CN106824117A - The preparation method of the one order mesoporous adsorbent of species cage type - Google Patents
The preparation method of the one order mesoporous adsorbent of species cage type Download PDFInfo
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- CN106824117A CN106824117A CN201710177177.2A CN201710177177A CN106824117A CN 106824117 A CN106824117 A CN 106824117A CN 201710177177 A CN201710177177 A CN 201710177177A CN 106824117 A CN106824117 A CN 106824117A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 229930003270 Vitamin B Natural products 0.000 claims abstract description 3
- 238000007792 addition Methods 0.000 claims abstract description 3
- 239000011720 vitamin B Substances 0.000 claims abstract description 3
- 235000019156 vitamin B Nutrition 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000001994 activation Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 3
- 229920003086 cellulose ether Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- -1 ultracapacitor Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000011715 vitamin B12 Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000186216 Corynebacterium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28042—Shaped bodies; Monolithic structures
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The preparation method of the one order mesoporous adsorbent of species cage type, it is characterised in that：With carboxymethylcellulose calcium as raw material; triblock copolymer F127 is soft template; after the treatment of HTHP hydrothermal condition; it is centrifugally separating to obtain dark brown solid product; distilled water, absolute ethanol washing is used to be clarified to filtrate for several times; the lower high-temperature calcination 2h of nitrogen protection, obtains the flourishing class cage type carbon microspheres of meso-hole structure, to vitamin B after 80 DEG C of drying12There is absorption property higher.The characteristics of this operating procedure is with cellulose ether as raw material, environmental protection is cheap and easy to get, triblock copolymer F127 is soft template, reacted with raw material and its hydrolysis intermediate product while F127 self assemblies, a large amount of meso-hole structures are formed after high-temperature activation, according to different F127 additions, different orderly meso-hole structures are formed, flourishing meso-hole structure makes it to mcroorganism molecule VB12There is preferable absorption property.The hydro-thermal reaction operating process that this law is used is simple, with low cost, and meso-hole structure is flourishing, with excellent adsorption effect.
Description
Art：
The present invention relates to field of nano material preparation, more particularly to the preparation side of an order mesoporous adsorbent of species cage modle
Method.
Background technology：
The research of a large amount of scholars in recent years shows the Carbon Materials with controlled dimensions and pattern as catalyst, absorption
The various fields such as agent, ultracapacitor, fuel cell have potential application value.Especially spherical Carbon Materials, have
High-specific surface area, low specific density, good conductive several heat conductivilitys have more expanded its application value.Recent research indicate that：It is spherical
Carbon Materials can be prepared by the hydro-thermal method of monose, polysaccharide, biomass material, for the preparation of Carbon Materials is provided simply
Easy method.
Orderly pore structure directly affects the every physics and chemical property for preparing Carbon Materials, what heavy metal ion caused
Water pollution is the environmental problem for sternness that the whole world faces.Soft template method is a kind of effective outstanding for preparing controllable hole structure
It is the method for meso-hole structure, with sympathy block copolymer F127, P123 or the two mixture for structure directing agent, before carbon
Body is connected with surfactant by hydrogen bond and Coulomb force, by the primary particle for being self-assembly of different-shape and size.
After high temperature removes template, 1-D ducts, 2-D hexagons and 3-D cage types ordered mesopore structure can control to prepare.
The Introduction To Cn Patent of the Publication No. CN103482596 A preparation method of a kind of ordered mesoporous carbon and its should
With.Based on the one-step method in hard template method, nonionic triblock copolymer and anion surfactant are mixed to form double
Surfactant system, tetraethyl orthosilicate does template, by being self-assembly of three component copolymers, then by crystallization, pre- oxygen
Change, high temperature carbonization, pickling remove silicon and ordered mesoporous carbon are obtained, and the degree of order is high, in corynebacterium, has very high as cell negative electrode material
The cyclical stability that capacity is become reconciled.Be related to nonionic surfactant and anion surfactant in reaction, activating agent it is dense
Degree has large effect to aperture and the degree of order.
