CN106914258A - Preparation method of silica gel column-supported mesoporous biomass carbon solid sulfonic acid - Google Patents
Preparation method of silica gel column-supported mesoporous biomass carbon solid sulfonic acid Download PDFInfo
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- CN106914258A CN106914258A CN201710017071.6A CN201710017071A CN106914258A CN 106914258 A CN106914258 A CN 106914258A CN 201710017071 A CN201710017071 A CN 201710017071A CN 106914258 A CN106914258 A CN 106914258A
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- silica gel
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000741 silica gel Substances 0.000 title claims abstract description 40
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 239000007787 solid Substances 0.000 title claims abstract description 26
- 239000002028 Biomass Substances 0.000 title claims abstract description 25
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 18
- 229910006069 SO3H Inorganic materials 0.000 claims abstract description 17
- 229930006000 Sucrose Natural products 0.000 claims abstract description 16
- 239000005720 sucrose Substances 0.000 claims abstract description 16
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 3
- 239000008103 glucose Substances 0.000 claims abstract description 3
- 238000009835 boiling Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 38
- 239000003575 carbonaceous material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 11
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 11
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 11
- 239000011425 bamboo Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005457 optimization Methods 0.000 claims 5
- 229930091371 Fructose Natural products 0.000 claims 1
- 239000005715 Fructose Substances 0.000 claims 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 125000000185 sucrose group Chemical group 0.000 claims 1
- 238000009830 intercalation Methods 0.000 abstract description 17
- 230000002687 intercalation Effects 0.000 abstract description 17
- 239000011229 interlayer Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008961 swelling Effects 0.000 abstract description 5
- 229920002522 Wood fibre Polymers 0.000 abstract description 2
- 239000002025 wood fiber Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 31
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 241001330002 Bambuseae Species 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 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 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CZKYLWACZPRYOR-UHFFFAOYSA-N [S].OS(O)(=O)=O Chemical compound [S].OS(O)(=O)=O CZKYLWACZPRYOR-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 aromatic alkene Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K3/00—Invert sugar; Separation of glucose or fructose from invert sugar
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Catalysts (AREA)
- Silicon Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing silica gel column-supported mesoporous biomass carbon solid sulfonic acid (SiO) by using wood fiber biomass2‑BC‑SO3H) And a method for preparing glucose by catalyzing sucrose hydrolysis by using the same. SiO 22‑BC‑SO3The H preparation comprises the steps of biomass thermal carbonization or concentrated sulfuric acid dehydration carbonization, boiling water swelling, acid silica sol intercalation, dehydration by heating in nitrogen (350 ℃), concentrated sulfuric acid sulfonation and the like. The invention proves that the SiO prepared by the steps2‑BC‑SO3The content of silica gel of H is about 15wt%, the sulfonic group density is more than 0.9 mmol/g, and the mesoporous silica gel has an interlayer mesoporous structure. The catalyst is used for catalyzing sucrose hydrolysis reaction, and shows better catalytic activity and reusability compared with non-porous biomass carbon solid sulfonic acid.
Description
Technical field
The invention belongs to the preparation field of the mesoporous type biomass carbon material of pillared interlayer, specially it is related to one kind Ludox
It is column-supporting agent, prepares the pillared interlayer mesoporous biological matter carbon solid sulfoacid SiO of silica gel2-BC-SO3H catalyst, and use the catalysis
The method of agent catalysing sucrose hydrolysis.
