CN105665018B - The preparation method and application of composite solid catalyst for production of superstrong - Google Patents
The preparation method and application of composite solid catalyst for production of superstrong Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 39
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011973 solid acid Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000005030 aluminium foil Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000004438 BET method Methods 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000004587 chromatography analysis Methods 0.000 claims description 7
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000003980 solgel method Methods 0.000 abstract description 7
- 239000003930 superacid Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- -1 compound Lewis acid Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method and applications of composite solid catalyst for production of superstrong, belong to solid super acid catalyst technical field.The preparation method of composite solid catalyst for production of superstrong of the present invention is that SiO is made using sol-gel processing2The solid particle for loading perfluorinated sulfonic resin, then solid particle is calcined, obtain perfluorinated sulfonic resin/SiO2Composite solid catalyst for production of superstrong.The preparation method of composite solid catalyst for production of superstrong of the present invention, its is simple and practicable, and the catalyst of preparation has certain crystal form, grain size, pore structure, specific surface area and high mechanical properties, acid centre exposure abundant, catalytic activity is stablized, and catalytic efficiency and repeatable utilization rate are high；The present invention provides a kind of applications of simple and convenient composite solid catalyst for production of superstrong simultaneously.
Description
Technical field
The present invention relates to a kind of preparation method and applications of composite solid catalyst for production of superstrong, belong to solid superacid as catalyst
Agent technical field.
Background technology
Ethyl acetate usually carries out esterification by ethyl alcohol and acetic acid and is made, and is a kind of widely used fine chemistry industry production
Product are a kind of very important Organic Chemicals and fabulous industrial solvent, are had in industrial production and organic synthesis wide
General application.In addition, it is also used as adhesive and fragrance etc., it is one of indispensable raw material in production and living.
The type of catalyst used in esterification has been a hot spot of research, but the catalyst of industry is usually dense
Sulfuric acid, p-methyl benzenesulfonic acid, thionyl chloride etc. have the shortcomings that separation is difficult, esterification yied is low etc., gradually by environmentally friendly
The new catalysts such as acidic resins, molecular sieve, superpower solid acid replace.The SO of CN101475475A synthesis4 2-/TiO2Catalyst
For catalytic esterification.But the acidity of catalyst group is easy to fall off, stability is bad, and recycling property is poor.
Perfluorinated sulfonic resin (PFSA) is a kind of cation exchange resin, is also a kind of solid super strong acid resin, organic
There is extensive catalytic action in reaction.Compared with liquid acid catalyst, perfluorinated sulfonic resin have it is non-corrosive, do not generate it is useless
Acid solution, product be easily separated, high selectivity and can multiple Reusability the advantages that, compared with general solid acid, perfluorinated sulfonic acid tree
Fat has the advantages such as yield is high, reaction condition is mild, reaction speed is fast；Compared with other acid cation exchange resins, perfluor
Sulfonate resin has the characteristics that stronger acidity, temperature in use are high.Therefore, perfluorinated sulfonic resin is comparatively ideal environmental sound
Solid acid catalyst.
But perfluorinated sulfonic resin is expensive.Before in Shandong Eastern Mountain, group can produce, the perfluor sulphur needed for China
Acid resin catalyst is both needed to from external import, the research work in domestic also only a small number of universities or research unit's progress laboratory.
CN1699450A and CN200510046751.8 is described in detail by discarded ionic membrane recycling extraction high-purity perfluorinated sulfonic resin
Method so that the recycling of expensive perfluorinated sulfonic resin becomes reality.
Further, since perfluorinated sulfonic resin specific surface area is relatively low, the acid centre being buried in fluorocarbon radical body is not easy anti-
Object is answered to approach, therefore, it can be to improve perfluorinated sulfonic resin catalysis to dive using the ratio in acid site to increase its specific surface area, improve
One important measures of power.
CN201310569897.5 has been synthesized with dipping-solvent evaporated method by the immobilized perfluorinated sulfonic resin of activated carbon
Superpower solid acid catalyst, and it is used for catalytic esterification, esterification yied is higher.The specific surface area of catalyst that this method obtains is big
Amplitude increases, and acidic site is easily approached by reactant.But the catalyst of this method synthesis is effective group in catalytic reaction process
Divide and be easy to run off, it is difficult to be used repeatedly.
CN201210347099.3 is prepared for being carried on the perfluorinated sulfonic acid tree of mesoporous polymer material with sol-gel processing
The superpower solid acid catalyst of fat, but prepare that the mesoporous polymer materials process needed for the catalyst is cumbersome, the period is long, cause to urge
Agent low production efficiency.
