shortcoming that dynamic performance declines, in addition pR due to number amino in its structure many, so utilize it to do carbon dioxide absorber have larger carbon dioxide adsorption capacity.
CO in adsorbent Absorbable rod power-plant flue gas and air
2gas, adsorption temp is 25-75 DEG C, and desorption temperature is 110 DEG C.
Compared with prior art, advantage of the present invention is:
(1) by chemistry polymerizing in situ mode, gained macromolecule ammonia is connected to hollow ball SiO by chemical bond mode
2surfaces externally and internally, solve the problem of long-time stability difference that existing physical absorption exists;
(2) compare with the silicon carrier of mesoporous yardstick, adopt the silicon carrier of macropore yardstick (diameter 50 ~ 550nm) effectively can increase the molecular weight of organic amine, eliminate the molecular weight restriction effect that mesoporous yardstick carrier exists, improve adsorption capacity, efficiently solve the problem that the capacity of current chemisorbed existence is low;
(3) by adopting the PLA molecule of line style, can solve branching type polyphosphazene polymer right high time cause sorption channel blocking, adsorption rate is slow, adsorption cycle is long problem.Therefore, this adsorbent has CO
2absorptive capacity is large, and absorption-desorption rate is fast, stability high.
In sum, a kind of novel carbon dioxide absorber provided by the present invention, has stability high, the advantages such as capacity is large.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art, seek design and a kind of solid amine carbon dioxide absorber and preparation method thereof is provided.Adsorbent provided by the present invention has the advantages such as stable, adsorbance large, absorption and desorption speed is fast.
To achieve these goals, the technical solution adopted in the present invention is:
A kind of carbon dioxide absorber, do carrier by the amidized hollow silica ball of surfaces externally and internally, line style pR (PLA) is fixed on the surfaces externally and internally of carrier by chemical bond with the form of in-situ polymerization.A preparation method for silica, utilizes amination reagent, by the surfaces externally and internally amination of hollow silica ball carrier, then adopts the mode of in-situ polymerization at the surfaces externally and internally polymerization PLA of hollow ball, namely obtains carbon dioxide absorber.
Described aminating agent is selected from, 3-aminopropyl trimethoxy silicon;
The aperture of described hollow silica ball is 50 ~ 550nm; When aperture is lower than 50nm, after high molecular polymerization, easily cause hole to block, reduce adsorption dynamics adsorption kinetics; And aperture is excessive, when being such as greater than 550nm, the specific area of adsorbent then declines too much, and adsorption capacity is reduced.
Described PLA is linear macromolecule; By adopting the PLA molecule of line style, can solve branching type polyphosphazene polymer right high time the sorption channel blockage problem that causes, the adsorption rate existed when solving amine molecule amount height is further slow, the problem that adsorption cycle is long.
Concrete steps are as follows:
1) preparation of hollow silica ball carrier: add ethyl orthosilicate in vial, polystyrene emulsion suspension, gained mixture continual ultrasonic 2 hours, then centrifugation, after overnight at room temperature drying, by polystyrene moulding by calcining removing;
The concentration of described polystyrene emulsion suspension is 2.5wt% ~ 2.62wt%;
The concentration of preferred polystyrene emulsion suspension is 2.60wt%;
Described ethyl orthosilicate with the volumetric usage ratio of polystyrene emulsion suspension is: 100:1 ~ 70:1;
Preferred ethyl orthosilicate is 85:1 with the volumetric usage ratio of polystyrene emulsion suspension;
2) amination of hollow silica ball: by step 1) hollow silica ball prepared at 100 DEG C of vacuum drying 12h, then add dry toluene and 3-aminopropyl trimethoxy silicon, mixture at room temperature stirred 24 hours; By gained solid product toluene, methyl alcohol, methanol/water volume ratio is that the mixture of 1:1 and methyl alcohol wash successively, and dry at 50 DEG C, vacuum, namely obtains amidized hollow silica ball carrier;
The mass ratio of described dry toluene and hollow silica ball carrier is 35:1;
The mass ratio of described hollow silica ball carrier and 3-aminopropyl trimethoxy silicon is 7:1;
3) preparation of carbon dioxide absorber: get step 2) the amidized hollow silica ball carrier prepared, be dissolved in N-carboxyl inner-acid anhydride arginine solution, stir 48 hours at 50 DEG C, centrifugation obtains powder, powder THF, DMF and chloroform are washed successively, by dry at 40 DEG C for the solids obtained, namely obtain carbon dioxide absorber, store in 40 DEG C of baking ovens;
N-carboxyl inner-acid anhydride arginine, as polymerization single polymerization monomer, utilizes the amine of silicon ball surfaces externally and internally grafting to be polymerized as initator, has synthesized PLA;
The concentration of described N-carboxyl inner-acid anhydride arginine solution is 0.2mol/L;
Described N-carboxyl inner-acid anhydride arginine foundation Master's thesis " preparation and property of biodegradable environmental response polymer ", Duan Pengxue, Northwest Normal University; The method preparation provided;
Described N-carboxyl inner-acid anhydride arginine is 20:1 ~ 80:1 with the mol ratio ratio of amidized hollow silica ball carrier.
