CN106215969B - 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
- Publication number
- CN106215969B CN106215969B CN201610592153.9A CN201610592153A CN106215969B CN 106215969 B CN106215969 B CN 106215969B CN 201610592153 A CN201610592153 A CN 201610592153A CN 106215969 B CN106215969 B CN 106215969B
- Authority
- CN
- China
- Prior art keywords
- sba
- cerium
- solid super
- acid catalyst
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000007787 solid Substances 0.000 title claims abstract description 43
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003930 superacid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 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 14
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 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 35
- 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
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- -1 Cerium ion Chemical class 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RWACICCRNCPMDT-UHFFFAOYSA-N cerium sulfuric acid Chemical compound [Ce].S(O)(O)(=O)=O RWACICCRNCPMDT-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 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
- ZJJWXAUNWSORPB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O ZJJWXAUNWSORPB-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 abstract description 22
- 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
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 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
- 239000000047 product Substances 0.000 description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 229930091371 Fructose Natural products 0.000 description 8
- 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 8
- 238000004458 analytical method Methods 0.000 description 8
- 229960002737 fructose Drugs 0.000 description 8
- 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
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 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
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000000034 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process 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
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 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
- 150000002240 furans Chemical class 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
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 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
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000000126 substance Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to multifunction solid catalyst field, a kind of cerium dopping solid super acid catalyst and preparation method thereof is specifically provided.There to be 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 that conventional solid superacid catalysis glucose isomerization degree existing in the prior art is not high, 5 HMF yields are undesirable, specific surface area is low, easily reunites in reaction process, lead to the shortcomings of active site loss late is excessively high, regenerability is poor, provide a kind of soda acid difunctionalization, catalytic reaction activity height, bigger serface, stabilization 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, high-specific surface area rare earth
Adulterate solid super acid catalyst and preparation method thereof.
Background technology
5 hydroxymethyl furfural (5-hydroxymethylfurfural, 5-HMF) is to contain 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 reacting,
It is the key intermediate for connecting biomass chemistry and petrochemistry.In general, using fructose as raw material, by dehydration it is available compared with
The 5-HMF of high yield.But fructose is expensive, while its application in field of food is more and more extensive, largely uses fruit
Sugar is that raw material preparation 5-HMF is economically infeasible, and certain competition is also will produce to food supply.Therefore, with cheap, money
The abundant glucose in source efficiently prepares 5-HMF for raw material becomes current research hotspot.
Glucose is the isomer of fructose, therefore, it is different to relate generally to glucose using glucose as raw material preparation 5-HMF
Structure turns to fructose, and fructose obtained by the reaction dehydration generates the two step cascade reactions of 5-HMF.Wherein, existAcid (B acid)
Under the catalytic action of active site, the reaction that fructose dehydration generates 5-HMF is easy to occur, and the isomerisation degree of glucose is
Influence the key factor of cascade reaction.Studies have shown that Lewis (L acid) or the presence of basic site are beneficial to Portugal in catalyst
Grape sugar is isomerized to fructose, and then improves the yield of 5-HMF.Solid super-strong acid is B acid and L acid compound action and shape in some way
At a kind of novel acid, also have certain alkalescent, activated centre is contained in the acid sites B (proton acid site) and L acid simultaneously
The heart (Lewis acid centers), the synergistic effect both in catalytic reaction process, has superpower acidity and high catalytic activity, becomes solid
Hot spot in the research of body acid catalyst.For the solid super acid catalyst occurred in this research field, mainly there are following a few sides
The problem of face, needs to solve：(1) glucose isomerization degree is still relatively low, and it is not high to show as reaction substrate conversion ratio, 5-HMF productions
Rate is undesirable；(2) specific surface area of catalyst is low, and active site load capacity is few；(3) catalyst is easily reunited in reaction process, is led
Cause active site loss late excessively high, regenerability is poor.
Invention content
The object of the present invention is to provide a kind of preparation methods of rare-earth cerium doped solid super acid catalyst, overcome existing skill
Conventional solid superacid catalysis glucose isomerization degree is not high present in art, 5-HMF yields are undesirable, specific surface area is low,
Easily reunite in reaction process, lead to the shortcomings of active site loss late is excessively high, regenerability is poor, it is difunctional to provide a kind of soda acid
Change, the rare-earth cerium doped solid super acid catalyst of catalytic reaction activity height, bigger serface, stabilization.