Background technology
As global environment deteriorates, fossil energy is nervous, seeks a kind of environmental protection, inexpensive high effect and sustainable development
The new energy of exhibition has turned into subject of development meeting the demand growing to the energy.Biomass as a kind of wide material sources, into
This is low, and the resource of environmental protection is increasingly valued by people, and developing biomass resource has turned into the heat of people's research
Point.The various charring process such as biomass can be carbonized by Vacuum Heat, the concentrated sulfuric acid is dehydrated carbonization, catalysis hydrothermal carbonization form bio-based
Carbon Materials, the material can introduce sulfonic acid group and obtain a kind of new and effective solid acid catalyst by sulfonation（S. N. Kang,
J. Ye, J. Chang, International Review of Chemical Engineering, 2013, 5 (2),
133-144）.This kind of biological carbon-based solid sulfoacid material is cheap and easy to get, catalysis activity is high, selectivity good, small to equipment corrosion,
And the study hotspot in acid catalysis field is become the advantages of good chemical stability.Yet with this kind of solid sulfoacid tool
The polymerizable aromatic alkene for having size about 1-1.5nm can stack the class stone to form densification by the strong hydrogen bond force of its edge polarities functional group
Black alkene stratiform non-pore structure（K Nakijima, M. Hara, ACS Catal., 2012, 2 1296-1304）, its sulfonic acid position
It is closed, there is repulsive interaction to the reaction of some non-polar compounds；It is low additionally, due to carbonizing degree, its part small molecule carbon
Sector-meeting comes off during acid catalysis from carbon body stacking of layers body, causes the re-usability of catalyst to be deteriorated（Xunhua
Mo, Dora E. López, Kaewta Suwannakarn, Yijun Liu, Edgar Lotero, James G.
Goodwin Jr, Changqing Lu, Journal of Catalysis 254 (2008) 332-338）.High-temperature catalytic heat
Charing can prepare to have stablizes the surface biological base solid sulfoacid material high of pore structure, but such catalyst micropore is more, sulfonic acid amount
It is low, cause its acid catalysis inefficient（Suganuma, S.; Nakajima, K.; Kitano, M.; Yamaguchi,
D.; Kato, H.; Hayashi, S.; Hara, M. J. Am. Chem. Soc. 2009, 131, 12787−
12793）.Although hard template can be used（Ryoo, R.; Joo, S. H.; Jun, S. J. Phys. Chem. B 1999,
103, 7743）Or soft template method（Meng, Y.; Gu, D.; Zhang, F. Q.; Shi, Y. F.; Yang, H. F.;
Li, Z.; Yu, C. Z.; Tu, B.; Zhao, D. Y. Angew. Chem., Int. Ed. 2005, 44, 7053）
Prepare the biological carbon-based material of ordered mesopore structure, but its cost of material for using is higher, preparation process is complicated, it is whard to control,
Yield is low, sulfonation ability is also poor, and the industrial application value as solid acid is not high.
In sum, in order to prepare with compared with Large ratio surface and the bio-based solid carbon sulfonic acid for stablizing pore passage structure, this hair
It is bright there is provided it is a kind of be column-supporting agent using inexpensive Ludox, dehydration is calcined and then with using concentrated sulfuric acid sulphur using hydro-thermal graft process
The method that change prepares the pillared mesoporous biological matter solid carbon sulfonic acid material of silica gel, the solid acid catalyst of preparation is hydrolyzed in catalysing sucrose
There is high mass transfer efficiency and excellent reusability in reaction, the mass transfer that traditional non-pass biomass carbon sulfonic acid is present is overcome
The shortcoming that efficiency is low, stability is poor.
The content of the invention
The silicagel column for having and stablizing interlayer meso-hole structure is prepared it is an object of the invention to provide a kind of utilization hydro-thermal graft process
The method for supportting biomass carbon-based solid sulfoacid.The method has that raw material is inexpensive, it is easy to prepare, the advantages of catalyst high income；Institute
The sulfonic group content for preparing catalyst is higher, and specific surface area and aperture are larger, the high catalytic efficiency in sucrose hydrolysis reaction, reclaims
Work well.