Accompanying drawing explanation
Absorption-desorption cycle the process of the adsorbent of Fig. 1 SH-LA-60 and SH-LA-80 two type;
The scanning electron microscopic picture of the hollow silica ball carrier of preparation in Fig. 2 embodiment 1;
Fig. 3 PLA is at SiO
2hollow ball in situ Polymerization schematic diagram;
English abbreviation lexical or textual analysis in the application:
PLA is pR, and arginine NCA is N-carboxyl inner-acid anhydride arginine, and THF is oxolane, and DMF is dimethyl formamide,
Detailed description of the invention
Below in conjunction with concrete embodiment, the present invention will be further explained.
Embodiment 1:
(1) preparation of hollow silica ball carrier: add ethyl orthosilicate 550mg and polystyrene emulsion suspension 6.96ml (diameter 526nm in the vial of 10ml, 2.62wt%), gained mixture continual ultrasonic is after 2 hours, centrifugal 40min under the rotating speed of 7000rmp, under room temperature after dry 12h, by polystyrene emulsion template in 600 DEG C of calcinings removing in 8 hours.Prepared hollow silica ball is expressed as SH.
(2) get 0.5g hollow silica ball carrier, vacuum and heating drying 12h at 100 DEG C, then add 30ml dry toluene and 3-aminopropyl trimethoxy silicon (0.398mmol), mixture is at room temperature stirred 24 hours.By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo.
(3) under nitrogen protection, in there-necked flask, benzyloxycarbonyl group arginine 13.2g and oxolane (THF) 50ml is added, Keep agitation, ice bath; In constant pressure funnel, add 2ml phosphorus tribromide and 8ml oxolane, be slowly added drop-wise to and be in the there-necked flask of ice bath, room temperature reaction 24 hours.Get layer oily matter, use a large amount of tetrafluoro furans to wash, arginine NCA can be obtained.Then the arginine NCA solution (20:1 monomers/initiator) of 37ml0.2M is joined 250ml to contain in the round-bottomed flask of silica supports.Mixture is stirred 48 hours at 50 DEG C.Gained powder is carried out centrifugation, and with THF, DMF and the chloroform of 50ml.The composite obtained is carried out drying, stores in 40 DEG C of baking ovens.The adsorbent of preparation is expressed as SH-LA-20, wherein the ratio of 20 monomers/initiator represented.
Embodiment 2
A kind of carbon dioxide absorber, do carrier by the amidized hollow silica ball of surfaces externally and internally, line style pR (PLA) is fixed on the surfaces externally and internally of carrier by chemical bond with the form of in-situ polymerization.
