CN102218342B - Preparation method of high efficient sulfonated carbon solid acid catalyst - Google Patents
Preparation method of high efficient sulfonated carbon solid acid catalyst Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 28
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- 150000001721 carbon Chemical class 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 5
- 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 description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 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 description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- 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 description 3
- ZDVDCDLBOLSVGM-UHFFFAOYSA-N [chloro(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(Cl)C1=CC=CC=C1 ZDVDCDLBOLSVGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- -1 phenmethylol Chemical compound 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003225 biodiesel Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract description 3
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003245 coal Substances 0.000 abstract 2
- 238000005838 aromatic sulfonation reaction Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 8
- 229920006362 Teflon® Polymers 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002479 acid--base titration Methods 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 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
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention relates to a preparation method of a high efficient sulfonated carbon solid acid catalyst. According to the method, biomasses and aromatics, which are treated as reaction monomers, are used to form carbon materials with abundant surface aromatic structures through a solvent heat carbonization method, and are sulfonated by concentrated sulfuric acid to obtain the solid acid catalyst with high acid amount and high stability. The method has the outstanding characteristics that: the biomasses are used as a precursor, the aromatics are introduced, effective aromatic sulfonation is guaranteed through providing a lot of aromatic nuclei, a lot of sulfonic acid groups can be introduced, the sulfonated coal solid acid prepared with the aromatics has a higher catalytic efficiency than sulfonated coal solid acids with no aromatics added, so aromatic adding plays an important role in sulfonation; and the catalyst has the advantages of controllable acid amount, high reaction activity and good stability, can be recovered, performs excellent activity and cyclical stability in a series of organic reactions such as synthesis of biodiesel and fine chemicals, conforms to the requirements of modern society, is environment friendly, and possesses a wide application prospect.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of preparation method of sulfonated carbon solid acid catalyst, particularly a kind of surface Carbon Materials of being rich in aromatic ring structure carries out sulfonation and prepares the preparation method of carbonaceous solid acid catalyst.
Background technology
Carbonaceous solid acid catalyst has that catalytic efficiency is high, good stability, easily recycle and reuse, environmentally friendly, the advantage such as cheap and renewable.And the carbonaceous solid acid of sulfonic acid group is rich on surface, due to sulfonic highly acid, it can replace the more acid catalyzed reactions of homogeneous phase such as the concentrated sulfuric acid, simultaneously also can some acidity of catalysis lower molecular sieve can't catalysis reaction, therefore, carbonaceous solid acid catalyst can be used for the synthetic of esterification, cellulosic hydrolysis, alkylated reaction, fine chemicals, in the reaction such as the preparation of biodiesel, have good application prospect, likely becoming 21 century has the green solid acid catalyst of development potentiality most.
Preparing Sulfonated carbonaceous solid acid catalyst has several different methods, and the method that usually adopts is the charing sulfonation method.This method is at first with living beings (starch, cellulose, sucrose, glucose; fructose etc.) or natural material (stalk, rice; leaf etc.) or polycyclic aromatic hydrocarbon (such as naphthalene, anthracene etc.) at high temperature carry out incomplete charing under inert atmosphere protection, then with the concentrated sulfuric acid or oleum, it is carried out sulfonated processing.This method operation is more loaded down with trivial details, needs the synthesis conditions such as high temperature, inert atmosphere, and synthetic material surface sulfonate radical is easy to run off.Therefore need to improve preparation technology, in gentle, simple mode, carry out the synthesizing efficient sulfonated carbon solid acid catalyst.
In recent years, utilize the hydrothermal carbonization method to synthesize material with carbon element and caused a lot of researchs.It utilizes living beings (sucrose, glucose, starch, celluloses etc.) Hydrothermal Synthesis obtains material with carbon element, because temperature is lower, generally between 160 ℃ to 200 ℃, resulting carbon material surface has also kept many hydroxyls, can further utilize organic reaction to carry out the mutual conversion of functional group, therefore can introduce multiple other surface groups.This method mild condition, relatively environmental protection, therefore, be subject to more and more people's attention.The present invention, take the hydro-thermal charcoal as basis, has designed, has synthesized a series of brand-new sulfonated carbon solid acid catalysts.