Present invention offer is a kind of to prepare the mesoporous pillared biomass carbon solid sulfoacid SiO of silica gel of stabilization interlayer2-BC-SO3H's
Method, described preparation method is comprised the following steps：
（1）Natural wooden fiber's biolobic material is converted into by char-forming material using heat charing in tube furnace or concentrated sulfuric acid dehydration carbonization
（BC）, the immersion of BC material with water is then obtained into swelling BC materials；
（2）By step（1）Swelling BC materials add acidic silicasol solution in, then stir process is certain at a certain temperature
Time, then filter, washing, in 60 DEG C of h of drying 3, finally 350 DEG C in the tube furnace, under blanket of nitrogen heat 3 h, obtain
The pillared biomass carbonization material of silica（SiO2-BC）；
（3）By step（2）Gained SiO2- BC materials use concentrated acid sulfonation, washing, and it is pillared mesoporous to obtain product silica gel after drying
Biomass carbon solid sulfoacid SiO2-BC-SO3H。
It is the method for monose invention additionally provides a kind of catalysing sucrose hydrolysis, the method is included in catalyst
Under effect, sucrose hydrolysis are converted into monose, and the catalyst is SiO2-BC-SO3H。
For prior art prepare non-pass biomass carbon solid sulfoacid generally existing acid catalysis efficiency it is low, reuse
Poor performance, and duct type biomass carbon solid sulfoacid the situation that preparation cost is high, sulfonic acid density is relatively low, invention of the invention
People has found on the basis of further investigation, and using Ludox column-supporting agent cheap and easy to get, be carbonized material to wood fiber biomass
Material is processed in a mild condition, can will be strutted to be formed to have between biomass carbon basic unit after dehydration is calcined and be stablized meso-hole structure
Biological carbon-based material.The material can obtain sulfonic acid base density higher, and meso-hole structure energy under relatively mild sulfonating conditions
Keep well, the high catalytic efficiency in sucrose hydrolysis reaction, recovering effect is good, more steady compared to Common sulfonation Carbon Materials
It is fixed.The present inventor is carrying out deep thinking and substantial amounts of exploration for reduces cost, the consideration of green chemical concept
It was found that after, carbonized stock and column-supporting agent are respectively with agricultural abandoned biomass and Ludox, not only low cost, source are wide, and
Can turn waste into wealth, the mesoporous biological carbon-based solid sulfoacid catalyst of preparation, function admirable same can be entered to realize economic synergy and environment
Protection.
Other features of the invention will be described in detail with advantage in subsequent specific embodiment part.
Specific embodiment
With reference to specific embodiment, the present invention is described further, however be not limited to the present invention list it is specific
The embodiment of embodiment description.
Embodiment 1：
The present embodiment is used for the method for illustrating to prepare the pillared biomass carbon solid sulfoacid of silica gel using bamboo powder and Ludox.
（1）The preparation of biomass carbon material：Bamboo powder 9g is weighed, tube furnace internal program is put in and is heated up with the speed of 2 DEG C/min
To 300 DEG C, 3 h are then stopped, obtain Carbon Materials（BC）3 g；
（2）The preparation of acidic silicasol：In 35 DEG C of water-baths of band stirring, the mL of sodium silicate solution 200 of 0.05 M is added
To 200 mL, in the oxalic acid solution of 0.12 M, regulation pH value, by sodium oxalate precipitation filtering removal, is obtained between 3.0 ~ 3.5
0.025 M silicon sol solutions；
(3) Carbon Materials pretreatment：3 g Carbon Materials are weighed, 30 mL distilled water are added, then 3h is boiled in 100 DEG C of water-baths,
So that Carbon Materials are swelling, fluffy, room temperature is cooled to standby；
（4）The preparation of the pillared mesoporous bamboo charcoal material of silica gel：By the mL of silicon sol solution 400 of above-mentioned preparation, (consumption is with titanium dioxide
Siliceous amount is calculated as 20%) being added in above-mentioned swelling Carbon Materials solution of BC mass, the h of stir process 48 at 50 DEG C, then
Filtering, washing, in 60 DEG C of h of drying 36, finally 350 DEG C of 3 h of dehydration in blanket of nitrogen, obtain the pillared mesoporous bamboo carbon materials of silica gel
Expect 3.45 g, be designated as SiO2-BC.Remaining ash content after this g of material 0.5 is burnt in Muffle furnace at 950 DEG C is weighed and obtains SiO2
Amount, SiO is calculated with this2The silica gel intercalation amount of-BC is 18.1 %；
（5）The preparation of the pillared mesoporous bamboo carbon solid sulfoacid of silica gel：Take SiO2The g of-BC- materials 3 mL of the concentrated sulfuric acid 45（By solid-to-liquid ratio
1:15）3 h are reacted at 100 DEG C, is washed with water repeatedly colourless to filtrate after cooling and is neutrality, 110 DEG C of drying in oven are obtained most
The g of end-product 3.17, the % of mass weight gain 5.67, is designated as SiO after sulfonation2-BC-SO3H.A small amount of dried solid (0.05g) is taken to add
Enter appropriate saturation NaCl solution ultrasound, filtering, filtrate is titrated with the NaOH of 0.01 M, it is 0. 964 to measure its sulfonic acid base density
mmol/g。
SiO2-BC-SO3The nitrogen absorption under low temperature of H-desorption measurement result shows：The material is in the typical mesoporous distribution of IV types
Curve, the surface area for measuring is 142 m2.g-1, total pore volume is 0.15 cm3.g-1, average pore size is 4.28 nm.