Prepare an a kind of method of carbon dioxide absorber, utilize amination reagent, by the surfaces externally and internally amination of hollow silica ball, then adopt the mode of in-situ polymerization at the surfaces externally and internally polymerization PLA of hollow ball, namely obtain carbon dioxide absorber;
Described amination reagent is selected from, 3-aminopropyl trimethoxy silicon;
The aperture of described hollow silica ball is 50nm;
Described PLA is linear macromolecule;
Concrete steps are as follows:
1) preparation of hollow silica ball carrier: add ethyl orthosilicate in vial, polystyrene emulsion suspension, gained mixture continual ultrasonic 2 hours, then centrifugation, after overnight at room temperature drying, by polystyrene emulsion template by calcining removing;
The concentration of described polystyrene emulsion suspension is 2.5wt%;
Described ethyl orthosilicate with the volumetric usage ratio of polystyrene emulsion suspension is: 100:1;
2) amination of hollow silica ball carrier: by step 1) the hollow silica ball carrier prepared 100 DEG C of vacuum drying a whole nights, then add dry toluene and 3-aminopropyl trimethoxy silicon, mixture at room temperature stirred 24 hours; By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo, namely obtain amidized hollow silica ball carrier;
The mass ratio of described dry toluene and hollow silica ball carrier is 35:1;
The mass ratio of described hollow silica ball carrier and 3-aminopropyl trimethoxy silicon is 7:1;
3) preparation of carbon dioxide absorber: get step 2) the amidized hollow silica ball carrier prepared, be dissolved in N-carboxyl inner-acid anhydride arginine solution, stir 48 hours at 50 DEG C, centrifugation obtains powder, powder THF, DMF and chloroform are washed successively, by dry at 40 DEG C for the solids obtained, namely obtain carbon dioxide absorber, store in 40 DEG C of baking ovens;
The concentration of described N-carboxyl inner-acid anhydride arginine solution is 0.2mol/L;
Described N-carboxyl inner-acid anhydride arginine foundation Master's thesis " preparation and property of biodegradable environmental response polymer ", Duan Pengxue, Northwest Normal University; The method preparation provided;
Described N-carboxyl inner-acid anhydride arginine and the mol ratio of amidized hollow silica ball carrier are 30:1, and prepared adsorbent is expressed as SH-LA-30.
Embodiment 3:
(1) preparation of hollow silica ball carrier: add ethyl orthosilicate 660mg and polystyrene emulsion suspension 8.35ml (diameter 526nm in the vial of 10ml, 2.62wt%), gained mixture continual ultrasonic is after 2 hours, centrifugal 40min under the rotating speed of 7000rmp, after overnight at room temperature drying, by polystyrene emulsion template in 600 DEG C of calcinings removing in 6 hours.
(2) get 0.6g hollow silica ball carrier, vacuum and heating drying a whole night at 100 DEG C, then add 36ml dry toluene and 3-aminopropyl trimethoxy silicon (0.478mmol), mixture is at room temperature stirred 24 hours.By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo.
(3) under nitrogen protection, in there-necked flask, benzyloxycarbonyl group arginine 13.2g and oxolane (THF) 50ml is added, Keep agitation, ice bath; In constant pressure funnel, add 2ml phosphorus tribromide and 8ml oxolane, be slowly added drop-wise to and be in the there-necked flask of ice bath, room temperature reaction 24 hours.Get layer oily matter, use a large amount of tetrafluoro furans to wash, arginine NCA can be obtained.Then the arginine NCA solution (40:1 monomers/initiator) of 74ml0.2M is joined 250ml to contain in the round-bottomed flask of silica supports.Mixture is stirred 48 hours at 50 DEG C.Gained powder is carried out centrifugation, and with THF, DMF and the chloroform of 50ml.The composite obtained is carried out drying, stores in 40 DEG C of baking ovens.The adsorbent of preparation is expressed as SH-LA-40, wherein the ratio of 40 monomers/initiator represented.
Embodiment 4
A kind of carbon dioxide absorber, do carrier by the amidized hollow silica ball of surfaces externally and internally, line style pR (PLA) is fixed on the surfaces externally and internally of carrier by chemical bond with the form of in-situ polymerization.
Prepare a method for carbon dioxide absorber, utilize amination reagent, by the surfaces externally and internally amination of hollow silica ball, then adopt the mode of in-situ polymerization at the surfaces externally and internally polymerization PLA of hollow ball, namely obtain carbon dioxide absorber;
Described amination reagent is selected from, 3-aminopropyl trimethoxy silicon;
The aperture of described hollow silica ball is 550nm;
Described PLA is linear macromolecule;
Concrete steps are as follows:
1) preparation of hollow silica ball carrier: add ethyl orthosilicate in vial, polystyrene emulsion suspension, gained mixture continual ultrasonic 2 hours, then centrifugation, after overnight at room temperature drying, by polystyrene emulsion template by calcining removing;
The concentration of described polystyrene emulsion suspension is 2.62wt%;
Described ethyl orthosilicate with the volumetric usage ratio of polystyrene emulsion suspension is: 70:1;
2) amination of hollow silica ball carrier: by step 1) the hollow silica ball carrier prepared 100 DEG C of vacuum drying a whole nights, then add dry toluene and 3-aminopropyl trimethoxy silicon, mixture at room temperature stirred 24 hours; By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo, namely obtain amidized hollow silica ball carrier;
The mass ratio of described dry toluene and hollow silica ball carrier is 35:1;
The mass ratio of described hollow silica ball carrier and 3-aminopropyl trimethoxy silicon is 7:1;
3) preparation of carbon dioxide absorber: get step 2) the amidized hollow silica ball carrier prepared, be dissolved in N-carboxyl inner-acid anhydride arginine solution, stir 48 hours at 50 DEG C, centrifugation obtains powder, powder THF, DMF and chloroform are washed successively, by dry at 40 DEG C for the solids obtained, namely obtain carbon dioxide absorber, store in 40 DEG C of baking ovens;
The concentration of described N-carboxyl inner-acid anhydride arginine solution is 0.2mol/L;
Described N-carboxyl inner-acid anhydride arginine foundation Master's thesis " preparation and property of biodegradable environmental response polymer ", Duan Pengxue, Northwest Normal University; The method preparation provided;
Described N-carboxyl inner-acid anhydride arginine and the mol ratio of amidized hollow silica ball carrier are 50:1, and prepared adsorbent is expressed as SH-LA-50.