Between being utilized in a kind of ethanol-water solution at room temperature of the Introduction To Cn Patent of Publication No. CN102977397 A
Benzenediol-formaldehyde resin and nonionic surfactant synthesize the preparation method of highly ordered mesosize pores charcoal.Under base catalyst
The macromolecule presoma of low polymerization degree is obtained, it is mixed with nonionic surfactant, add acidic catalyst, be high score
Sub- presoma is further polymerized, Precipitation, and centrifugation obtains lower sediment, and high temperature removes surfactant and obtains high-sequential Jie
Hole macromolecular material, carbonization obtains corresponding ordered mesoporous carbon material under further high temperature, and reaction is carried out at room temperature, but reaction
It is related to acid base catalysator, while needing two step high-temperature activations, is unfavorable for high-volume actual production.
A kind of preparation method of ordered mesoporous carbon material of the Introduction To Cn Patent of Publication No. CN103896250 A.It is first
First prepare mesoporous silicon dioxide hard template material and determine pore volume, add the isometric presoma of pore volume therewith, heated up under vacuum
To presoma boiling point, presoma enters template duct after being kept for a period of time, realizes equivalent impregnation, and the powder after dipping is added
Polymerization initiator solution carries out polymerization conversion, high temperature carbonization after drying, and is put into treatment in HF solution, obtains order mesoporous carbon materials
Material, with specific surface area and pore volume higher, but reacts tediously long, is related to multistep, increased and also increases reaction reaction time
Cost.
A kind of preparation method of mesoporous sphere carbon material of the Introduction To Cn Patent of Publication No. CN103848413 A.With
Polystyrene spheres are template, are dispersed in water or organic solvent, and carbon source is added under ultrasound condition, and ultrasound 0.5~6 is small
When, by the high-temperature roasting under an inert atmosphere of isolated solid, the mesoporous sphere Carbon Materials of above-mentioned preparation being obtained, the method is simple
It is easy, low cost, without extra catalyst or oxidant, reaction is related to carbon source usually phenolic resin, and solvent is mostly organic
Reagent, it is big to carrying capacity of environment, it is unfavorable for large-scale commercial application.
A kind of New Type of Mesoporous for adsorbing heavy metal ions in wastewater of the Introduction To Cn Patent of Publication No. CN102908982
The preparation method of material.This law prepares specific template first, after silicon source and rare earths salt then are hydrolyzed to form into sol-gel
Crystallization is carried out to it, synthesising mesoporous molecular sieve precursor obtains ordered meso-porous silicon oxide rare earth product after removing removing template.To specific
Heavy metal ion includes Pb2+, Zn2+, Cu2+And Ag2+Deng with preferable absorption property.Silicon source in reaction is generally metasilicic acid
Sodium, methyl silicate etc., are unfavorable for environment-friendly development while the ratio of silicon source and rare-earth salts has considerable influence to pore structure.
In sum, order mesoporous adsorbent is prepared at present mainly with phenolic resin, silicon source etc. as raw material, and polystyrene is small
Ball or predetermined substance are template, with organic reagent as solvent, by high temperature or the complicated processing procedure of a few steps, obtain mesoporous
Abundant Carbon Materials.These methods generally need in the reaction add acid base catalysator, reaction condition to be difficult to control to and have to product
The preparation of sequence pore structure has a significant impact, and increased reaction cost, and is unfavorable for commercially producing on a large scale.And biomass are former
Expect that the ordered mesoporous carbon material for preparing shows stabilization and excellent properties in terms of macromolecules adsorption, therefore, explore a kind of simple
The ordered mesoporous carbon material that easy, environmentally friendly method prepares specific morphology is significant.
The content of the invention：
It is an object of the invention to provide the preparation method of an order mesoporous adsorbent of species cage type.