A kind of preparation method of rare-earth cerium doped solid super acid catalyst, comprises the steps of：
(1) take it is dry after silicon-based mesoporous molecular sieve SBA-15 dispersion in organic solvent, under stirring conditions, to mixed
Hydrolyzable zirconium salt solution is added dropwise in zoarium system；Gained reaction system after hydrolysis is complete, by products therefrom washing, from
The heart is collected and vacuum drying, obtains the zirconium oxide product (1ML-ZrO of SBA-15 load single layers2@SBA-15)；
(2) by 1ML-ZrO obtained by step (1)2Silicon-based mesoporous molecular sieve SBA-15 in@SBA-15 alternative steps (1) repeats
Hydrolysis in step (1) obtains the zirconium oxide product (2ML-ZrO that SBA-15 loads two layers2@SBA-15)；
(3) by the 2ML-ZrO obtained by step (2)2@SBA-15 are immersed in sulfuric acid solution, and after the completion of immersion, centrifugation is received
Collect product, vacuum dried to be placed in Muffle furnace, temperature programming to calcination temperature obtains the 2ML- of SBA-15 loads after calcining
ZrO2/SO4 2-Type solid super-strong acid (2SZ@SBA-15)；
(4) certain density cerium solution is configured, the 2SZ@SBA-15 samples obtained by step (3) are immersed in the cerium salt
In solution, after ultrasonic disperse is uniform, it is evaporated solution；
(5) sample obtained by step (4) is placed in Muffle furnace, temperature programming to calcination temperature obtains cerium after calcining
Adulterate solid super acid catalyst (CeO2-2SZ@SBA-15)。
In step (1), the organic solvent is n-hexane, hexamethylene, normal propyl alcohol or isopropanol；Hydrolyzable zirconates is positive third
Alcohol zirconium or zirconium iso-propoxide.
In step (1), the SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-10g：1.0-58.5g：10-
600mL, hydrolysising reacting temperature are 50-120 DEG C, reaction time 6-48h, and vacuum drying temperature is 40-120 DEG C.
In step (2), the 1ML-ZrO2@SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-10g：0.6-
28.5g：10-600mL, hydrolysising reacting temperature are 50-120 DEG C, reaction time 6-48h, and vacuum drying temperature is 40-120
℃。
In step (3), the sulfuric acid solution concentration range is 0.005-0.25mol/L.
In step (3), the 2ML-ZrO2@SBA-15, sulfuric acid solution ratio be 0.2-1.8g：10-90mL, when immersion
Between be 4-24h；Vacuum drying temperature is 60-150 DEG C；Heating rate is 1.0-10 DEG C/min, calcination temperature 400-1200
DEG C, calcination time 1-10h.
In step (4), the cerium solution is nitric acid cerium solution or sulfuric acid cerium solution, in the cerium solution cerium from
A concentration of 0.1-10g/L of son.
In step (4), 2SZ@SBA-15, cerium solution ratio be 0.1-10g：10-300mL, it is described be evaporated it is molten
Temperature when liquid is 25-180 DEG C.
In step (5), the heating rate is 1.0-10 DEG C/min, and calcination temperature is 350-1000 DEG C, calcination time 1-
8h。
Rare-earth cerium doped solid super acid catalyst prepared by the present invention, aperture 4.5nm, acidity value are
0.28mmol·g-1, basicity value 0.12mmolg-1。
It is 5-HMF's that rare-earth cerium doped solid super acid catalyst prepared by the present invention, which is applied to catalysis glucose degradation,
Reaction.The advantage of the invention is 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, while the thermal stability of catalyst is enhanced, catalyst regeneration performance is significantly improved.
(2) introducing of cerium improves the basicity of solid super-strong acid, and obtained solid catalyst not only has superpower acidity (B
Acid and L acid), while there is certain alkalinity, it is prepared in 5-HMF reaction process in the acid sites B, L acid in catalytic degradation glucose
The heart and basic site synergistic effect, considerably improve the isomerisation degree of glucose, the yield and selectivity of 5-HMF.
(3) present invention uses technology, and preparation process is simple, easy to operate, suitable for industrialized production.
Description of the drawings
Fig. 1 is the scanning electron microscope (a) and transmission electron microscope (b) figure of prepared solid catalyst in embodiment 1.
