CN106215969A - A kind of cerium dopping solid super acid catalyst and preparation method thereof - Google Patents
A kind of cerium dopping solid super acid catalyst and preparation method thereof Download PDFInfo
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- CN106215969A CN106215969A CN201610592153.9A CN201610592153A CN106215969A CN 106215969 A CN106215969 A CN 106215969A CN 201610592153 A CN201610592153 A CN 201610592153A CN 106215969 A CN106215969 A CN 106215969A
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000007787 solid Substances 0.000 title claims abstract description 44
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003930 superacid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 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 19
- 239000008103 glucose Substances 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 31
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- -1 cerium ion Chemical class 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- ZJJWXAUNWSORPB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O ZJJWXAUNWSORPB-UHFFFAOYSA-N 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 abstract description 22
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006317 isomerization reaction Methods 0.000 abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 229910000420 cerium oxide Inorganic materials 0.000 abstract 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 8
- 229930091371 Fructose Natural products 0.000 description 7
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 7
- 239000005715 Fructose Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-VANKVMQKSA-N aldehydo-L-glucose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-VANKVMQKSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B01J35/61—
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
Abstract
The invention belongs to multifunction solid catalyst field, specifically provide a kind of cerium dopping solid super acid catalyst and preparation method thereof.To there is the ZrO of high catalytic reaction activity2/SO4 2‑Type solid super-strong acid and cerium oxide nanoparticles are supported on silicon-based mesoporous molecular sieve SBA 15, overcome present in prior art that conventional solid superacid catalysis glucose isomerization degree is the highest, 5 HMF yield are undesirable, specific surface area is low, course of reaction is easily reunited, cause the shortcomings such as avtive spot loss rate is too high, regenerability is poor, it is provided that a kind of soda acid difunctionalization, catalytic reaction activity height, bigger serface, stable rare-earth cerium doped solid super acid catalyst.
Description
Technical field
The present invention relates to solid catalyst field, be related specifically to a kind of soda acid difunctionalization, the rare earth of high-specific surface area
Doping solid super acid catalyst and preparation method thereof.
Background technology
5 hydroxymethyl furfural (5-hydroxymethylfurfural, 5-HMF), is containing active aldehyde in a kind of structural formula
The biomass-based platform chemicals of base, hydroxyl and furan nucleus, can derive numerous downstream product by further reaction,
It is to connect the chemical and petrochemical key intermediate of biomass.Generally, with fructose as raw material, available relatively by dehydration
The 5-HMF of high yield.But fructose is expensive, its application in field of food simultaneously is more and more extensive, uses fruit in a large number
It is the most infeasible that sugar prepares 5-HMF for raw material, and food supply also can produce certain competition.Therefore, with cheap, money
The abundant glucose in source is that raw material is efficiently prepared 5-HMF and become current study hotspot.
Glucose is the isomers of fructose, and therefore, preparing 5-HMF with glucose for raw material, to relate generally to glucose different
Structure turns to fructose, and the fructose that reaction obtains is dehydrated the two step cascade reactions generating 5-HMF.Wherein, existAcid (B-acid)
Under the catalytic action of avtive spot, fructose dehydration generates the reaction of 5-HMF and is easy to occur, and the isomerisation degree of glucose is
Affect the key factor of cascade reaction.Research shows, in catalyst, the existence of Lewis (L acid) or basic site is beneficial to Portugal
Grape sugar is isomerized to fructose, and then improves the productivity of 5-HMF.Solid super-strong acid is B-acid and L acid compound action in some way and shape
The novel acid of one become, also has certain alkalescence, and its active center is contained in B-acid center (Bronsted acid center) and L acid simultaneously
The heart (Lewis acid centers), in catalytic reaction process, the two synergism, has superpower acidity and high catalytic activity, becomes solid
Focus in the research of body acid catalyst.For the solid super acid catalyst occurred in this research field, mainly there is following a few side
The problem in face needs to solve: (1) glucose isomerization degree is the most relatively low, shows as reaction substrate conversion ratio the highest, and 5-HMF produces
Rate is undesirable；(2) specific surface area of catalyst is low, and avtive spot load capacity is few；(3) in course of reaction, catalyst is easily reunited, and leads
Causing avtive spot loss rate too high, regenerability is poor.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of rare-earth cerium doped solid super acid catalyst, overcome existing skill
Present in art, conventional solid superacid catalysis glucose isomerization degree is the highest, 5-HMF productivity is undesirable, specific surface area is low,
Course of reaction is easily reunited, causes the shortcomings such as avtive spot loss rate is too high, regenerability is poor, it is provided that a kind of soda acid is difunctional
Change, catalytic reaction activity height, bigger serface, stable rare-earth cerium doped solid super acid catalyst.