In order to achieve the above object, the technical solution adopted by the present invention includes：The one order mesoporous adsorbent of species cage type
Preparation method, it is characterised in that：With carboxymethylcellulose calcium as raw material, surfactant triblock copolymer F127 is soft template,
Pure water is solvent, after the treatment of HTHP hydrothermal condition, centrifugation, isolated dark brown solid product, by brown solid
Clarified to filtrate for several times with distilled water, absolute ethanol washing, high-temperature calcination 2h under nitrogen protection after 80 DEG C of drying obtains mesoporous
The flourishing class cage type carbon microspheres of structure, to macromolecular vitamin B12There is absorption property higher.The main feature of this operating procedure
It is that, with cellulose ether carboxymethylcellulose calcium as raw material, environmental protection is cheap and easy to get, water is solvent, triblock copolymer F127 is soft mode
Plate, F127 can be self-assembly of different-shape while occur with raw material carboxymethylcellulose calcium and its hydrolysis intermediate product it is anti-
Should, a large amount of meso-hole structures are formed after high-temperature activation, according to different F127 additions, form the mesoporous of different ordered structures, hair
The meso-hole structure for reaching makes it to mcroorganism molecule VB12There is preferable absorption property.The hydro-thermal reaction operating process letter that this law is used
Single, with low cost, meso-hole structure is flourishing and controllable, with excellent adsorption effect.
It is an advantage of the invention that：
1st, with cellulose ether carboxymethylcellulose calcium as raw material, natural cellulosic feedstocks are made full use of, abundant raw material is inexpensively easy
, environmental-friendly natural is pollution-free, and HTHP hydrothermal conditions can make its rapid hydrolysis dehydrating condensation, beneficial to further anti-
Should utilize；
2nd, instant invention overcomes deficiency of the prior art, traditional production technology is changed, using hydro-thermal reaction, with water
It is solvent, raw material is not required to pretreatment, reduces reaction temperature, shortens the reaction time, and reaction condition is gentle, and process operation is simple, raw
Low cost is produced, yield is high.
3rd, the present invention with triblock copolymer F127 as template, by self assembly simultaneously and raw material reaction, promote to be formed
Substantial amounts of ordered mesopore structure is formed while special defects cage type, its scope of application has been expanded.
4th, process environmentally safe without any additional high temperature in present invention reaction, a large amount of orderly meso-hole structures make it
To vitamin B12There is more excellent absorption property.
Brief description of the drawings：
Fig. 1 is the order mesoporous adsorbent SEM pictures of class cage type that the embodiment of the present invention 1 is prepared；
Fig. 2 is the order mesoporous adsorbent TEM pictures of class cage type that the embodiment of the present invention 1 is prepared；
Fig. 3 is the order mesoporous adsorbent of class cage type for preparing of the embodiment of the present invention 1 to VB12Saturation adsorption curve.
Specific embodiment：
Present invention implementation is described in further detail below：
The preparation method of the one order mesoporous adsorbent of species cage type, it is characterised in that：With carboxymethylcellulose calcium as raw material, table
Face activating agent triblock copolymer F127 is soft template, and pure water is solvent, after the treatment of HTHP hydrothermal condition, centrifugation, separation
Dark brown solid product is obtained, brown solid distilled water, absolute ethanol washing are clarified to filtrate for several times, 80 DEG C of drying
High-temperature calcination 2h under nitrogen protection, obtains the flourishing class cage type carbon microspheres of meso-hole structure, to macromolecular vitamin B afterwards12Have compared with
Absorption property high.
Below, the present invention will be further detailed with embodiment, but it is not limited to any of these embodiments
Individual or similar example.
Embodiment 1：
Take F127 0.7g to be dissolved in 20ml water, be stirred continuously in 60 DEG C of water-baths up to being completely dissolved, separately take the fibre of drying
The plain ether carboxymethylcellulose calcium 1.5g of dimension, mixes two solution after being dissolved in 20ml water.Polytetrafluoroethylene (PTFE) is put into reactor, is protected
Card liquor capacity is 13 with kettle volume:20,10 DEG C/min heating rates are warming up to 220 DEG C of target temperature, constant temperature 10h, cooling drop
To room temperature, obtain brown solid with the rotating speed centrifugation 30min of 8000r/min twice.Priority distilled water and anhydrous
Ethanol is washed 2 times, and 850 DEG C of high-temperature process 2h in calcining furnace are put into after 80 DEG C of vacuum drying, and the adsorbent for preparing is class cage
Type shape, mesoporous average grain diameter is 2.5nm, as shown in Fig. 1 Fig. 2.