Wide-angle (a) He little Jiao (b) X-ray diffractograms of prepared solid catalyst in Fig. 2 embodiments 1.
Fig. 3 is the nitrogen adsorption desorption curve figure of prepared solid catalyst in embodiment 1, and wherein insert pictures are hole
Diameter distribution map.
Fig. 4 is SBA-15 carriers in embodiment 1, the middle gained 2ML-Zr O of 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 desorbs attached drawing.
Fig. 6 is the infrared figure of pyridine in situ of prepared solid catalyst in embodiment 1.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
It is without being limited thereto.
Embodiment 1
(1) preparation of rare-earth cerium doped solid super acid catalyst
The silicon-based mesoporous molecular sieve SBA-15s of 0.2g after drying are dispersed in 10mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 1.0g is added dropwise into mixed system.Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains the zirconium oxide product (1ML-ZrO that SBA-15 loads single layer with 40 DEG C of vacuum drying2@
SBA-15)。
1ML-ZrO obtained by 0.2g previous steps2@SBA-15 are dispersed in again in 10mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 0.6g is added dropwise into mixed system.Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains the zirconium oxide product (2ML-ZrO that SBA-15 loads two layers with 40 DEG C of vacuum drying2@
SBA-15)。
By the 2ML-ZrO obtained by 0.2g previous steps2@SBA-15 are immersed in 10mL, in the sulfuric acid solution of 0.005mol/L,
It impregnates and centrifuges collected product after 4h and 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 is increased to 400 DEG C, and keeps 1h at a temperature of 400 DEG C, obtains the 2ML-ZrO of SBA-15 loads2/SO4 2-Type solid super-strong acid
(2SZ@SBA-15)。
The cerous nitrate solution that cerium ion concentration is 0.1g/L is configured, by the 2SZ@SBA-15 samples obtained by 0.1g previous steps
It is immersed in the above-mentioned cerium solution of 10mL, after ultrasonic disperse is uniform, is stood under 25 DEG C of room temperature environments, wait for that solution is evaporated.
Sample obtained by previous step is placed in Muffle furnace, 350 are increased to from room temperature with the heating rate of 1.0 DEG C/min
DEG C, and 1h is kept at a temperature of 350 DEG C, obtain rare-earth cerium doped solid super acid catalyst (CeO2-2SZ@SBA-15)。
Can be seen that prepared solid catalyst is corynebacterium by Fig. 1 scanning electron microscope (SEM) photographs, length is about 1 μm or so,
Diameter is about 360nm or so；It can clearly observe that solid catalyst surface distribution is a large amount of orderly from transmission electron microscope picture
Mesoporous, aperture is about 4.5nm or so.
There was only the spy of SBA-15 carriers by the solid catalyst prepared by Wide angle X-ray diffraction it can be seen from the figure that in Fig. 2
Diffraction maximum is levied, loaded ZrO does not occur2And CeO2Characteristic peak, this phenomenon may be the ZrO by being loaded2With colloid
State occurs, and particle very little, and CeO2The load capacity of nano-particle is seldom and dispersion degree is very high, cause its characteristic peak be difficult to by
It detects.Small angle X-ray diffraction figure proves that the meso-hole structure of prepared solid catalyst still remains the typical case of high-sequential
Hexagonal symmetry.
Nitrogen adsorption desorption is attached to typical meso-hole structure in Fig. 3, and prepared solid catalyst specific surface area is
227.7cm2g-1, while its aperture integrated distribution is almost the same in 4.4nm or so and the obtained result of transmission electron microscope observing.
Gained 2ML-ZrO in step (2) in Fig. 42The appearance of Zr 3d signal peaks 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 proof of S 2p signal peaks is successfully prepared
Solid super-strong acid, meanwhile, in final prepared solid catalyst there is the signal peak of Ce 3d, it was demonstrated that this method successfully incite somebody to action
There is the solid super-strong acid 2ML-ZrO of catalytic activity2/SO4 2-And CeO2Nano particle is supported on SBA-15, prepares CeO2-
2SZ@SBA-15 solid catalysts.
(a) NH in Fig. 53And CO2(b) 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 catalysts
It is a kind of soda acid difunctionalization solid catalyst.