E.I.Du Pont Company discloses the method for modifying that perfluorinated ion exchanges composite catalyst in patent US6133493：
Perfluorinated ion exchange polymer is highly dispersed in the network structure of inorganic oxide and forms compound, then uses compound
Lewis acid is modified.SiO is pointed out in the patent of invention2It is dispersion perfluorinated ion exchange polymer in inorganic oxide
Most preferably.In order to which using perfluorinated sulfonic resin catalysis of solid catalyst, efficient, easy recycling, renewable, polar ring are protected, using model
Wide advantage is enclosed, and overcomes the disadvantage that its specific surface area is small, activated centre exposed amount is low, up to the present, has lot of documents
It reports and perfluorinated sulfonic resin is carried on SiO using sol-gel method2Loaded catalyst is made, such as：Fine oil
Work, 2006,23 (4):29-32；Chemistry world, 2010 (5):260-263 etc..
CN201110318266.7 is prepared for a kind of magnetism perfluorinated sulfonic resin/SiO with sol-gel method2-
Co0.5Fe2.5O4Solid catalyst, and for the synthesis of ethyl acetate, catalytic efficiency may be up to 90%.The catalyst introduces magnetic
Property nano particle Co0.5Fe2.5O4, by by externally-applied magnetic field, achieving the effect that be easily isolated after the completion of reaction.But it is magnetic
Nano particle Co0.5Fe2.5O4Introducing result in catalyst preparation process it is relatively complicated.
Invention content
It is simple and practicable the purpose of the present invention is to provide a kind of preparation method of composite solid catalyst for production of superstrong, system
Standby catalyst has certain crystal form, grain size, pore structure, specific surface area and high mechanical properties, acid centre sudden and violent
Dew is abundant, and catalytic activity is stablized, and catalytic efficiency and repeatable utilization rate are high；The present invention provides a kind of simple and convenient to answer simultaneously
Close the application of solid super acid catalyst.
The preparation method of composite solid catalyst for production of superstrong of the present invention is that SiO is made using sol-gel processing2
The solid particle for loading perfluorinated sulfonic resin, then solid particle is calcined, obtain perfluorinated sulfonic resin/SiO2Complex solid is super
Strong acid catalyst.
The exchange capacity of the perfluorinated sulfonic resin is 0.98~1.10.
SiO is first made using sol-gel method2The gel for loading perfluorinated sulfonic resin, then dries gel successively
Dry, crushing, acidification, washing and drying, obtain SiO2Load the solid particle of perfluorinated sulfonic resin.
Prepare perfluorinated sulfonic resin/SiO2When gel, the mass ratio of perfluor sulfoacid resin solution used and NaOH solution is
1:1.0~1.5.
The solid content of the perfluor sulfoacid resin solution is 5%, a concentration of 0.05~0.09mol/L of NaOH solution.
Prepare perfluorinated sulfonic resin/SiO2When gel, ethyl orthosilicate used, pure water, HCl solution mass ratio be 500:
165~175:120~130.A concentration of 0.03~0.04mol/L of the HCl solution.
It is impregnated 3~5 times, every time 3~5min with HCl solution when acidification, the molar concentration of HCl solution is 3.0~4.0mol/
L；With pure water 3~5 times when washing, 3~5min every time.
The calcination temperature is 250~320 DEG C, and calcination time is 1.5~2.5h.
The preparation method of the composite solid catalyst for production of superstrong, specifically includes following steps：
(1) perfluorinated sulfonic resin aqueous solution is prepared：Perfluorinated sulfonic resin is added in alcohol-water solution, high pressure, reflux dress
It sets down, 250 DEG C of 5.0~8.0h of mechanical agitation.Methanol, ethyl alcohol, propyl alcohol, butanol or their mixture can be selected in alcohol.It evaporates dense
The perfluor sulfoacid resin solution that solid content is 5% is obtained after contracting.
(2) hydrolysis of ethyl orthosilicate：Ethyl orthosilicate is added in the mixture of pure water and HCl solution, magnetic force stirs
Mix 30~50min of processing so that solution clarification completely reaches complete hydrolysis.
(3) under mechanical agitation, the perfluor sulfoacid resin solution that solid content is 5% is mixed with NaOH solution.
(4) under mechanical agitation, the solution that step (2) obtains is poured slowly into the solution that step (3) obtains,
Continue stir about 1min so that solution is sufficiently mixed.At this point, solution gel quickly.
(5) gel that step (4) generates at 75 DEG C is covered into aluminium-foil paper, dries 1~2d, remove liquid water；Then it goes
Fall aluminium-foil paper, is placed in 95 DEG C of thermostatic drying chambers dry 1~2d, obtains solid particle；Finally, solid particle is placed
In 140 DEG C of vacuum drying chambers, dry 1~2d removes all water, the solid particle being completely dried.
