CN108325515A - A kind of porous carbon-based solid acid catalyst of tin supported and the preparation method and application thereof - Google Patents
A kind of porous carbon-based solid acid catalyst of tin supported and the preparation method and application thereof Download PDFInfo
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- CN108325515A CN108325515A CN201810105927.XA CN201810105927A CN108325515A CN 108325515 A CN108325515 A CN 108325515A CN 201810105927 A CN201810105927 A CN 201810105927A CN 108325515 A CN108325515 A CN 108325515A
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- solid acid
- porous carbon
- based solid
- acid catalyst
- tin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 239000011973 solid acid Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002028 Biomass Substances 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012190 activator Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 36
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 20
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920001221 xylan Polymers 0.000 claims description 6
- 150000004823 xylans Chemical class 0.000 claims description 6
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 5
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 240000008042 Zea mays Species 0.000 claims description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- 244000099147 Ananas comosus Species 0.000 claims description 2
- 235000007119 Ananas comosus Nutrition 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 240000008790 Musa x paradisiaca Species 0.000 claims description 2
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 240000000111 Saccharum officinarum Species 0.000 claims 1
- 235000007201 Saccharum officinarum Nutrition 0.000 claims 1
- FRYDSOYOHWGSMD-UHFFFAOYSA-N [C].O Chemical compound [C].O FRYDSOYOHWGSMD-UHFFFAOYSA-N 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 239000002893 slag Substances 0.000 claims 1
- 238000007171 acid catalysis Methods 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 51
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- CDVZCUKHEYPEQS-IBVPOFDWSA-N (2r,3s,4r)-2,3,4,5-tetrahydroxypentanal Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@H](O)[C@@H](O)C=O CDVZCUKHEYPEQS-IBVPOFDWSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 229920002522 Wood fibre Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 structure) Chemical compound 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 150000003742 xyloses Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
Abstract
The invention discloses porous carbon-based solid acid catalysts of a kind of tin supported and the preparation method and application thereof.After the preparation method impregnates biomass class waste and activator in tin salt aqueous solution, then by the taking-up of biomass class waste, the drying after dipping, it is subsequently placed in tube furnace, is carbonized, obtains char-forming material；Again by char-forming material as being stirred in water, sand core funnel filtration washing, drying obtains the porous carbon-based solid acid catalyst of the tin supported.It after the present invention mixes the porous carbon-based solid acid catalyst of tin supported with carbohydrate and solvent, is placed in hydrothermal reaction kettle and is reacted, reaction product obtains furfural through isolating and purifying.The porous carbon-based solid acid catalyst of tin supported of the present invention has larger specific surface area and pore volume, and higher sour density, during the catalyst is prepared furfural for catalysis, it shows excellent solid acid catalysis performance, furfural yield is 40~90%, and has and preferably recycle performance.
Description
Technical field
The invention belongs to solid acid catalyst preparation technique and application fields, and in particular to a kind of tin supported is porous carbon-based solid
Body acid catalyst and preparation method thereof and the application in catalysis carbohydrate production furfural.
Background technology
With the increasingly depleted of non-renewable primary energy-fossil energy, countries in the world start to pay attention to non-renewable energy one after another
The saving in source, and accelerate the research and development to the renewable sources of energy-biomass energy.Wood fiber biomass is because its is environmental-friendly, storage
The advantages that amount is abundant, cheap, will play an important role on industrial development, problem of environmental pollution.
Biomass can prepare kinds of platform compound, wherein furfural, be one of furans system important derivatives, by agricultural and sideline production
Product gained poly-pentose after high temperature acidolysis is dehydrated and obtains, and is that one kind being widely used in petroleum industry, Chemical Manufacture, medicine, food
And the important Organic Chemicals and chemical solvent of the industries such as synthesis macromolecule.Dilute sulphur is mainly used in industrial production at present
Acid catalysis prepares furfural, but due to its with corrosivity, be not easily recycled, waste liquor contamination is big the problems such as, and in order to adapt to country
It is extremely urgent to find a kind of solid acid catalyst of green high-efficient for the demand of green chemical industry.Research about solid catalyst has
Many kinds, such as acid cation exchange resin, metal oxide, H-type zeolite, carbon-based solid acid.Carbon-based solid acid early stage quilt
Applied to the preparation of biodiesel, and recent years is just applied in the production of furfural, in these researchs, is seldom related to porous
Carbon-supported catalysts, wherein Zhu et al. (Y.Zhu, RSC Adv, 2017,729916) are prepared for a kind of porous C catalyst, be with
Resorcinol-formaldehyde resin is carbon source, and with mantle plate method drilling, carbon source does not have the feature of environmental protection.And biomass have it is rich, can
As green carbon source.