By CeO in Fig. 62It is in the pyridine infrared spectrogram in situ of -2SZ@SBA-15 solid catalysts as can be seen that prepared
Catalyst simultaneously have bronsted acid (1542cm-1) and lewis acid (1447cm-1) active site characteristic peak, it was demonstrated that should
Contain B acid and L sour two kinds of acidic sites while solid catalyst prepared by method.The above characterization proves, which can be with
A kind of solid catalyst acid, basic site containing B/L is successfully prepared, the presence of L acidic sites and basic site can be very
The isomerization that glucose is improved in big degree, to enhance catalyst activity.
(2) catalytic test
In general, the hydrolysis of the monosaccharides such as glucose carries out in dimethyl sulfoxide (DMSO) (DMSO), DMSO is in reaction process
In not only serve as solvent, while also certain catalytic effect.But since DMSO is a kind of high boiling solvent, have certain
Toxicity, a large amount of use can cause environment certain harm, the product that simultaneous reactions obtain to be difficult to separating-purifying.The present invention uses
The mixed system of isopropanol and DMSO serve as solvent, can effectively reduce the utilization rate of DMSO.The glucose of 50mg is added to
In the mixed solution system of isopropanol (4.5mL) and DMSO (0.5mL) compositions, 20mg catalyst is then added to reaction system
In, system reacts 6h in 120 DEG C of oil bath pan under the rotating speed of 1200r/min.After the completion of reaction, products therefrom constant volume to appearance
In measuring bottle, after be diluted to 5000 times, be detected with efficient liquid phase (HPLC).Testing conditions are：Column temperature：30℃；Mobile phase
For water and methanol, ratio 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 indicates the corresponding concentration of 5-HMF, unit mg/L, x expression to y=0.0019x+3.4903
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 yield, is 66.5%.
(3) regeneration test
Reaction solution obtained by catalytic test puts into it by centrifuging, detaching, being drying to obtain regeneration catalyst again
It states in catalytic test, tests its catalytic effect；Four regeneration tests are carried out in this approach.Measured catalysate detection method
With experimental condition with above-mentioned catalytic test.
The result shows that：Loss of catalyst activity is relatively low in regenerative process, and during regenerating one to five experiment, glucose turns
The yield for 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
The silicon-based mesoporous molecular sieve SBA-15s of 5.0g after drying are dispersed in 300mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 25g is added dropwise into mixed system.Reaction system at 80 DEG C after hydrolyzing 30h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains the zirconium oxide product (1ML-ZrO that SBA-15 loads single layer with 80 DEG C of vacuum drying2@
SBA-15)。
1ML-ZrO obtained by 5.0g previous steps2@SBA-15 are dispersed in again in 300mL n-hexanes, in the condition of stirring
Under, the zirconium-n-propylate of 15g is added dropwise into mixed system.Reaction system at 80 DEG C after hydrolyzing 30h, and products therefrom is through steaming
Distilled water washs 3-5 times, the zirconium oxide product (2ML-ZrO for being dried in vacuo with 80 DEG C and obtaining SBA-15 and loading two layers is collected by centrifugation2@
SBA-15)。
By the 2ML-ZrO obtained by 1.0g previous steps2@SBA-15 are immersed in 50mL, in the sulfuric acid solution of 0.1mol/L, leaching
Collected product is centrifuged after bubble 15h to be placed in Muffle furnace through 80 DEG C of vacuum drying, with the heating rate of 5.0 DEG C/min from room temperature
800 DEG C are increased to, and 5h is kept at a temperature of 800 DEG C, obtains the 2ML-ZrO of SBA-15 loads2/SO4 2-Type solid super-strong acid
(2SZ@SBA-15)。
The cerous nitrate solution that cerium ion concentration is 5.0g/L is configured, by the 2SZ@SBA-15 samples obtained by 5.0g previous steps
It is immersed in the above-mentioned cerium solution of 150mL, after ultrasonic disperse is uniform, solution is evaporated at 120 DEG C.
Sample obtained by previous step is placed in Muffle furnace, 700 are increased to from room temperature with the heating rate of 5.0 DEG C/min
DEG C, and 5h is kept at a temperature of 700 DEG C, obtain rare-earth cerium doped solid super acid catalyst (CeO2-2SZ@SBA-15)。
(2) catalytic performance analysis test
Catalytic performance analysis test method is the same as embodiment 1, the results showed that, within the reaction time of 6h, product can reach compared with
High yield is 66.7%, and the catalytic performance of the catalyst is higher.