Embodiment 5:
(1) preparation of hollow silica ball carrier: add ethyl orthosilicate 550mg and polystyrene emulsion suspension 6.96ml (diameter 526nm in the vial of 10ml, 2.62wt%), gained mixture continual ultrasonic is after 2 hours, centrifugal 40min under the rotating speed of 7000rmp, after overnight at room temperature drying, by polystyrene emulsion template in 650 DEG C of calcinings removing in 5 hours.
(2) get 0.5g hollow silica ball carrier, vacuum and heating drying a whole night at 110 DEG C, then add 40ml dry toluene and 3-aminopropyl trimethoxy silicon (0.398mmol), mixture is at room temperature stirred 24 hours.By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo.
(3) under nitrogen protection, in there-necked flask, benzyloxycarbonyl group arginine 13.2g and oxolane (THF) 50ml is added, Keep agitation, ice bath; In constant pressure funnel, add 2ml phosphorus tribromide and 8ml oxolane, be slowly added drop-wise to and be in the there-necked flask of ice bath, room temperature reaction 24 hours.Get layer oily matter, use a large amount of tetrafluoro furans to wash, arginine NCA can be obtained.Then the arginine NCA solution (60:1 monomers/initiator) of 111ml0.2M is joined 250ml to contain in the round-bottomed flask of silica supports.Mixture is stirred 48 hours at 60 DEG C.Gained powder is carried out centrifugation, and with THF, DMF and the chloroform of 50ml.The composite obtained is carried out drying, stores in 40 DEG C of baking ovens.The adsorbent of preparation is expressed as SH-LA-60, wherein the ratio of 60 monomers/initiator represented.
Embodiment 6
A kind of carbon dioxide absorber, do carrier by the amidized hollow silica ball of surfaces externally and internally, line style pR (PLA) is fixed on the surfaces externally and internally of carrier by chemical bond with the form of in-situ polymerization.
Prepare a method for carbon dioxide absorber, utilize amination reagent, by the surfaces externally and internally amination of hollow silica ball, then adopt the mode of in-situ polymerization at the surfaces externally and internally polymerization PLA of hollow ball, namely obtain carbon dioxide absorber;
Described amination reagent is selected from, 3-aminopropyl trimethoxy silicon;
The aperture of described hollow silica ball is 500nm;
Described PLA is linear macromolecule;
Concrete steps are as follows:
1) preparation of hollow silica ball carrier: add ethyl orthosilicate in vial, polystyrene emulsion suspension, gained mixture continual ultrasonic 2 hours, then centrifugation, after overnight at room temperature drying, by polystyrene emulsion template by calcining removing;
The concentration of described polystyrene emulsion suspension is 2.60wt%;
Described ethyl orthosilicate with the volumetric usage ratio of polystyrene emulsion suspension is: 80:1;
2) amination of hollow silica ball carrier: by step 1) the hollow silica ball carrier prepared 100 DEG C of vacuum drying a whole nights, then add dry toluene and 3-aminopropyl trimethoxy silicon, mixture at room temperature stirred 24 hours; By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo, namely obtain amidized hollow silica ball carrier;
The mass ratio of described dry toluene and hollow silica ball carrier is 35:1;
The mass ratio of described hollow silica ball carrier and 3-aminopropyl trimethoxy silicon is 7:1;
3) preparation of carbon dioxide absorber: get step 2) the amidized hollow silica ball carrier prepared, be dissolved in N-carboxyl inner-acid anhydride arginine solution, stir 48 hours at 50 DEG C, centrifugation obtains powder, powder THF, DMF and chloroform are washed successively, by dry at 40 DEG C for the solids obtained, namely obtain carbon dioxide absorber, store in 40 DEG C of baking ovens;
The concentration of described N-carboxyl inner-acid anhydride arginine solution is 0.2mol/L;
Described N-carboxyl inner-acid anhydride arginine foundation Master's thesis " preparation and property of biodegradable environmental response polymer ", Duan Pengxue, Northwest Normal University; The method preparation provided;
Described N-carboxyl inner-acid anhydride arginine and the mol ratio of amidized hollow silica ball carrier are 70:1, and prepared adsorbent is expressed as SH-LA-70.