In addition, the research for being applied to furfural production about tin supported carbon-based solid acid catalyst also has not been reported.Tin from
During son can act on xylose dehydration generation furfural as a kind of Lewis acid, liquid acid SnCl4, which is considered as one kind, to be had
Effect ground catalysis xylose and biomass material prepare the catalyst of furfural, while tin supported Montmorillonite Solid Acid is also proved to furfural
Production have good facilitation.Therefore tin is carried on porous carbon as a kind of non-noble metal j element and prepares solid acid and urge
Agent has a good application prospect.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of porous carbon-based solid acid catalysis of tin supported
Agent, the porous carbon-based solid acid catalyst of the tin supported have larger specific surface area, suitable for the porous structure of reaction medium transmission
With good catalytic performance, and good stability is shown.
The present invention also aims to provide the method for preparing the porous carbon-based solid acid catalyst of a kind of tin supported.
Another object of the present invention, which also resides in, provides a kind of answering for the porous carbon-based solid acid catalyst of tin supported
With specially using the application of the above-mentioned porous carbon-based solid acid catalyst catalysis carbohydrate production furfural of tin supported.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of the porous carbon-based solid acid catalyst of tin supported, including following preparation process：
Biomass class waste and activator are impregnated 1~3 week in tin salt aqueous solution, then by the biomass after dipping
Class waste takes out and 60~80 DEG C of dry 6~12h in baking oven, is subsequently placed in tube furnace, heating carbonization 2 under nitrogen atmosphere
~10h, obtains char-forming material；Char-forming material is obtained as 3~12h, sand core funnel filtration washing, drying in water, is stirred again
The porous carbon-based solid acid catalyst of tin supported.
Preferably, the biomass class waste is furfural dregs, bean dregs, vinasse, banana skin, granatum, pineapple peel, corn
One or more of palpus, shrimp shell and crab shell.
Preferably, the activator is H3PO4Or ZnCl2。
Preferably, the pink salt is SnCl4、SnCl2、Sn(NO3)2And SnSO4One or more of.
Preferably, in the biomass class waste, activator, pink salt and tin salt aqueous solution in tin salt aqueous solution
The mass ratio of water is 1: 0.5~4: 0.5~4: 10~100.
Preferably, the carburizing temperature is 400~800 DEG C.
A kind of porous carbon-based solid acid catalyst of tin supported, is prepared by preparation method described in any of the above-described.
Preferably, the surface area of the porous carbon-based solid acid catalyst of the tin supported is 800~1200m2/ g, pore volume are
0.1~0.3cm3/ g, sour density are 0.2~3mmol/g.
The porous carbon-based solid acid catalyst of tin supported of the present invention has larger specific surface area (800~1200m2/ g) and
Pore volume (0.1~0.3cm3/ g) and higher sour density (0.2~3mmol/g), which is prepared into chaff for catalysis
During aldehyde, excellent solid acid catalysis performance is shown, and have and preferably recycle performance.
A method of furfural is prepared using the porous carbon-based solid acid catalyst catalysis carbohydrate of above-mentioned tin supported, is wrapped
Include following preparation process：
By carbohydrate, the porous carbon-based solid acid catalyst of the tin supported and solvent with mass ratio be 0.01~
Mixed at 0.05: 0.001~0.03: 1, then is placed in hydrothermal reaction kettle, and 30~180min is reacted at 140~200 DEG C；Instead
It after answering, is quickly cooled down with ice water, reaction mixture is centrifuged, isolate the porous carbon-based solid acid catalysis of tin supported
Agent；Product liquid is filtered with filter, and high performance liquid chromatography is used in combination to be detected, and collection obtains furfural.
Preferably, the carbohydrate is in xylose, arabinose, xylan, hemicellulose, corncob and bagasse
One kind.
Preferably, the solvent is water, dimethyl sulfoxide (DMSO), acetone, dichloromethane, n,N-Dimethylformamide, N, N- bis-
The mixture of one or both of methylacetamide, N-Methyl pyrrolidone, gamma-valerolactone and gamma-butyrolacton.