(3) regenerability analysis test
Regenerability analysis test method is the same as embodiment 1.The result shows that：Loss of catalyst activity is relatively low in regenerative process,
During one to five experiment of regeneration, yield that glucose is converted into 5-HMF is 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
The silicon-based mesoporous molecular sieve SBA-15s of 10g after drying are dispersed in 600mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 58.5g is added dropwise into mixed system.Reaction system at 120 DEG C after hydrolyzing 48h, and products therefrom is through steaming
Distilled water washs 3-5 times, the zirconium oxide product (1ML-ZrO for being dried in vacuo with 120 DEG C and obtaining SBA-15 and loading single layer is collected by centrifugation2@
SBA-15)。
1ML-ZrO obtained by 10g previous steps2@SBA-15 are dispersed in again in 600mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 28.5g is added dropwise into mixed system.Reaction system at 120 DEG C after hydrolyzing 48h, and products therefrom is through steaming
Distilled water washs 3-5 times, the zirconium oxide product (2ML-ZrO for being dried in vacuo with 120 DEG C and obtaining SBA-15 and loading two layers is collected by centrifugation2@
SBA-15)。
By the 2ML-ZrO obtained by 1.8g previous steps2@SBA-15 are immersed in 90mL, in the sulfuric acid solution of 0.25mol/L,
It impregnates and centrifuges collected product afterwards for 24 hours and be placed in Muffle furnace through 150 DEG C of vacuum drying, with the heating rate of 10 DEG C/min from room
Temperature is increased to 1200 DEG C, and keeps 10h at a temperature of 1200 DEG C, obtains the 2ML-ZrO of SBA-15 loads2/SO4 2-Type solid is super
Strong acid (2SZ@SBA-15).
The cerous nitrate solution that cerium ion concentration is 10g/L is configured, the 2SZ@SBA-15 samples obtained by 10g previous steps are soaked
Stain is in the above-mentioned cerium solution of 300mL, and after ultrasonic disperse is uniform, solution is evaporated under 180 DEG C of environment.
Sample obtained by previous step is placed in Muffle furnace, 1000 are increased to from room temperature with the heating rate of 10 DEG C/min
DEG C, and 8h is kept at a temperature of 1000 DEG C, obtain rare-earth cerium doped solid super acid catalyst (CeO2-2SZ@SBA-15)。
(2) catalytic performance analysis test
Catalytic performance analysis test method is the same as embodiment 1, the results showed that, within the reaction time of 6h, product can reach compared with
High yield is 66.4%, and the catalytic performance of the catalyst is higher.
(3) regenerability analysis test
Regenerability analysis test method is the same as embodiment 1.The result shows that：Loss of catalyst activity is relatively low in regenerative process,
During one to five experiment of regeneration, yield that glucose is converted into 5-HMF is followed successively by 66.3%, 66.1%, 65.8%,
65.6% and 65.3%.
The embodiment is the preferred embodiments of the present invention, but present invention is not limited to the embodiments described above, not
Away from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
Or modification all belongs to the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of cerium dopping solid super acid catalyst, which is characterized in that include the following steps：
(1) the silicon-based mesoporous molecular sieve SBA-15 dispersion after drying is taken in organic solvent, under stirring conditions, to mixture
Hydrolyzable zirconium salt solution is added dropwise in system；Gained reaction system receives products therefrom washing, centrifugation after hydrolysis is complete
Collection and vacuum drying obtain the zirconium oxide product 1ML-ZrO of SBA-15 load single layers2@SBA-15；The SBA-15, hydrolyzable
Zirconates, organic solvent ratio be 0.2-10g：1.0-58.5g：10-600mL；
(2) by 1ML-ZrO obtained by step (1)2Silicon-based mesoporous molecular sieve SBA-15 in@SBA-15 alternative steps (1) repeats step
(1) hydrolysis in obtains the zirconium oxide product 2ML-ZrO that SBA-15 loads two layers2@SBA-15；The 1ML-ZrO2@
SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-10g：0.6-28.5g：10-600mL；
(3) by the 2ML-ZrO obtained by step (2)2@SBA-15 are immersed in sulfuric acid solution, after the completion of immersion, centrifuge collected production