(6) it after pulverizing dry solid particle, is impregnated with HCl solution, then uses pure water again.
(7) solid particle that step (6) obtains is dried in air dry oven, is then placed into Muffle furnace and calcines,
Obtain PFSA/SiO2Catalyst.
The application of the composite solid catalyst for production of superstrong is using acetic acid and ethyl ester as raw material, in the composite solid
Under the action of body super acidic catalyst, under the conditions of 95 DEG C reaction prepare ethyl acetate.
The method that the present invention is combined using sol-gel processing with calcining, with SiO2For carrier, by perfluorinated sulfonic resin
Solution is directly scattered in porous SiO2Colloid is and strictly to probe into the proportion relation between raw material on skeleton, develop one kind
Presence of compound solid superacid catalyst with certain crystal form, grain size, pore structure, specific surface area and high mechanical properties
Agent-PFSA/SiO2Catalyst.
Compared with prior art, the present invention having the advantages that：
(1) preparation method described in has the features such as simple and practicable, short preparation period.
(2) composite solid catalyst for production of superstrong-PFSA/SiO made from2Catalyst, acid strong, high catalytic efficiency is easy to
Separation and recycling, acid centre exposure is abundant, and catalytic activity is stablized, and repeats the features such as utilization rate is high, can replace sulfuric acid catalysis
Esterification.
(3) composite solid catalyst for production of superstrong is prepared into ethyl acetate for being catalyzed reaction, not only high catalytic efficiency, simply
It is convenient, and easily recycling, renewable, polar ring are protected, have a wide range of application, and have apparent economic benefit.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the implementation of the present invention.
Embodiment 1
The perfluorinated sulfonic resin that exchange capacity is 1.05 is added in alcohol-aqueous solution, under high pressure, reflux, 250
DEG C mechanical agitation 5.0h obtains the perfluor sulfoacid resin solution that solid content is 5% after evaporation, concentration.
17.30g deionized waters are added into 50.00g ethyl orthosilicates, are added with stirring the HCl solution of 0.04mol/L
12.50g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 42.39g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of resin solution and 46.63g 0.05mol/L, solution gel quickly；By gel in 75 DEG C of conditions
Lower covering aluminium-foil paper dries 2d, removes liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry
2d obtains solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water,
The solid particle being completely dried.After pulverizing, with molar concentration be 3.0mol/L HCl solution impregnate 5 times, every time about
3min, then uses pure water 5 times again, every time about 3min, drying.Solid particle after drying is forged in 300 DEG C of Muffle furnaces
It burns, obtains PFSA/SiO2Superpower solid acid catalyst.
The PFSA/SiO analyzed with BET methods2The specific surface area of superpower solid acid catalyst is 538.139m2/ g, hole
It is 0.596cm to hold3/ g, aperture 3.853nm.
With blender, thermometer, reflux condensing tube 250mL three-necked flasks in absolute ethyl alcohol 40.00g, ice is added
Acetic acid 62.60g and above-mentioned superpower solid acid catalyst 8.00g flows back under the conditions of 95 DEG C, mechanical agitation 5.0h, waits for that reaction finishing,
It negates and supernatant is answered to carry out gas chromatographic analysis, calculate analysis and show that the conversion ratio of ethyl alcohol is 89.57%.
Embodiment 2
The perfluorinated sulfonic resin that exchange capacity is 1.10 is added in alcohol-aqueous solution, under high pressure, reflux, 250
DEG C mechanical agitation 8.0h obtains the perfluor sulfoacid resin solution that solid content is 5% after evaporation, concentration.
17.30g deionized waters are added into 50.00g ethyl orthosilicates, are added with stirring the HCl solution of 0.04mol/L
12.50g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 48.05g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of resin solution and 48.05g 0.05mol/L, solution gel quickly；By gel under 75 DEG C of parts
It covers aluminium-foil paper and dries 2d, remove liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry 2d,
Obtain solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water, obtains
To the solid particle being completely dried.After pulverizing, the HCl solution for being 3.5mol/L with molar concentration impregnates 5 times, every time about 3min,
Then pure water is used again 5 times, every time about 3min, drying.Solid particle after drying is calcined in 300 DEG C of Muffle furnaces, is obtained
To PFSA/SiO2Superpower solid acid catalyst.
The PFSA/SiO analyzed with BET methods2The specific surface area of superpower solid acid catalyst is 584.633m2/ g, hole
It is 0.611cm to hold3/ g, aperture 4.003nm.