The preparation method of a kind of rare-earth cerium doped solid super acid catalyst, comprises the steps of
(1) take dried silicon-based mesoporous molecular sieve SBA-15 to disperse in organic solvent, under conditions of stirring, to mixed
Fit system is added dropwise over hydrolyzable zirconium salt solution；Gained reaction system through hydrolysis completely after, products therefrom is washed, from
The heart is collected and vacuum drying, obtains the zirconium oxide product (1ML-ZrO of SBA-15 load monolayer2@SBA-15)；
(2) by step (1) gained 1ML-ZrO2Silicon-based mesoporous molecular sieve SBA-15 in@SBA-15 alternative steps (1), repeats
Hydrolysis in step (1), obtains the zirconium oxide product (2ML-ZrO of SBA-15 load two-layer2@SBA-15)；
(3) by the 2ML-ZrO of step (2) gained2@SBA-15 is immersed in sulfuric acid solution, after having soaked, centrifugal is received
Collection product, vacuum dried is placed in Muffle furnace, temperature programming to calcining heat, obtains the 2ML-that SBA-15 loads after calcining
ZrO2/SO4 2-Type solid super-strong acid (2SZ@SBA-15)；
(4) configure certain density cerium solution, the 2SZ@SBA-15 sample of step (3) gained is immersed in described cerium salt
In solution, after ultrasonic disperse is uniform, it is evaporated solution；
(5) step (4) gained sample is placed in Muffle furnace, temperature programming to calcining heat, after calcining, obtains cerium
Doping solid super acid catalyst (CeO2-2SZ@SBA-15)。
In step (1), described organic solvent is normal hexane, hexamethylene, normal propyl alcohol or isopropanol；Hydrolyzable zirconates is positive third
Alcohol zirconium or zirconium iso-propoxide.
In step (1), described SBA-15, hydrolyzable zirconates, the ratio of organic solvent are 0.2-10g:1.0-58.5g:10-
600mL, hydrolysising reacting temperature is 50-120 DEG C, and the response time is 6-48h, and vacuum drying temperature is 40-120 DEG C.
In step (2), described 1ML-ZrO2@SBA-15, hydrolyzable zirconates, the ratio of organic solvent are 0.2-10g:0.6-
28.5g:10-600mL, hydrolysising reacting temperature is 50-120 DEG C, and the response time is 6-48h, and vacuum drying temperature is 40-120
℃。
In step (3), described sulfuric acid solution concentration range is 0.005-0.25mol/L.
In step (3), described 2ML-ZrO2@SBA-15, the ratio of sulfuric acid solution are 0.2-1.8g:10-90mL, during immersion
Between be 4-24h；Vacuum drying temperature is 60-150 DEG C；Heating rate is 1.0-10 DEG C/min, and calcining heat is 400-1200
DEG C, calcination time 1-10h.
In step (4), described cerium solution is cerous nitrate saline solution or cerous sulfate saline solution, in described cerium solution cerium from
Sub-concentration is 0.1-10g/L.
In step (4), described 2SZ@SBA-15, the ratio of cerium solution are 0.1-10g:10-300mL, described in be evaporated molten
Temperature during liquid is 25-180 DEG C.
In step (5), described heating rate is 1.0-10 DEG C/min, and calcining heat is 350-1000 DEG C, calcination time 1-
8h。
Rare-earth cerium doped solid super acid catalyst prepared by the present invention, its aperture is 4.5nm, and acidity value is
0.28mmol·g-1, basicity value is 0.12mmol g-1。
It is 5-HMF's that rare-earth cerium doped solid super acid catalyst prepared by the present invention is applied to be catalyzed glucose degradation
Reaction.It is an advantage of the current invention that:
(1) by ZrO2/SO4 2-Type solid super-strong acid is supported on silicon-based mesoporous molecular sieve SBA-15, not only increases catalysis
The specific surface area of agent, enhances the heat stability of catalyst simultaneously, and catalyst regenerability is significantly improved.
(2) introducing of cerium improves the basicity of solid super-strong acid, and gained solid catalyst not only has superpower acidity (B
Acid and L acid), there is certain alkalescence simultaneously, in catalytic degradation glucose prepares 5-HMF course of reaction ZhongBSuan center, L acid
The heart and basic site synergism, considerably improve the isomerisation degree of glucose, the productivity of 5-HMF and selectivity.