Preferably, it is 40~90% to be catalyzed the furfural yield being prepared, and catalyst recycling performance is good.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) present invention is prepared in the method for the porous carbon-based solid acid catalyst of tin supported, using biomass class waste as
The raw materials for production of the porous carbon-based solid acid catalyst of tin supported, realization are turned waste into wealth, and solve the problems, such as disposal of pollutants；
(2) the porous carbon-based solid acid catalyst of tin supported of the invention has loaded metallic tin so that the catalyst has
The attribute of Lewis acid, at the same pass through adjust tin-salt solution concentration and ingredient, thus it is possible to vary the acidic site intensity of catalyst with point
Cloth, optimization catalyst prepare the performance of furfural；
(3) the porous carbon-based solid acid catalyst of tin supported of the invention has porous structure (average pore size is 2~10nm),
Reactant can be increased to contact with the effective of catalyst activity position, improve the transformation efficiency of raw material, while product chaff can be improved
Effective diffusion of aldehyde is left away, and product is avoided to occur the side reactions such as further to polymerize and hydrolyze on acid centre；
(4) method that the present invention prepares furfural using the porous carbon-based solid acid catalyst catalysis carbohydrate of tin supported
In, after the completion of reaction, carbon-based solid acid catalyst can be separated easily from reaction medium, and activity is high,
It is reusable, help to realize the process for cleanly preparing of furfural.
Description of the drawings
Fig. 1 is the XRD spectra of the porous carbon-based solid acid catalyst of tin supported prepared in embodiment 1；
Fig. 2 is the N of the porous carbon-based solid acid catalyst of tin supported prepared in embodiment 12Adsorption-desorption attached drawing；
Fig. 3 is the graph of pore diameter distribution of the porous carbon-based solid acid catalyst of tin supported prepared in embodiment 1；
Fig. 4 is the FTIR and raman spectrum of the porous carbon-based solid acid catalyst of tin supported prepared in embodiment 1.
Specific implementation mode
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but the present invention
Protection domain and specific implementation mode are without being limited thereto.
Embodiment 1
(1) the porous carbon-based solid acid catalyst of tin supported is prepared：By 1g furfural dregs, 0.5g ZnCl2With 0.5g SnCl4With
10g ultra-pure waters mix, and impregnate one week, 60 DEG C of dry 6h, are subsequently placed in tube furnace, are warming up under nitrogen atmosphere in baking oven
400 DEG C of charing 2h, obtain carbonization furfural dregs；Furfural dregs will be carbonized as in water, stir 3h with stirrer, sand core funnel crosses diafiltration
It washs, dries, obtain required solid acid catalyst.
The acidity of the catalyst of preparation is 1.43mmol/g, and tin load capacity is 9.81wt%.
The XRD spectra of the porous carbon-based solid acid catalyst of tin supported of preparation is as shown in Figure 1, as seen from Figure 1, be catalyzed
Tin atom has been loaded in agent.
The N2 adsorption/desorption curves figure of the porous carbon-based solid acid catalyst of tin supported of preparation is as shown in Fig. 2, can by Fig. 2
Know, catalyst and the nitrogen of preparation have strong effect power, i.e., with the presence of more micropore in catalyst.At the same time it can also see song
Occur hysteresis loop in line, can speculate that in catalyst be slit pore, is some similar holes generated by layer structure.
By survey calculation it is found that the porous carbon-based solid acid catalyst of tin supported prepared has higher specific surface area, reach
To 836.95m2/g。
The graph of pore diameter distribution of the porous carbon-based solid acid catalyst of tin supported of preparation is as shown in figure 3, from graph of pore diameter distribution (figure
3) average as can be seen that catalyst mainly contains micropore (＜ 2nm) and mesoporous (2nm-50nm), average pore size 3.46nm in
Pore volume is 0.12cm3/g；The molecular diameter of xylose is 0.68nm, and the molecular diameter of furfural is 0.57nm, it may thus be appreciated that this is urged
Agent is conducive to xylose and the activated centre of catalyst surface comes into full contact with, and is also conducive to the removal of furfural product.
The FTIR of the porous carbon-based solid acid catalyst of tin supported of preparation is with raman spectrum as shown in figure 4, Raman spectrum can
To distinguish the allotrope of carbon material, D wave bands (1360~1370cm-1) represent sp3 keys (tetrahedral structure) or hydridization and lack
Sunken sp2 keys (graphene edge structure), G-band (1580~1590cm-1) sp2 keys (plane body structure) are represented, generally use the peaks D
With the intensity at the peaks G than weighing the degree of disorder of carbon material, as shown in Figure 4, the degree of disorder of the catalyst is 2.1.