Comparison example 1：This comparison example is used to illustrate the preparation method of non-intercalation bamboo carbon solid sulfoacid.
Directly take the step of above-described embodiment 1（1）The BC materials of preparation are according to the step of above-described embodiment 1（5）Prepare non-intercalation
Bamboo carbon solid sulfoacid, the % of mass weight gain 2.88, is designated as BC-SO after sulfonation3H.Take a small amount of dried solid and add appropriate saturation
NaCl solution ultrasound, filtering, filtrate is titrated with the NaOH of 0.01M, measures its sulfonic acid base density for 1.830 mmol/g.
Embodiment 1 and comparative example 1 are contrasted, SiO2-BC-SO3The sulfonic acid amount of H substantially compares BC-SO3H's is low, and this should be attributed to
The former precursor body is unfavorable for follow-up sulfonation in 350 DEG C of dewater treatments, but the former has sulfonation mass weight gain higher than the latter,
Show that silica gel is pillared to be conducive to stablizing carbon material.
SiO2-BC-SO3H and BC-SO3All can be in 1034 and 581 cm in the infrared spectrum of H-1Show that the feature of S=O is inhaled
Take-up.In addition, SiO2-BC-SO3The infrared spectrum of H is in 1094,797 and 461 cm-1Also Si-O-Si and Si- is given
The symmetrical and asymmetric stretching vibration band of OH.
Knowable to above-mentioned two sample thermal gravimetric analysis results, SiO2-BC-SO3The sulfonic group decomposition temperature of H is 257 DEG C, compares BC-
SO3H's is higher by 11 DEG C, illustrates the heat endurance of the pillared p-sulfonic acid base of silica gel and has certain improvement.
Embodiment 2：The present embodiment is used to illustrate to prepare the pillared mesoporous solid sulfonic acid of silica gel using concentrated sulfuric acid dehydration carbonization
Preparation method.
By the method for examples detailed above 1, it is a difference in that in the step of embodiment 1（1）Prepare the BC materials concentrated sulfuric acid and be dehydrated carbonization
Method, subsequent step by the step of embodiment 1 (2),（3）、（4）(5) step is carried out.
Wherein in step（1）Carbonization Conditions are described as follows：In 100mL reaction bulbs, bamboo powder 6g, the mL of the concentrated sulfuric acid 48 are added,
It is heated to 80 DEG C, the h of stirring reaction 3 is washed with water colourless to filtrate and is neutrality repeatedly after cooling, 110 DEG C of drying in oven are obtained most
The g of BC materials 2.4 is carbonized eventually；The SiO prepared using the BC materials2-BC-SO3The silica gel intercalation amount of H catalyst is 17.1 %, sulphur
The % of mass weight gain 5.18 after change, sulfonic acid base density is 0.958 mmol/g, and the channel surfaces product that nitrogen absorption under low temperature desorption is measured is
113 m2.g-1, total pore volume is 0.14 cm3.g-1, average pore size is 4.88 nm.