Summary of the invention
The purpose of this invention is to provide a kind of simple, efficient, the preparation method of the sulfonated carbon solid acid catalyst that the acid amount is controlled.
Technical scheme of the present invention is as follows: a kind of preparation method of high efficient sulfonated carbon solid acid catalyst, and living beings and aromatic are fully mixed, carried out solvent thermal reaction 16~72 hours in 150~200 ℃, generate the Carbon Materials that is rich in surperficial aromatic ring; Add the concentrated sulfuric acid to carry out sulfonation, synthetic surface is rich in the carbonaceous solid acid catalyst of acidic group again.Described living beings are glucose, fructose, sucrose, maltose, cellulose, furfural, starch; Described aromatic is benzyl chloride, phenmethylol, diphenyl-chloromethane, phenol, chlorobenzene.Described carbonaceous solid acid catalyst can regulate and control the amount of sulfonic acid surfactant root according to the addition of aromatic compound, its scope is at 0.5~2.4mmol/g.The mass ratio of described living beings and aromatic is 4: 1~3.
Advantage of the present invention is: 1. adopt living beings as predecessor, and take aromatic as additive, the synthetic material with carbon element that is rich in surperficial aromatic ring, thus can introduce easily sulfonic acid group; 2. preparation process is simple, need not high temperature cabonization, need not inert atmosphere protection, and the reaction condition gentleness is controlled, greatly reduces the danger of the synthetic sulfonated solid acid catalyst of conventional method, and is safer reliable; 3. high, the good stability of catalyst reaction activity, recyclable recycling: at a series of excellent activity and cyclical stabilities that acid has been showed in demanding organic reaction,, higher than the sulfonation charcoal solid acid that does not add the aromatics deposits yields, so add aromatic, sulfonation has been played vital effect far away; 4. the catalyst acid amount is controlled, sulfonic acid surfactant root amount can be prepared according to the requirement of concrete reaction, the solid acid catalyst of preparation is synthetic esterification, cellulosic hydrolysis, alkylated reaction, fine chemicals, and the aspects such as the preparation of biodiesel are with a wide range of applications.
Description of drawings
Fig. 1 is the XRD spectra of the solid acid catalyst that obtains in embodiment 1;
Fig. 2 is the aerial thermogravimetric curve of solid acid catalyst that obtains in embodiment 1, has shown certain stability;
Fig. 3 is the infrared spectrum of the solid that in embodiment 1, the first step obtains, and the figure acceptance of the bid understands the characteristic peak that phenyl ring exists;
Fig. 4 is the infrared spectrum of the solid acid catalyst that obtains in embodiment 1, and the figure acceptance of the bid understands sulfonic characteristic peak;
Fig. 5 is left does not add catalyst that benzyl chloride obtains recycles in acetic acid isoamyl alcohol esterification yield for the first step in Kaolinite Preparation of Catalyst process in embodiment 1, right is the yield that the solid catalyst in embodiment 1 recycles, both compare, the latter has shown high activity and cyclical stability (reaction condition: acetic acid: 0.07mol; Isoamyl alcohol: 0.05mol; Catalyst: 0.5g; Reaction temperature: 90 ℃; Reaction time: 4h).
The specific embodiment
[embodiment 1]
After cellulose and benzyl chloride are taken in mass ratio at 4: 1, be placed in the stainless steel pressure still with teflon lined, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding, with deionized water and ethanol filtering and washing, with the solid that obtains 90 ℃ of drying in oven; Get this solid and the concentrated sulfuric acid and be placed in mass ratio stainless steel pressure still with teflon lined at 1: 10, after uniform stirring mixes, sulfonation is 24 hours in 160 ℃ of baking ovens, take out cooling, after grinding,, with 90 ℃ of deionized waters and ethanol filtering and washing, after then putting into 90 ℃ of drying in oven, namely obtain needed catalyst.Recording Surface acidity through acid base titration is 4.59mmol/g, and the sulfonate radical amount is 1.38mmol/g.