(2) catalyst Furfural Production from Xylose：The porous carbon-based solid acid of tin supported prepared by 0.1g xyloses, 0.01g
After catalyst, the mixing of 10mL dimethyl sulfoxide (DMSO)s, it is placed in hydrothermal reaction kettle, reacts 30min at 140 DEG C；After reaction, it uses
Ice water is quickly cooled down, and reaction mixture is centrifuged, and isolates the porous carbon-based solid acid catalyst of tin supported；Product liquid is used
0.22 μm of filter filtering, is used in combination high performance liquid chromatography to be detected, collection obtains furfural.
(3) recycling of catalyst：The porous carbon-based solid acid catalyst of tin supported out will be centrifuged with ultrapure
After water washing, drying is re-used in the operation of catalysis xylose production furfural.
Using high performance liquid chromatography, furfural percentage yield, xylose rate and furfural selectivity are calculated according to the following formula.
Furfural yield=(initial moles of molal quantity/xylose of furfural in solution) × 100%；
Xylose rate=(initial moles of (initial moles of xylose-xylose from solutions molal quantity)/xylose) ×
100%；
Furfural selectivity=(furfural yield/xylose rate) × 100%；
By calculating, furfural yield 40.5%, xylose rate is 50.7%, and furfural is selectively 79.9%.Catalysis
Catalytic performance reduces by 1.2% after agent reuses 1 time；After catalyst reuses 2 times, catalytic performance reduces by 2.5%, shows to urge
Recycling property of agent is good.
Embodiment 2
(1) the porous carbon-based solid acid catalyst of tin supported is prepared：By 1g bean dregs, 2g H3PO4With 2g SnCl2It is ultrapure with 30g
Water mixes, and impregnates two weeks, 70 DEG C of dry 9h, are subsequently placed in tube furnace in baking oven, and 600 DEG C of charcoals are warming up under nitrogen atmosphere
Change 6h, obtains carbonization bean dregs；Carbonization bean dregs are obtained into tin supported as 6h, sand core funnel filtration washing, drying in water, is stirred
Porous carbon-based solid acid catalyst.
The acidity of the catalyst of preparation is 1.09mmol/g, specific surface area 986.51m2/ g, tin load capacity are
8.56wt%；It includes micropore and mesoporous porous structure, pore volume 0.23cm that catalyst, which has,3/ g, central hole structure are put down
Equal aperture is 4.69nm.
(2) catalyst xylan prepares furfural：The porous carbon-based solid of tin supported prepared by 0.3g xylans, 0.1g
After acid catalyst, the mixing of 10mL dichloromethane, it is placed in hydrothermal reaction kettle, reacts 100min at 170 DEG C；After reaction,
It is quickly cooled down with ice water, reaction mixture is centrifuged, isolate the porous carbon-based solid acid catalyst of tin supported；Product liquid
It is filtered with 0.22 μm of filter, high performance liquid chromatography is used in combination to be detected, collection obtains furfural.
(3) recycling of catalyst：The porous carbon-based solid acid catalyst of tin supported out will be centrifuged with ultrapure
After water washing, drying is re-used in the operation of catalysis xylan production furfural.
Using high performance liquid chromatography, furfural percentage yield and xylose percentage yield are calculated according to the following formula.
Furfural yield=(initial moles of xylose in molal quantity/xylan of furfural in solution) × 100%；
By calculating, furfural yield 63.9%.Catalytic performance reduces by 0.9% after catalyst reuses 1 time；Catalyst
After recycling 2 times, catalytic performance reduces by 1.6%, shows that catalyst recycling is good.
Embodiment 3
(1) the porous carbon-based solid acid catalyst of tin supported is prepared：By 1g corn stigmas, 4g H3PO4 and 4g SnCl4And 100mL
Ultra-pure water mixes, and impregnates three weeks, 80 DEG C of dry 12h, are subsequently placed in tube furnace, are warming up under nitrogen atmosphere in baking oven
800 DEG C of charing 10h, obtain carbonization corn stigma；Carbonization corn stigma is dried as 12h, sand core funnel filtration washing in water, is stirred
It is dry, obtain the porous carbon-based solid acid catalyst of tin supported.
The acidity of the catalyst of preparation is 1.09mmol/g, specific surface area 1026.35m2/ g, tin load capacity are
10.26wt%；It includes micropore and mesoporous porous structure, pore volume 0.33cm that catalyst, which has,3/ g, central hole structure are put down
Equal aperture is 4.82nm.