Object, vacuum dried to be placed in Muffle furnace, temperature programming to 400-1200 DEG C of calcination temperature, calcination time 1-10h, after calcining
Obtain the 2ML-ZrO of SBA-15 loads2/SO4 2-Type solid super-strong acid 2SZ@SBA-15；The 2ML-ZrO2@SBA-15, sulfuric acid are molten
The ratio of liquid is 0.2-1.8g：10-90mL, the sulfuric acid solution concentration range are 0.005-0.25mol/L；
(4) certain density cerium solution is configured, the 2SZ@SBA-15 samples obtained by step (3) are immersed in the cerium solution
In, after ultrasonic disperse is uniform, it is evaporated solution；Cerium ion concentration is 0.1-10g/L in the cerium solution；The 2SZ@SBA-
15, the ratio of cerium solution is 0.1-10g：10-300mL；
(5) sample obtained by step (4) is placed in Muffle furnace, with heating rate 1.0-10 DEG C/min temperature programmings to calcination temperature
350-1000 DEG C, calcination time 1-8h, rare-earth cerium doped solid super acid catalyst CeO is obtained after calcining2-2SZ@SBA-15。
2. a kind of preparation method of cerium dopping solid super acid catalyst according to claim 1, which is characterized in that step
(1) in, the organic solvent is n-hexane, hexamethylene, normal propyl alcohol or isopropanol；Hydrolyzable zirconates is zirconium-n-propylate or isopropanol
Zirconium.
3. a kind of preparation method of cerium dopping solid super acid catalyst according to claim 1, which is characterized in that step
(1) in, hydrolysising reacting temperature is 50-120 DEG C, reaction time 6-48h, and vacuum drying temperature is 40-120 DEG C.
4. a kind of preparation method of cerium dopping solid super acid catalyst according to claim 1, which is characterized in that step
(2) in, hydrolysising reacting temperature is 50-120 DEG C, reaction time 6-48h, and vacuum drying temperature is 40-120 DEG C.
5. a kind of preparation method of cerium dopping solid super acid catalyst according to claim 1, which is characterized in that step
(3) in, soaking time 4-24h；Vacuum drying temperature is 60-150 DEG C；Heating rate is 1.0-10 DEG C/min.
6. a kind of preparation method of cerium dopping solid super acid catalyst according to claim 1, which is characterized in that step
(4) in, the cerium solution is nitric acid cerium solution or sulfuric acid cerium solution.
7. a kind of preparation method of cerium dopping solid super acid catalyst according to claim 1, which is characterized in that step
(4) in, temperature when being evaporated solution is 25-180 DEG C.
8. according to cerium dopping solid super acid catalyst, feature made from any one of claim 1~7 preparation method
It is, aperture 4.5nm, acidity value 0.28mmolg-1, basicity value 0.12mmolg-1。
9. a kind of application of cerium dopping solid super acid catalyst as claimed in claim 8, which is characterized in that by the cerium
It adulterates solid super acid catalyst and is applied to the reaction that catalysis glucose degradation is 5-HMF.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610592153.9A CN106215969B (en) | 2016-07-25 | 2016-07-25 | A kind of cerium dopping solid super acid catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610592153.9A CN106215969B (en) | 2016-07-25 | 2016-07-25 | A kind of cerium dopping solid super acid catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106215969A CN106215969A (en) | 2016-12-14 |
| CN106215969B true CN106215969B (en) | 2018-08-21 |
Family
ID=57534065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610592153.9A Expired - Fee Related CN106215969B (en) | 2016-07-25 | 2016-07-25 | A kind of cerium dopping solid super acid catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106215969B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499586A (en) * | 2018-12-05 | 2019-03-22 | 怀化学院 | Rare earth modified solid super acid catalyst and preparation method thereof |
| CN113304743B (en) * | 2021-05-14 | 2022-01-04 | 安徽海华科技集团有限公司 | Method for preparing high-purity carvacrol by using o-cresol |
| CN113318697A (en) * | 2021-06-29 | 2021-08-31 | 西安热工研究院有限公司 | For CO desorption of amine solutions2Is loaded with SO42Filler of metal oxide and process for its preparation |