(3) present invention uses technology, preparation technology simply, easily operate, production suitable for industrialized.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (a) and transmission electron microscope (b) figure of prepared solid catalyst in embodiment 1.
Radix Rumicis (a) He little Jiao (b) X-ray diffractogram of prepared solid catalyst in Fig. 2 embodiment 1.
Fig. 3 is the nitrogen adsorption desorption curve figure of prepared solid catalyst in embodiment 1, and wherein insert pictures is hole
Footpath scattergram.
Fig. 4 is SBA-15 carrier in embodiment 1, gained 2ML-Zr O in step (2)2@SBA-15,2SZ@in step (3)
SBA-15, and final prepared solid catalyst CeO2The xps energy spectrum figure of-2SZ@SBA-15.
Fig. 5 is the NH of prepared solid catalyst in embodiment 13(a) and CO2(b) temperature programming desorbing accompanying drawing.
Fig. 6 is the infrared figure of original position pyridine of prepared solid catalyst in embodiment 1.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is also
It is not limited to this.
Embodiment 1
(1) preparation of rare-earth cerium doped solid super acid catalyst
0.2g silicon-based mesoporous molecular sieve SBA-15 after drying is dispersed in 10mL normal hexane, under conditions of stirring,
The zirconium-n-propylate of 1.0g it is added dropwise in mixed system.Reaction system is hydrolyzing 6h after at 50 DEG C, and products therefrom is through distillation
Water washs 3-5 time, centrifugal collection and 40 DEG C of vacuum drying and obtains SBA-15 and load the zirconium oxide product (1ML-ZrO of monolayer2@
SBA-15)。
0.2g previous step gained 1ML-ZrO2@SBA-15 is dispersed in 10mL normal hexane again, under conditions of stirring,
The zirconium-n-propylate of 0.6g it is added dropwise in mixed system.Reaction system is hydrolyzing 6h after at 50 DEG C, and products therefrom is through distillation
Water washs 3-5 time, centrifugal collection and 40 DEG C of vacuum drying and obtains SBA-15 and load the zirconium oxide product (2ML-ZrO of two-layer2@
SBA-15)。
2ML-ZrO by 0.2g previous step gained2@SBA-15 is immersed in the sulfuric acid solution of 10mL, 0.005mol/L,
Soak centrifugal collected product after 4h to be placed in Muffle furnace through 60 DEG C of vacuum drying, with the heating rate of 1.0 DEG C/min from room
Temperature rise to 400 DEG C, and at a temperature of 400 DEG C, keep 1h, obtain the 2ML-ZrO of SBA-15 load2/SO4 2-Type solid super-strong acid
(2SZ@SBA-15)。
Configuration cerium ion concentration is the cerous nitrate solution of 0.1g/L, by the 2SZ@SBA-15 sample of 0.1g previous step gained
It is immersed in the above-mentioned cerium solution of 10mL, after ultrasonic disperse is uniform, stands under 25 DEG C of room temperature environments, treat that solution is evaporated.
Previous step gained sample is placed in Muffle furnace, is increased to 350 with the heating rate of 1.0 DEG C/min from room temperature
DEG C, and at a temperature of 350 DEG C, keep 1h, obtain rare-earth cerium doped solid super acid catalyst (CeO2-2SZ@SBA-15)。
Be can be seen that prepared solid catalyst is corynebacterium by Fig. 1 scanning electron microscope (SEM) photograph, its length is about about 1 μm,
Diameter is about about 360nm；Can clearly observe that from transmission electron microscope picture solid catalyst surface distribution is the most orderly
Mesoporous, aperture is about about 4.5nm.
By Wide angle X-ray diffraction figure in Fig. 2 can be seen that, prepared solid catalyst only has the spy of SBA-15 carrier
Levy diffraction maximum, loaded ZrO does not occur2And CeO2Characteristic peak, this phenomenon is likely due to loaded ZrO2With colloid
State occurs, and granule is the least, and CeO2The load capacity of nanoparticle is seldom and dispersion is the highest, cause its characteristic peak be difficult to by
Detect.The meso-hole structure of the solid catalyst prepared by small angle X-ray diffraction figure proof still remains the typical case of high-sequential
Hexagonal symmetry.
In Fig. 3, nitrogen adsorption desorption belongs to typical meso-hole structure, and prepared solid catalyst specific surface area is
227.7cm2g-1, its aperture integrated distribution result obtained by about 4.4nm, and transmission electron microscope observing is basically identical simultaneously.