Embodiment 3-6, the present embodiment 3-6 are used to illustrate the step of embodiment 1（4）The influence of the concentration of middle Ludox, according to
The method of embodiment 1 is carried out, and wherein Ludox consumption (in terms of silica) is 20 wt%, and pillared temperature is 50 DEG C.Its influence
Result is as shown in table 1 below.
0. 5 M thickness of silica gel are prepared：Using the operating procedure that 0.025 M Ludox is prepared in embodiment 1, by 1 M's
The mL of sodium silicate solution 10 is added to 10 mL, and in the oxalic acid solution of 2 M, pH is between 3.5 ~ 4.0 for regulation；0.05 M Ludox
Concentration is prepared：The mL of sodium silicate solution 100 of 0.1 M is added to 100 mL, in the oxalic acid solution of 0.12 M, regulation pH exists
Between 3.5 ~ 4.0；0.033 M thickness of silica gel is prepared：The mL of sodium silicate solution 100 of 0.1 M is added to 200 mL, 0.12
In the oxalic acid solution of M, regulation pH value is between 3.5 ~ 4.0.
Influence of the thickness of silica gel of table 1 to pillared amount, duct parameter and sulfonic acid amount.
As can be seen from Table 1, decline with thickness of silica gel, the intercalation time can extend to 48-96 h, the insertion of silica gel by
Gradually improve；Sulfonic acid base unit weight is substantially to decline with the raising of silica gel intercalation amount, but is dropped when silica gel insertion is more than 17%
Width is very small.From the point of view of the characterization result of BET, the duct parameter specific surface area of its pillared composite（Sg）, pore volume（Vg）Be with
Thickness of silica gel decline, intercalation time lengthening, the insertion of silica gel improve and it is gradually increased.Being compared by embodiment 1,3 and 4 can
Know, in thickness of silica gel as little as 0.05M or following, specific surface area can be prepared in 130 m2.g-1SiO above2-BC-SO3H materials
Material.And compared from embodiment 1 and 6, the intercalation time extends to 96h and silica gel intercalation amount and duct parameter is changed by 48h
Enter unobvious.Comprehensive analysis thinks that suitable thickness of silica gel is 0.033-0.25M, and the suitable intercalation time is 48h.
Embodiment 7-8, the present embodiment 7-8 are used to illustrate the step of above-described embodiment 1（4）The Ludox addition of pillared reaction
To pillared amount and the influence of sulfonation when different, using 0. 5 M thickness of silica gel, intercalation temperature is 50 DEG C, and the intercalation time is 3h,
Method according to experimental example 1 is carried out, and changes the consumption of Ludox, its influence result such as table 2.
Influence of the Ludox addition of table 2 to pillared amount, duct parameter and sulfonic acid amount.
From table 2 it can be seen that with the increase of Ludox consumption, SiO in Carbon Materials2Content be consequently increased.Three
The sulfonic group content highest of the sample prepared by embodiment 3 in material.BET tests are carried out by three materials, its duct ginseng
Number（Specific surface area Sg, pore volume Vg and average pore size D）It is to rise with the increase of Ludox consumption, but embodiment 3 and 8
The duct parameter of two samples for preparing is approached, it is therefore preferable that the wt% of Ludox amount 20.
Embodiment 9-11, the present embodiment 9-11 are used to illustrate the step of above-described embodiment 1（4）Shadow of the pillared temperature to reaction
Ring, carried out according to the method for embodiment 1, using 0. 5 M thickness of silica gel, the intercalation time is 3h, Ludox consumption（With dioxy
SiClx quality meter）It is 10 wt% of BC mass, changes pillared temperature, its influence result is as shown in table 3 below.
Influence of the pillared temperature of table 3 to the pillared amount of silica gel, duct parameter and sulfonic acid amount.