Embodiment 7:
(1) preparation of hollow silica ball carrier: add ethyl orthosilicate 660mg and polystyrene emulsion suspension 8.35ml (diameter 50nm in the vial of 10ml, 2.5wt%), gained mixture continual ultrasonic is after 2 hours, centrifugal 40min under the rotating speed of 7000rmp, after overnight at room temperature drying, by polystyrene emulsion template 340 DEG C of calcinings 3 hours, then temper removing in 3 hours at 600 DEG C.
(2) get 0.6g hollow silica ball carrier, vacuum and heating drying a whole night at 100 DEG C, then add 36ml dry toluene and 3-aminopropyl trimethoxy silicon (0.478mmol), mixture is at room temperature stirred 24 hours.By gained solid product toluene, methyl alcohol, methanol/water (1:1) and methyl alcohol wash successively, and dry under vacuo.
(3) under nitrogen protection, in there-necked flask, benzyloxycarbonyl group arginine 13.2g and oxolane (THF) 50ml is added, Keep agitation, ice bath; In constant pressure funnel, add 2ml phosphorus tribromide and 8ml oxolane, be slowly added drop-wise to and be in the there-necked flask of ice bath, room temperature reaction 24 hours.Get layer oily matter, use a large amount of tetrafluoro furans to wash, arginine NCA can be obtained.Then the arginine NCA solution (80:1 monomers/initiator) of 148ml0.2M is joined 250ml to contain in the round-bottomed flask of silica supports.Mixture is stirred 48 hours at 50 DEG C.Gained powder is carried out centrifugation, and with THF, DMF and the chloroform of 80ml.The composite obtained is carried out drying, stores in 40 DEG C of baking ovens.The adsorbent of preparation is expressed as SH-LA-80, wherein the ratio of 80 monomers/initiator represented.
Experimental example
Choose product prepared by embodiment 1 ~ 7 as examination object, respectively with regard to its physical property, to CO
2the index such as adsorption capacity, stability is examined or check, and data are as follows:
1. physical property,
Test with regard to its performance such as surface area, cell volume respectively, test result is in table 1, hollow ball prepared as can be seen from the table has high surface area and cell volume, and along with being aggregated in the increase of hollow ball surfaces externally and internally PLA content, amine content increases gradually, and surface area and cell volume reduce gradually.
The physical property of the product prepared by table 1 embodiment 1 ~ 7
2. adsorbent is to CO in simulated flue gas
2the investigation of adsorption capacity
Simulated flue gas (10%CO is utilized by TGA
2, use argon gas balance) evaluate in dry conditions.At different temperatures, absorbent to the adsorption capacity of carbon dioxide and amine efficiency as shown in table 2.Test result shows, and adsorption capacity and the amine efficiency of carbon dioxide absorber provided by the present invention are all obviously better than commercially available prod.The all tests at 50 DEG C of the data of commercially available prod.
Table 2 adsorbent is to CO in simulated flue gas
2adsorption capacity
3. adsorbent is to CO in air
2the investigation of capture ability
In the dry environment of 50 DEG C, dissimilar absorbent is as shown in table 3 for the uptake of CO2 in simulated air (400ppm CO2), shows that this adsorbent can be used in the absorption of Carbon Dioxide in Air.Test result shows, and adsorption capacity and the amine efficiency of carbon dioxide absorber provided by the present invention are all obviously better than commercially available prod.
Table 3: dissimilar adsorbent at 50 DEG C to simulated air (400ppmCO
2) middle CO
2absorption
4. test absorption, the desorption ability of adsorbent
With the absorption of the adsorbent of SH-LA-60 and SH-LA-80 two type-desorption cycle process, the results are shown in Figure 1.Wherein SH-LA-80 50 DEG C time adsorption capacity up to 4.975mmol CO
2g
-1, be the peak that this type of adsorbent current can reach, the carbon dioxide absorption amount of the absorbent of two types only have dropped about 2% in 120 De contamination processes, illustrates that adsorbent has good stability in the process of Temp .-changing adsorption.