Gained 2ML-ZrO in step (2) in Fig. 42The appearance of Zr 3d signal peak in the xps energy spectrum figure of@SBA-15, it was demonstrated that
ZrO2Successfully it is supported on SBA-15；By the sulfurization of step (3), the appearance of S 2p signal peak proves to be successfully prepared
, meanwhile, there is the signal peak of Ce 3d in solid super-strong acid in final prepared solid catalyst, it was demonstrated that the method successfully incite somebody to action
There is the solid super-strong acid 2ML-ZrO of catalysis activity2/SO4 2-And CeO2Nano-particle is supported on SBA-15, prepares CeO2-
2SZ@SBA-15 solid catalyst.
By (a) NH in Fig. 53And CO2B () temperature programming desorption curve can calculate prepared solid catalyst
Acidity value is 0.28mmol g-1, basicity value is 0.12mmol g-1, it was demonstrated that prepared CeO2-2SZ@SBA-15 solid catalyst
It it is a kind of soda acid difunctionalization solid catalyst.
By CeO in Fig. 62It can be seen that prepared in the original position pyridine infrared spectrogram of-2SZ@SBA-15 solid catalyst
Catalyst have bronsted acid (1542cm simultaneously-1) and lewis acid (1447cm-1) characteristic peak of avtive spot, it was demonstrated that should
Containing B-acid and two kinds of acidic sites of L acid while solid catalyst prepared by method.More than characterizing proof, this invention is permissible
Successfully preparing a kind of, solid catalyst of basic site acid containing B/L, the existence of L acid site and basic site can be very
Improve the isomerization of glucose in big degree, thus strengthen catalyst activity.
(2) catalytic test
Generally, the hydrolysis of the monosaccharide such as glucose is carried out in dimethyl sulfoxide (DMSO), and DMSO is in course of reaction
In not only serve as solvent, the most certain catalytic effect.But, owing to DMSO is a kind of high boiling solvent, have certain
Toxicity, environment can be caused certain harm, the product that simultaneous reactions obtains to be difficult to separating-purifying by a large amount of uses.The present invention uses
The mixed system of isopropanol and DMSO serves as solvent, can effectively reduce the utilization rate of DMSO.The glucose of 50mg is joined
In the mixed solution system that isopropanol (4.5mL) and DMSO (0.5mL) form, then 20mg catalyst is joined reaction system
In, system, in the oil bath pan of 120 DEG C, reacts 6h under the rotating speed of 1200r/min.After having reacted, products therefrom constant volume is to holding
In the middle of measuring bottle, after be diluted to 5000 times, detect by efficient liquid phase (HPLC).Testing conditions is: column temperature: 30 DEG C；Flowing phase
For water and methanol, ratio is 3:7；Flow velocity is 0.7mL/min；Detection wavelength is 283nm；Sample size is 22.5 μ L.
Sample standard curve is that (y represents the concentration that 5-HMF is corresponding to y=0.0019x+3.4903, and unit is that mg/L, x represent
Peak area), the concentration of 5-HMF can be calculated according to standard curve, be converted into molar concentration.The calculation of yield formula of 5-HMF
For Y (molar yield)=n1/no× 100, n1Represent the molar yield of 5-HMF, noRepresent the mole of glucose.Result of calculation
Show that product can reach higher productivity, be 66.5%.
(3) regeneration test
It, through being centrifuged, separate, being drying to obtain regeneration catalyst, is put into by catalytic test gained reactant liquor again
State in catalytic test, test its catalytic effect；Carry out four regeneration tests in this approach.Measured catalysate detection method
With experimental condition with above-mentioned catalytic test.
Result shows: in regenerative process, loss of catalyst activity is relatively low, regenerates in one to five process of the test, and glucose turns
The productivity turning to 5-HMF is followed successively by 66.4%, 66.2%, 65.9%, 65.6% and 65.2%.