Compound concentration is the VB of 1000mg/L12The aqueous solution, is diluted to 20~200mg/L respectively, takes order mesoporous in example 1
Spherical adsorbent 0.01g is distributed in the conical flask equipped with the above-mentioned solution of 10ml that concentration is V, and 24 are vibrated in 30 DEG C of waters bath with thermostatic control
Hour, adsorption equilibrium is reached, remove solid particle, the liquid ultraviolet specrophotometer for obtaining with 0.45 μm of membrane filtration of diameter
(TU-1900) situation of change of the characteristic absorption peak after detection absorption at 361nm.Result shows, the adsorbent room temperature in example 1
Lower test is to VB12Saturation adsorptive value be respectively 98mg/g.
Embodiment 2：
Take F127 1.5g to be dissolved in 20ml water, be stirred continuously in 60 DEG C of water-baths up to being completely dissolved, separately take the fibre of drying
The plain ether carboxymethylcellulose calcium 1.0g of dimension, mixes two solution after being dissolved in 20ml water.Polytetrafluoroethylene (PTFE) is put into reactor, is protected
Card liquor capacity is 4 with kettle volume:5,10 DEG C/min heating rates are warming up to 200 DEG C of target temperature, and constant temperature 14h is cooled down to
Room temperature, obtains brown solid with the rotating speed centrifugation 20min of 10000r/min twice.Priority distilled water and anhydrous
Ethanol is washed 2 times, and 800 DEG C of high-temperature process 2h in calcining furnace are put into after 80 DEG C of vacuum drying, and the adsorbent for preparing is class cage
Type shape, mesoporous average grain diameter is 2.8nm.
Compound concentration is the VB of 1000mg/L12The aqueous solution, is diluted to 20~200mg/L respectively, takes order mesoporous in example 1
Spherical adsorbent 0.01g is distributed in the conical flask equipped with the above-mentioned solution of 10ml that concentration is V, and 24 are vibrated in 30 DEG C of waters bath with thermostatic control
Hour, adsorption equilibrium is reached, remove solid particle, the liquid ultraviolet specrophotometer for obtaining with 0.45 μm of membrane filtration of diameter
(TU-1900) situation of change of the characteristic absorption peak after detection absorption at 361nm.Result shows, the adsorbent room temperature in example 1
Lower test is to VB12Saturation adsorptive value be respectively 86mg/g.
Claims (8)
1. the preparation method of an order mesoporous adsorbent of species cage type, it is characterised in that：With carboxymethylcellulose calcium as raw material, surface
Activating agent triblock copolymer F127 is soft template, and pure water is solvent, after the treatment of HTHP hydrothermal condition, is centrifuged, separates
To dark brown solid product, brown solid distilled water, absolute ethanol washing are clarified to filtrate for several times, after 80 DEG C of drying
High-temperature calcination 2h, obtains the flourishing class cage type carbon microspheres of meso-hole structure, to macromolecular vitamin B under nitrogen protection12Have higher
Absorption property.
2. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：Hydro-thermal is anti-
Carboxymethylcellulose calcium material concentration is 1.25%~7.5% in answering, and solvent capacity is 3 with reaction capacity ratio:5~4:5.
3. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：Soft template
The addition concentration of surfactant F127 is 1%~7%.
4. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：Prepare anti-
Temperature is answered in 190~240 DEG C, 10~15 hours reaction time.
5. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：This legal system
The centrifugation speed of standby order mesoporous adsorbent is 4000~12000rpm, and centrifugation time is 15~30min.
6. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：This legal system
Standby high absorption property spherical adsorbent first with distillation water washing 1-3 times, then with absolute ethanol washing 1-3 times.
7. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：High temperature is forged
Temperature needed for burning is between 700-950 DEG C.
8. according to the preparation method of the order mesoporous adsorbent of species cage type described in claim 1, it is characterised in that：This legal system
The order mesoporous average-size of standby adsorbent is in 2.3-3.8nm.
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