As shown in Table 3, with the raising of pillared temperature, the SiO in Carbon Materials2Content also gradually increases, its sulfonic acid amount under
Drop.BET analyses by us to intercalation material find that pore-creating effect is substantially risen with the raising of pillared temperature.Due to
Higher temperature can accelerate the reunion of silica sol particle, and then cause that a part of colloidal particle is attached to the surface of Carbon Materials and does not enter
Enter interlayer；Therefore preferably pillared temperature is 50 DEG C.
Embodiment 12-13, the present embodiment 12-13 are used to illustrate the step of above-described embodiment 1（4）The pH value of middle Ludox is to inserting
The influence of layer amount and sulfonation process, is carried out according to the method for embodiment 1, and the pH value of Ludox is the addition by changing oxalic acid
Come what is adjusted, wherein the concentration of Ludox is 0. 5 M, and as 20wt%, pillared temperature is 50 DEG C to consumption (in terms of silica), when
Between be 3h.
Its influence result is as shown in table 4 below.
The pH value of the silicon sol solution of table 4 is to intercalation and the influence of sulfonation.
| Example No. | Ludox pH | Sulfonation weightening/wt % | Sulfonic group/(mmol/g) | |
| 3 | 3.5-4.0 | 12.73 | +8.06 | 1.245 |
| 12 | 4.0-4.5 | 18.28 | +6.87 | 1.254 |
| 13 | 3.0-3.5 | 10.8 | +9.4 | 1.323 |
As can be seen from Table 4, with the rising of Ludox pH, the SiO in Carbon Materials2Content is also increased, its sulfonic acid
Base is influenceed smaller by Ludox pH.In view of solution pH value be higher than 4.5 when, sol particles is easily grown up, coagulation and influence molten
The stability of glue.Therefore suitable Ludox pH is 3.5-4.0.
Embodiment 14-15, the present embodiment 14-15 are used to illustrate the step of embodiment 1（1）It is middle with different biomass peanut shells,
Rice husk influences on pillared and sulfonation process, is carried out according to the method for embodiment 1, wherein the consumption (in terms of silica) of Ludox
It is 20 wt%, thickness of silica gel is 0.025 M, and pillared temperature is 50 DEG C, and the time is 48h.
Its influence result is as shown in table 5 below.
Table 5 peanut shell, rice husk are raw material on the influence of pillared and sulfonation process.
As can be seen from Table 5, two SiO that peanut shell, rice husk are prepared for raw material are used2-BC-SO3H materials, either silicon
Glue intercalation amount, or sulfonic group content all be raw material with bamboo powder（Embodiment 1）What is prepared is close；The duct parameter for measuring and use
Bamboo powder is raw material（Embodiment 1）What is prepared compares, and is declined slightly.
Test example 1：This test example is used to illustrate to use the made SiO of the present embodiment 12-BC-SO3The H and made BC- of comparative example 1
SO3The contrast of the method and catalytic effect of the hydrolysis of H catalysing sucroses.
The specific reaction condition of the catalysis process includes：0.1g sucrose, 5mL distilled water, 0.05g catalyst of the invention
SiO2-BC-SO3H or BC-SO3H, reacts, reaction solution centrifugation under 100 DEG C of counterflow conditions, takes 1mL reaction solutions and adds 2mL
DNS coloring agents are dyeed, then the mensuration absorbance at 520nm, and conversion ratio is calculated according to glucose standard curve, and sucrose turns
Rate is as shown in table 6 below with the change in reaction time；The catalyst that will have been reacted is recycled, so with water washing is distilled 4 ~ 5 times
Carry out reclaiming catalyst reaction determination of activity according to above-mentioned reaction condition afterwards, the reaction time is 1h, and catalyst reclaims the reaction of 4 times
Result is as shown in table 7 below.
As known from Table 6, although SiO2-BC-SO3The sulfonic group content of H is more than BC-SO3H's is low, but in the water of catalysing sucrose
The former is substantially better than the latter on solution conversion capability；And the former repeat performance is also better than the latter（It is shown in Table 7）.This explanation
The meso-hole structure of the pillared formation of silica gel can not only improve the mass-transfer efficiency of carbon sulfonic acid catalytic reaction, and can improve carbon sulfonic acid
Stability.