Embodiment 2
(1) preparation of rare-earth cerium doped solid super acid catalyst
5.0g silicon-based mesoporous molecular sieve SBA-15 after drying is dispersed in 300mL normal hexane, under conditions of stirring,
The zirconium-n-propylate of 25g it is added dropwise in mixed system.Reaction system is hydrolyzing 30h after at 80 DEG C, and products therefrom is through distillation
Water washs 3-5 time, centrifugal collection and 80 DEG C of vacuum drying and obtains SBA-15 and load the zirconium oxide product (1ML-ZrO of monolayer2@
SBA-15)。
5.0g previous step gained 1ML-ZrO2@SBA-15 is dispersed in 300mL normal hexane again, in the condition of stirring
Under, in mixed system, it is added dropwise over the zirconium-n-propylate of 15g.Reaction system is hydrolyzing 30h after at 80 DEG C, and products therefrom is through steaming
Distilled water is washed 3-5 time, centrifugal collection and 80 DEG C of vacuum drying and is obtained SBA-15 and load the zirconium oxide product (2ML-ZrO of two-layer2@
SBA-15)。
2ML-ZrO by 1.0g previous step gained2@SBA-15 is immersed in the sulfuric acid solution of 50mL, 0.1mol/L, leaching
After bubble 15h, centrifugal collected product is placed in Muffle furnace through 80 DEG C of vacuum drying, with the heating rate of 5.0 DEG C/min from room temperature
It is increased to 800 DEG C, and at a temperature of 800 DEG C, keeps 5h, obtain the 2ML-ZrO of SBA-15 load2/SO4 2-Type solid super-strong acid
(2SZ@SBA-15)。
Configuration cerium ion concentration is the cerous nitrate solution of 5.0g/L, by the 2SZ@SBA-15 sample of 5.0g previous step gained
It is immersed in the above-mentioned cerium solution of 150mL, after ultrasonic disperse is uniform, at 120 DEG C, is evaporated solution.
Previous step gained sample is placed in Muffle furnace, is increased to 700 with the heating rate of 5.0 DEG C/min from room temperature
DEG C, and at a temperature of 700 DEG C, keep 5h, obtain rare-earth cerium doped solid super acid catalyst (CeO2-2SZ@SBA-15)。
(2) catalytic performance analysis test
Catalytic performance analysis test method is with embodiment 1, and result shows, within the response time of 6h, product can reach relatively
High productivity is 66.7%, and the catalytic performance of this catalyst is higher.
(3) regenerability analysis test
Regenerability analysis test method is with embodiment 1.Result shows: in regenerative process, loss of catalyst activity is relatively low,
Regenerate in one to five process of the test, glucose be converted into the productivity of 5-HMF be followed successively by 66.5%, 66.4%, 66.2%,
66.0% and 65.8%.Embodiment 3
(1) preparation of rare-earth cerium doped solid super acid catalyst
10g silicon-based mesoporous molecular sieve SBA-15 after drying is dispersed in 600mL normal hexane, under conditions of stirring,
The zirconium-n-propylate of 58.5g it is added dropwise in mixed system.Reaction system is hydrolyzing 48h after at 120 DEG C, and products therefrom is through steaming
Distilled water is washed 3-5 time, centrifugal collection and 120 DEG C of vacuum drying and is obtained SBA-15 and load the zirconium oxide product (1ML-ZrO of monolayer2@
SBA-15)。
10g previous step gained 1ML-ZrO2@SBA-15 is dispersed in 600mL normal hexane again, under conditions of stirring,
The zirconium-n-propylate of 28.5g it is added dropwise in mixed system.Reaction system is hydrolyzing 48h after at 120 DEG C, and products therefrom is through steaming
Distilled water is washed 3-5 time, centrifugal collection and 120 DEG C of vacuum drying and is obtained SBA-15 and load the zirconium oxide product (2ML-ZrO of two-layer2@
SBA-15)。
2ML-ZrO by 1.8g previous step gained2@SBA-15 is immersed in the sulfuric acid solution of 90mL, 0.25mol/L,
Soak centrifugal collected product after 24h to be placed in Muffle furnace through 150 DEG C of vacuum drying, with the heating rate of 10 DEG C/min from room
Temperature rise to 1200 DEG C, and at a temperature of 1200 DEG C, keep 10h, obtain the 2ML-ZrO of SBA-15 load2/SO4 2-Type solid surpasses
Strong acid (2SZ@SBA-15).
Configuration cerium ion concentration is the cerous nitrate solution of 10g/L, is soaked by the 2SZ@SBA-15 sample of 10g previous step gained
Stain, in the above-mentioned cerium solution of 300mL, after ultrasonic disperse is uniform, is evaporated solution under 180 DEG C of environment.
Previous step gained sample is placed in Muffle furnace, is increased to 1000 with the heating rate of 10 DEG C/min from room temperature
DEG C, and at a temperature of 1000 DEG C, keep 8h, obtain rare-earth cerium doped solid super acid catalyst (CeO2-2SZ@SBA-15)。
(2) catalytic performance analysis test
Catalytic performance analysis test method is with embodiment 1, and result shows, within the response time of 6h, product can reach relatively
High productivity is 66.4%, and the catalytic performance of this catalyst is higher.