| CN114874026B (en) * | 2022-05-23 | 2023-05-12 | 哈尔滨工业大学 | Preparation method of high-strength fiber composite zirconia foam ceramic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706384A (en) * | 2013-12-24 | 2014-04-09 | 内蒙古农业大学 | Preparation method of bio-diesel catalyst |
| CN105642345A (en) * | 2015-04-03 | 2016-06-08 | 江苏大学 | Preparation method of hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7304199B2 (en) * | 2004-04-14 | 2007-12-04 | Abb Lummus Global Inc. | Solid acid catalyst and method of using same |
-
2016
- 2016-07-25 CN CN201610592153.9A patent/CN106215969B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706384A (en) * | 2013-12-24 | 2014-04-09 | 内蒙古农业大学 | Preparation method of bio-diesel catalyst |
| CN105642345A (en) * | 2015-04-03 | 2016-06-08 | 江苏大学 | Preparation method of hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst |
Non-Patent Citations (2)
| Title |
|---|
| High selective production of 5-hydroymethylfurfural from fructose by a solid heteropolyacid catalyst;Qian Zhao et al.;《Fuel》;20110302;第90卷;第2289-2293页 * |
| 固体酸催化单糖制备5-羟甲基糠醛(5-HMF)的研究进展;安士云 等;《化学世界》;20121231(第7期);第441-445页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106215969A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106215969B (en) | A kind of cerium dopping solid super acid catalyst and preparation method thereof | |
| CN106311345A (en) | Acid-base bifunctional solid catalyst and preparation method thereof | |
| Jiménez-Morales et al. | Glucose dehydration to 5-hydroxymethylfurfural on zirconium containing mesoporous MCM-41 silica catalysts | |
| Agirrezabal-Telleria et al. | Functionalized partially hydroxylated MgF2 as catalysts for the dehydration of d-xylose to furfural | |
| Ordomsky et al. | Glucose Dehydration to 5‐Hydroxymethylfurfural in a Biphasic System over Solid Acid Foams | |
| CN107213915A (en) | A kind of difunctional metal organic framework catalyst of soda acid and its production and use | |
| Marianou et al. | Cellulose conversion into lactic acid over supported HPA catalysts | |
| Feng et al. | Efficient synthesis of glucose into 5-hydroxymethylfurfural with SO42−/ZrO2 modified H+ zeolites in different solvent systems | |
| CN108940313A (en) | A kind of biomass carbon based solid acid catalyst and its preparation method and application | |
| CN105797711A (en) | Preparation method of catalyst for catalyzing glucose to generate 5-hydroxymethylfurfural through dehydration process | |
| CN106166499B (en) | A kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system | |
| CN105251514B (en) | Carbon containing multi-stage porous, bronsted acid/lewis acid difunctionalization catalyst and preparation method thereof and purposes | |
| CN107952486A (en) | A kind of compound acidic solid catalyst PVP-HNTs@UiO-66-SO3H and preparation method thereof | |
| Hua et al. | Preparation of solid acid catalyst packing AAO/SBA-15-SO3H and application for dehydration of xylose to furfural | |
| CN108499607A (en) | A kind of Preparation method and use of Quito aqueous acid medium alkali bifunctional MOFs pore catalyst | |
| CN104959162A (en) | Preparation method for in-situ zirconium-doped molecular sieve solid superacid | |
| Zhang et al. | Catalytic self-etherification of 5-hydroxymethylfurfural to 5, 5′(oxy-bis (methylene)) bis-2-furfural over zeolite catalysts: effect of pore structure and acidity | |
| Wang et al. | Production of levulinic acid via cellulose conversion over metal oxide-loaded MOF catalysts in aqueous medium | |
| Behera et al. | Fascinating and challenging role of tungstate promoted vanadium phosphate towards solvent free esterification of oleic acid | |
| CN104628682B (en) | A kind of method for being catalyzed 5 hydroxymethylfurfurals and preparing alkoxymethylfurfural | |
| CN108435253A (en) | A kind of C3N4Carry difunctional MOFs based composite catalysts of soda acid and its preparation method and application | |
| CN102989499A (en) | Catalyst for preparing p-tertbutyl benzaldehyde and preparation method | |
| CN106669652B (en) | A kind of catalysis ethanol prepares the catalyst and its preparation process and application method of low-carbon alkene | |
| CN106513014A (en) | Hierarchical-pore carbon-supported acidic solid catalyst and preparation method thereof | |
| CN100450609C (en) | Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180821 Termination date: 20190725 |