(2) catalyst corncob prepares furfural：The porous carbon-based solid of tin supported prepared by 0.5g corncobs, 0.3g
After acid catalyst, the mixing of 10mL gamma-valerolactones, it is placed in hydrothermal reaction kettle, reacts 180min at 200 DEG C；After reaction,
It is quickly cooled down with ice water, reaction mixture is centrifuged, isolate the porous carbon-based solid acid catalyst of tin supported；Product liquid
It is filtered with 0.22 μm of filter, high performance liquid chromatography is used in combination to be detected, collection obtains furfural.
(3) recycling of catalyst：The porous carbon-based solid acid catalyst of tin supported out will be centrifuged with ultrapure
After water washing, drying is re-used in the operation of catalysis corncob production furfural.
Using high performance liquid chromatography, furfural percentage yield and xylose percentage yield are calculated according to the following formula.
Furfural yield=(initial moles of xylose in molal quantity/corncob of furfural in solution) × 100%；
By calculating, furfural yield 78.9%.Catalytic performance reduces by 1.34% after catalyst reuses 1 time；Catalysis
After agent reuses 2 times, catalytic performance reduces by 1.97%, shows that catalyst recycling is good.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the porous carbon-based solid acid catalyst of tin supported, which is characterized in that including following preparation process：
Biomass class waste and activator are impregnated 1~3 week in tin salt aqueous solution, then the biomass class after dipping is given up
Gurry takes out and 60~80 DEG C of dry 6~12h in baking oven, is subsequently placed in tube furnace, and the carbonization 2 that heats up under nitrogen atmosphere~
10h obtains char-forming material；Char-forming material is obtained into institute as 3~12h, sand core funnel filtration washing, drying in water, is stirred again
State the porous carbon-based solid acid catalyst of tin supported.
2. a kind of preparation method of the porous carbon-based solid acid catalyst of tin supported according to claim 1, which is characterized in that
The biomass class waste is in furfural dregs, bean dregs, vinasse, banana skin, granatum, pineapple peel, corn stigma, shrimp shell and crab shell
More than one.
3. a kind of preparation method of the porous carbon-based solid acid catalyst of tin supported according to claim 1, which is characterized in that
The activator is H3PO4Or ZnCl2；The pink salt is SnCl4、SnCl2、Sn(NO3)2And SnSO4One or more of.
4. a kind of preparation method of the porous carbon-based solid acid catalyst of tin supported according to claim 1, which is characterized in that
The biomass class waste, activator, water in pink salt and tin salt aqueous solution in tin salt aqueous solution mass ratio be 1:
0.5~4: 0.5~4: 10~100.
5. a kind of preparation method of the porous carbon-based solid acid catalyst of tin supported according to claim 1, which is characterized in that
The temperature of the carbonization is 400~800 DEG C.
6. a kind of porous carbon-based solid acid catalyst of tin supported made from Claims 1 to 5 any one of them preparation method,
It is characterized in that, surface area is 800~1200m2/ g, pore volume are 0.1~0.3cm3/ g, sour density are 0.2~3mmol/g.
7. a kind of porous carbon-based solid acid catalyst catalysis carbohydrate of tin supported using described in claim 6 prepares furfural
Method, which is characterized in that including following preparation process：
By carbohydrate, the porous carbon-based solid acid catalyst of the tin supported and solvent with mass ratio for 0.01~0.05
: mixed at 0.001~0.03: 1, then is placed in hydrothermal reaction kettle, and 30~180min is reacted at 140~200 DEG C；Reaction knot
Shu Hou is quickly cooled down with ice water, and reaction mixture is centrifuged, and isolates the porous carbon-based solid acid catalyst of tin supported；Liquid
Body product is filtered with filter, and collection obtains furfural.
8. the porous carbon-based solid acid catalyst catalysis carbohydrate of a kind of tin supported according to claim 7 prepares furfural
Method, which is characterized in that the carbohydrate be xylose, arabinose, xylan, hemicellulose, corncob and sugarcane
One kind in slag.
9. the porous carbon-based solid acid catalyst catalysis carbohydrate of a kind of tin supported according to claim 7 prepares furfural
Method, which is characterized in that the solvent be water, dimethyl sulfoxide (DMSO), acetone, dichloromethane, n,N-Dimethylformamide, N, N-
The mixture of one or both of dimethylacetylamide, N-Methyl pyrrolidone, gamma-valerolactone and gamma-butyrolacton.
10. being catalyzed carbon hydrate according to a kind of porous carbon-based solid acid catalyst of tin supported of claim 7~9 any one of them
The method that object prepares furfural, which is characterized in that furfural yield is 40~90%.
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