(3) regenerability analysis test
Regenerability analysis test method is with embodiment 1.Result shows: in regenerative process, loss of catalyst activity is relatively low,
Regenerate in one to five process of the test, glucose be converted into the productivity of 5-HMF be followed successively by 66.3%, 66.1%, 65.8%,
65.6% and 65.3%.
Described embodiment be the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment, not
In the case of deviating from the flesh and blood of the present invention, any conspicuously improved, the replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (10)
1. the preparation method of a cerium dopping solid super acid catalyst, it is characterised in that comprise the steps:
(1) take dried silicon-based mesoporous molecular sieve SBA-15 to disperse in organic solvent, under conditions of stirring, to mixture
System is added dropwise over hydrolyzable zirconium salt solution；Products therefrom, after hydrolysis is complete, is washed, is centrifuged and receives by gained reaction system
Collection and vacuum drying, obtain the zirconium oxide product 1ML-ZrO of SBA-15 load monolayer2@SBA-15；
(2) by step (1) gained 1ML-ZrO2Silicon-based mesoporous molecular sieve SBA-15 in@SBA-15 alternative steps (1), repeats step
(1) hydrolysis in, obtains the zirconium oxide product 2ML-ZrO of SBA-15 load two-layer2@SBA-15；
(3) by the 2ML-ZrO of step (2) gained2@SBA-15 is immersed in sulfuric acid solution, after having soaked, and centrifugal collected product
Thing, vacuum dried is placed in Muffle furnace, temperature programming to calcining heat, obtains the 2ML-of SBA-15 load after calcining
ZrO2/SO4 2-Type solid super-strong acid 2SZ@SBA-15；
(4) configure certain density cerium solution, the 2SZ@SBA-15 sample of step (3) gained is immersed in described cerium solution
In, after ultrasonic disperse is uniform, it is evaporated solution；
(5) step (4) gained sample is placed in Muffle furnace, temperature programming to calcining heat, obtains rare-earth cerium doped after calcining
Solid super acid catalyst CeO2-2SZ@SBA-15。
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(1), in, described organic solvent is normal hexane, hexamethylene, normal propyl alcohol or isopropanol；Hydrolyzable zirconates is zirconium-n-propylate or isopropanol
Zirconium.
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(1) in, described SBA-15, hydrolyzable zirconates, the ratio of organic solvent are 0.2-10g:1.0-58.5g:10-600mL, and hydrolysis is anti-
Answering temperature to be 50-120 DEG C, the response time is 6-48h, and vacuum drying temperature is 40-120 DEG C.
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(2) in, described 1ML-ZrO2@SBA-15, hydrolyzable zirconates, the ratio of organic solvent are 0.2-10g:0.6-28.5g:10-
600mL, hydrolysising reacting temperature is 50-120 DEG C, and the response time is 6-48h, and vacuum drying temperature is 40-120 DEG C.
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(3) in, described 2ML-ZrO2@SBA-15, the ratio of sulfuric acid solution are 0.2-1.8g:10-90mL, described sulfuric acid solution concentration model
Enclose for 0.005-0.25mol/L；Soak time is 4-24h；Vacuum drying temperature is 60-150 DEG C；Heating rate is 1.0-10
DEG C/min, calcining heat is 400-1200 DEG C, calcination time 1-10h.
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(4) in, described cerium solution is cerous nitrate saline solution or cerous sulfate saline solution, and in described cerium solution, cerium ion concentration is 0.1-
10g/L。
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(4), in, described 2SZ@SBA-15, the ratio of cerium solution are 0.1-10g:10-300mL, described in temperature when being evaporated solution be
25-180℃。
The preparation method of a kind of cerium dopping solid super acid catalyst the most according to claim 1, it is characterised in that step
(5) in, described heating rate is 1.0-10 DEG C/min, and calcining heat is 350-1000 DEG C, calcination time 1-8h.
9. the rare-earth cerium doped solid super acid catalyst prepared according to preparation method according to any one of claim 1～8, its
Being characterised by, its aperture is 4.5nm, and acidity value is 0.28mmol g-1, basicity value is 0.12mmol g-1。
10. the application of a rare-earth cerium doped solid super acid catalyst as claimed in claim 9, it is characterised in that by institute
It is the reaction of 5-HMF that the rare-earth cerium doped solid super acid catalyst stated is applied to be catalyzed glucose degradation.
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