The catalyst of table 6 is used for the reaction of sucrose hydrolysis.
The recyclability test of the catalyst sucrose hydrolysis of table 7.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention is no longer separately illustrated to various possible combinations.Additionally, a variety of implementations of the invention
Can also be combined between mode, as long as it is without prejudice to thought of the invention, it is public that it should equally be considered as institute of the invention
The content opened.
Claims (11)
1. a kind of method of the pillared mesoporous biological matter carbon solid sulfoacid of silica gel, the pillared mesoporous biological matter carbon solid sulfoacid of silica gel
SiO2-BC-SO3H, it is characterised in that the described method comprises the following steps：
（1）Natural wooden fiber's biolobic material is converted into by char-forming material using heat charing in tube furnace or concentrated sulfuric acid dehydration carbonization
（BC）；
（2）By step（1）Gained BC materials boiling water soaks, is as cold as room temperature, is subsequently adding acidic silicasol solution, is heated to one
Determine stir process certain hour at temperature, then filter, washing, dry, finally 350 DEG C in the tube furnace, under blanket of nitrogen heat
3 h are processed, the pillared biomass carbonization material of silica is obtained（SiO2-BC）；
（3）By step（2）Gained SiO2- BC materials use concentrated acid sulfonation, washing, and it is pillared mesoporous to obtain product silica gel after drying
Biomass carbon solid sulfoacid SiO2-BC-SO3H。
2. method according to claim 1, the biomass are natural wooden fiber's biolobic material, including bamboo powder, peanut
Shell, rice husk etc..
3. method according to claim 1, wherein, in step（1）In heat charing, carbonization temperature is 300 DEG C, and the time is 3
h;In concentrated sulfuric acid dehydration carbonization, concentrated sulfuric acid consumption（Volume, mL）It is carbon material consumption（Quality, g）8 times, dehydration temperaturre is 80
DEG C, the time is 3 h.
4. method according to claim 1, wherein, in step（2）In middle BC material with water immersion, relative to 100 weight
The BC materials of part, water used is 1000 weight point, and water temperature is 100 DEG C, and soak time is 3 h.
5. the method according to claim 1-4 any one, wherein, in step（2）In, the pH of the sour Ludox of acid used
It is 3.0-4.5, the pH of optimization is 3.5-4.0；Thickness of silica gel is 0.50-0.025moL/L, and the concentration of optimization is 0.033-
0.025moL/L。
6. the method according to claim 1-5 any one, wherein, in step（2）In, in terms of 100 weight point BC materials,
The consumption of Ludox（In terms of silica）It is 10-30 weight point, the weight of consumption 20 point of optimization.
7. the method according to claim 1-6 any one, wherein, in step（2）In, the temperature processed with Ludox is
40-60 DEG C, the temperature of optimization is 50 DEG C；Process time is 3-96 h, and the time of optimization is 48 h.
8. the method according to claim 1-7 any one, wherein, in step（2）In, drying temperature is 60 DEG C, time
It is 12 h；Dehydration temperaturre is 350 DEG C, and the time is 3h.
9. the method according to claim 1-9 any one, wherein, step（3）In, sulfonating agent is the concentrated sulfuric acid.
10. sulfonating agent consumption（Volume, mL）It is carbon material consumption（Quality, g）15 times, sulfonation temperature is 100 DEG C, sulfonation time
It is 3 h.
A kind of 11. methods of catalysing sucrose hydrolysis, the method is included in the presence of catalyst, and sucrose hydrolysis are converted into list
Sugar（Glucose and fructose）, it is characterised in that the catalyst is the SiO described in claim 12-BC-SO3H；
Preferably, relative to the sucrose of 100 weight portions, the consumption of the catalyst is 50 weight portions, and reaction temperature is 100 DEG C,
Reaction time is 1 h.
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