5. the pattern test of hollow silica ball carrier
In embodiment 1, the scanning electron microscopic picture of the hollow silica ball carrier of preparation the results are shown in Figure 2.As can be seen from Figure 2 prepared hollow ball has monodispersity, and each hollow ball there is a size be about the perforate of 100nm, the existence of these perforates can guarantee that the inner surface of hollow ball is utilized fully, and increases sorption and desorption speed simultaneously.
To sum up data display: carbon dioxide absorber physical property provided by the present invention is better, the advantages such as stability is high, and absorbing carbon dioxide ability is strong.
Claims (4)
1. a carbon dioxide absorber, is characterized in that, does carrier by the amidized hollow silica ball of surfaces externally and internally, and line style pR is fixed on the surfaces externally and internally of carrier by chemical bond with the form of in-situ polymerization.
2. prepare a method for a kind of carbon dioxide absorber as claimed in claim 1, it is characterized in that,
Utilize amination reagent, by the surfaces externally and internally amination of hollow silica ball, then adopt the mode of in-situ polymerization at the surfaces externally and internally polymerization pR of amidized hollow silica ball, namely obtain carbon dioxide absorber;
Described amination reagent is selected from 3-aminopropyl trimethoxy silicon;
The aperture of described hollow silica ball is 50 ~ 550nm;
Described pR is linear macromolecule;
Concrete steps are as follows:
1) preparation of hollow silica ball: add ethyl orthosilicate in vial, polystyrene emulsion suspension, gained mixture continual ultrasonic 2 hours, then centrifugation, under room temperature after dry 12h, by polystyrene moulding by calcining removing;
The concentration of described polystyrene emulsion suspension is 2.5wt% ~ 2.62wt%;
Described ethyl orthosilicate with the volumetric usage ratio of polystyrene emulsion suspension is: 100:1 ~ 70:1;
2) amination of hollow silica ball: by step 1) hollow silica ball prepared at 100 DEG C of vacuum drying 12h, then add dry toluene and 3-aminopropyl trimethoxy silicon, mixture at room temperature stirred 24 hours; By gained solid product toluene, methyl alcohol, methanol/water volume ratio is that the mixture of 1:1 and methyl alcohol wash successively, and dry at 50 DEG C under vacuo, namely obtains amidized hollow silica ball carrier;
The mass ratio of described dry toluene and hollow silica ball carrier is 35:1;
The mass ratio of described hollow silica ball carrier and 3-aminopropyl trimethoxy silicon is 7:1;
3) preparation of carbon dioxide absorber: get step 2) the amidized hollow silica ball carrier prepared, be dissolved in N-carboxyl inner-acid anhydride arginine solution, stir 48 hours at 50 DEG C, centrifugation obtains powder, powder THF, DMF and chloroform are washed successively, by dry at 40 DEG C for the solids obtained, namely obtain carbon dioxide absorber, store in 40 DEG C of baking ovens;
The concentration of described N-carboxyl inner-acid anhydride arginine solution is 0.2mol/L;
Described N-carboxyl inner-acid anhydride arginine and the mol ratio of amidized hollow silica ball carrier are 20:1 ~ 80:1.
3. a kind of method preparing a kind of carbon dioxide absorber as claimed in claim 1 as claimed in claim 2, is characterized in that, step 1) in the volumetric usage of ethyl orthosilicate and polystyrene emulsion suspension than being 85:1.
4. a kind of method preparing a kind of carbon dioxide absorber as claimed in claim 1 as claimed in claim 2, is characterized in that, step 1) in the concentration of polystyrene emulsion suspension be 2.60wt%.
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| CN110075812A (en) * | 2019-05-17 | 2019-08-02 | 上海大学 | A kind of preparation method and application of amination silica dioxide granule adsorbent |
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| CN110075812A (en) * | 2019-05-17 | 2019-08-02 | 上海大学 | A kind of preparation method and application of amination silica dioxide granule adsorbent |
| CN110075812B (en) * | 2019-05-17 | 2022-02-25 | 上海大学 | Preparation method and application of silicon dioxide particle adsorbent |
| CN110548486A (en) * | 2019-08-09 | 2019-12-10 | 中国华电科工集团有限公司 | CO 2 adsorbent and preparation method thereof |
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