With blender, thermometer, reflux condensing tube 250mL three-necked flasks in absolute ethyl alcohol 40.00g, ice is added
Acetic acid 62.60g and above-mentioned superpower solid acid catalyst 8.00g flows back under the conditions of 95 DEG C, mechanical agitation 5.0h, waits for that reaction finishing,
It negates and supernatant is answered to carry out gas chromatographic analysis, calculate analysis and show that the conversion ratio of ethyl alcohol is 90.44%.
Embodiment 3
The perfluorinated sulfonic resin that exchange capacity is 0.98 is added in alcohol-aqueous solution, under high pressure, reflux, 250
DEG C mechanical agitation 6.0h obtains the perfluor sulfoacid resin solution that solid content is 5% after evaporation, concentration.
16.50g deionized waters are added into 50.00g ethyl orthosilicates, are added with stirring the HCl solution of 0.04mol/L
12.00g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 48.05g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of resin solution and 52.86g 0.05mol/L, solution gel quickly；By gel in 75 DEG C of conditions
Lower covering aluminium-foil paper dries 2d, removes liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry
2d obtains solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water,
The solid particle being completely dried.After pulverizing, with molar concentration be 3.5mol/L HCl solution impregnate 5 times, every time about
3min, then uses pure water 5 times again, every time about 3min, drying.Solid particle after drying is forged in 250 DEG C of Muffle furnaces
It burns, obtains PFSA/SiO2Superpower solid acid catalyst.
The PFSA/SiO analyzed with BET methods2The specific surface area of superpower solid acid catalyst is 446.386m2/ g, hole
It is 0.519cm to hold3/ g, aperture 4.001nm.
With blender, thermometer, reflux condensing tube 250mL three-necked flasks in absolute ethyl alcohol 40.00g, ice is added
Acetic acid 62.60g and above-mentioned superpower solid acid catalyst 8.00g flows back under the conditions of 95 DEG C, mechanical agitation 5.0h, waits for that reaction finishing,
It negates and supernatant is answered to carry out gas chromatographic analysis, calculate analysis and show that the conversion ratio of ethyl alcohol is 86.73%.
Embodiment 4
The perfluorinated sulfonic resin that exchange capacity is 1.05 is added in alcohol-aqueous solution, under high pressure, reflux, 250
DEG C mechanical agitation 7.0h obtains the perfluor sulfoacid resin solution that solid content is 5% after evaporation, concentration.
17.30g deionized waters are added into 50.00g ethyl orthosilicates, are added with stirring the HCl solution of 0.03mol/L
13.00g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 48.05g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of resin solution and 72.08g 0.05mol/L.Solution gel quickly；By gel in 75 DEG C of conditions
Lower covering aluminium-foil paper dries 2d, removes liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry
2d obtains solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water,
The solid particle being completely dried.After pulverizing, with molar concentration be 4.0mol/L HCl solution impregnate 5 times, every time about
3min, then uses pure water 5 times again, every time about 3min, drying.Solid particle after drying is forged in 300 DEG C of Muffle furnaces
It burns, obtains PFSA/SiO2Superpower solid acid catalyst.
The PFSA/SiO analyzed with BET methods2The specific surface area of superpower solid acid catalyst is 408.441m2/ g, hole
It is 0.432cm to hold3/ g, aperture 3.849nm.
With blender, thermometer, reflux condensing tube 250mL three-necked flasks in absolute ethyl alcohol 40.00g, ice is added
Acetic acid 62.60g and above-mentioned superpower solid acid catalyst 8.00g flows back under the conditions of 95 DEG C, mechanical agitation 5.0h, waits for that reaction finishing,
It negates and supernatant is answered to carry out gas chromatographic analysis, calculate analysis and show that the conversion ratio of ethyl alcohol is 83.14%.
Embodiment 5
The perfluorinated sulfonic resin that exchange capacity is 1.05 is added in alcohol-aqueous solution, under high pressure, reflux, 250
DEG C mechanical agitation 5.0h obtains the perfluor sulfoacid resin solution that solid content is 5% after evaporation, concentration.
17.50g deionized waters are added into 50.00g ethyl orthosilicates, are added with stirring the HCl solution of 0.04mol/L
13.00g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 48.05g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of resin solution and 52.86g 0.09mol/L, solution gel quickly；By gel in 75 DEG C of conditions
Lower covering aluminium-foil paper dries 2d, removes liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry
2d obtains solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water,
The solid particle being completely dried.After pulverizing, with molar concentration be 3.5mol/L HCl solution impregnate 5 times, every time about
3min, then uses pure water 5 times again, every time about 3min, drying.Solid particle after drying is forged in 320 DEG C of Muffle furnaces
It burns, obtains PFSA/SiO2Superpower solid acid catalyst.