[embodiment 2]
After glucose and phenol are taken in mass ratio at 4: 2, add a small amount of N, dinethylformamide is as solvent, be placed in the stainless steel pressure still with teflon lined, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding, with deionized water and ethanol filtering and washing, with the solid that obtains 90 ℃ of drying in oven; Get this solid and the concentrated sulfuric acid and be placed in mass ratio stainless steel pressure still with teflon lined at 1: 10, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding,, with 90 ℃ of deionized waters and ethanol filtering and washing, after then putting into 90 ℃ of drying in oven, namely obtain needed catalyst.Recording Surface acidity through acid base titration is 4.18mmol/g, and the sulfonate radical amount is 1.25mmol/g.
[embodiment 3]
After sucrose and diphenyl-chloromethane are taken in mass ratio at 4: 2, be placed in the stainless steel pressure still with teflon lined, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding, with deionized water and ethanol filtering and washing, with the solid that obtains 90 ℃ of drying in oven; Get this solid and the concentrated sulfuric acid and be placed in mass ratio stainless steel pressure still with teflon lined at 1: 10, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding,, with 90 ℃ of deionized waters and ethanol filtering and washing, after then putting into 90 ℃ of drying in oven, namely obtain needed catalyst.Recording Surface acidity through acid base titration is 4.25mmol/g, and the sulfonate radical amount is 1.43mmol/g.
[embodiment 4]
After furfural and phenmethylol are taken in mass ratio at 4: 2, be placed in the stainless steel pressure still with teflon lined, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding, with deionized water and ethanol filtering and washing, with the solid that obtains 90 ℃ of drying in oven; Get this solid and the concentrated sulfuric acid and be placed in mass ratio stainless steel pressure still with teflon lined at 1: 10, after uniform stirring mixes, 160 ℃ of baking oven internal reactions 24 hours, take out cooling, after grinding,, with 90 ℃ of deionized waters and ethanol filtering and washing, after then putting into 90 ℃ of drying in oven, namely obtain needed catalyst.Recording Surface acidity through acid base titration is 3.8mmol/g, and the sulfonate radical amount is 1.05mmol/g.
Claims (2)
1. the preparation method of a high efficient sulfonated carbon solid acid catalyst, at first make living beings and aromatic fully mix, and carried out solvent thermal reaction 16~72 hours in 150~200 ℃, generates the Carbon Materials that is rich in surperficial aromatic ring; Add the concentrated sulfuric acid to carry out sulfonation, synthetic surface is rich in the carbonaceous solid acid catalyst of acidic group again; Described living beings are glucose, fructose, sucrose, maltose, cellulose, furfural, starch; Described aromatic is benzyl chloride, phenmethylol, diphenyl-chloromethane, phenol, chlorobenzene; Described carbonaceous solid acid catalyst can regulate and control the amount of sulfonic acid surfactant root according to the addition of aromatic compound, its scope is at 0.5~2.4mmol/g.
2. preparation method according to claim 1, it is characterized in that: the mass ratio of described living beings and aromatic is 4: 1~3.
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CN107876088B (en) * | 2017-11-07 | 2020-06-19 | 济南大学 | Method for preparing stable solid acid catalyst by electrophilic substitution reaction |
CN110270371B (en) * | 2019-05-31 | 2021-09-28 | 青岛科技大学 | Lignin-based solid acid catalytic benzylation reaction method |
CN113333001A (en) * | 2021-05-18 | 2021-09-03 | 济南大学 | Preparation method and application of lignin-derived carbon-based solid acid catalyst |
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CN114471465B (en) * | 2022-03-09 | 2024-02-23 | 湖北第二师范学院 | Preparation method and application of coupling agent surface modified orange peel derived carbon material |
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