The PFSA/SiO analyzed with BET methods2The specific surface area of superpower solid acid catalyst is 385.116m2/ g, hole
It is 0.403cm to hold3/ g, aperture 3.629nm.
With blender, thermometer, reflux condensing tube 250mL three-necked flasks in absolute ethyl alcohol 40.00g, ice is added
Acetic acid 62.60g and above-mentioned superpower solid acid catalyst 8.00g flows back under the conditions of 95 DEG C, mechanical agitation 5.0h, waits for that reaction finishing,
It negates and supernatant is answered to carry out gas chromatographic analysis, calculate analysis and show that the conversion ratio of ethyl alcohol is 85.51%.
Comparative example 1
The perfluorinated sulfonic resin that exchange capacity is 1.05 is added in alcohol-aqueous solution, under high pressure, reflux, 250
DEG C mechanical agitation 8.0h obtains the perfluor sulfoacid resin solution that solid content is 5% after evaporation, concentration.
17.30g deionized waters are added into 50.00g ethyl orthosilicates, are added with stirring the HCl solution of 0.04mol/L
12.50g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 48.05g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of resin solution and 52.86g 0.05mol/L, solution gel quickly；By gel in 75 DEG C of conditions
Lower covering aluminium-foil paper dries 2d, removes liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry
2d obtains solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water,
The solid particle being completely dried.After pulverizing, with molar concentration be 3.5mol/L HCl solution impregnate 3 times, every time about
5min, then uses pure water 3 times again, every time about 5min, drying.It will be calcined in 300 DEG C of Muffle furnaces of solid particle after drying,
Obtain PFSA/SiO2Superpower solid acid catalyst.
The specific surface area for the solid particle catalyst analyzed with BET methods is 377.213m2/ g, Kong Rongwei
0.389cm3/ g, aperture 3.508nm.
With blender, thermometer, reflux condensing tube 250mL three-necked flasks in absolute ethyl alcohol 40.00g, ice is added
Acetic acid 62.60g and above-mentioned superpower solid acid catalyst 8.00g flows back under the conditions of 95 DEG C, mechanical agitation 5.0h, waits for that reaction finishing,
It negates and supernatant is answered to carry out gas chromatographic analysis, calculate analysis and show that the conversion ratio of ethyl alcohol is 84.21%.
Claims (1)
1. a kind of preparation method of composite solid catalyst for production of superstrong, it is characterised in that：The perfluor sulphur for being 1.10 by exchange capacity
Acid resin is added in alcohol-aqueous solution, and under high pressure, reflux, 250 DEG C of 8.0 h of mechanical agitation are consolidated after evaporation, concentration
The perfluor sulfoacid resin solution that content is 5%；
17.30 g deionized waters are added into 50.00 g ethyl orthosilicates, are added with stirring the HCl solution of 0.04 mol/L
12.50g is stirred always to solution and is clarified；The teos solution after hydrolysis is added to 48.05 g perfluorinated sulfonic acids under stirring
In the mixed liquor of the NaOH solution of 0.05 mol/L of resin solution and 48.05 g, solution gel quickly；By gel at 75 DEG C
It covers aluminium-foil paper and dries 2d, remove liquid water；Then remove aluminium-foil paper, be placed in 95 DEG C of thermostatic drying chambers dry 2d,
Obtain solid particle；Finally, by solid particle in being positioned over 140 DEG C of vacuum drying chambers, dry 2d removes all water, obtains
To the solid particle being completely dried；After pulverizing, impregnated 5 times, every time 3 min with the HCl solution that molar concentration is 3.5 mol/L,
Then pure water is used again 5 times, every time 3 min, drying；Solid particle after drying is calcined in 300 DEG C of Muffle furnaces, is obtained
PFSA/SiO2Superpower solid acid catalyst；
The PFSA/SiO analyzed with BET methods2The specific surface area of superpower solid acid catalyst is 584.633 m2/ g, Kong Rong
For 0.611cm3/ g, aperture are 4.003 nm；
With blender, thermometer, reflux condensing tube 250 mL three-necked flasks in absolute ethyl alcohol 40.00 g, ice vinegar is added
62.60 g of acid and above-mentioned 8.00 g of superpower solid acid catalyst flow back under the conditions of 95 DEG C, and 5.0 h of mechanical agitation waits having reacted
Finish, negate and supernatant is answered to carry out gas chromatographic analysis, calculates analysis and show that the conversion ratio of ethyl alcohol is 90.44%.
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