CN115477568A - Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid - Google Patents
Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid Download PDFInfo
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006482 condensation reaction Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 21
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003980 solgel method Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 241001168730 Simo Species 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 238000010478 Prins reaction Methods 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JRFKHZNULLDOGQ-UHFFFAOYSA-N 2,5-dimethylhexa-1,4-diene Chemical compound CC(C)=CCC(C)=C JRFKHZNULLDOGQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- UUIRDIWGVMSEBE-UHFFFAOYSA-N acetylene propan-2-one Chemical compound C#C.CC(C)=O UUIRDIWGVMSEBE-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
-
- 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
- B01J21/12—Silica and alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/51—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- C07C2527/19—Molybdenum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the technical field of catalysts, in particular to SiO for catalytically synthesizing 2, 5-dimethyl-2, 4-hexadiene 2 A supported heteropoly acid catalyst is prepared from Isobutene (IB)/Isobutyraldehyde (IBA) as reactant through reaction on SiO 2 Carrying out Prins condensation reaction under the condition of a supported heteropoly acid catalyst. The invention has the advantages that: simple process, high yield, wide reactant source, moderate cost, easy preparation of catalyst, and suitability for use in preparation of catalystLarge-scale production; the content of the prepared product 2, 5-dimethyl-2, 4-hexadiene can reach 60 percent and meet the requirement of industrial products; strong reaction specificity, easy separation, repeated use and environmental protection.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on a Prins condensation reaction catalyzed by heteropoly acid.
Background
2, 5-dimethyl-2, 4-hexadiene is an important chemical raw material for synthesizing pyrethroid and is also an important organic intermediate for preparing pesticides, medicines and various organic syntheses. In the prior art, many methods for preparing 2,5-dimethyl-2,4-hexadiene are disclosed, for example, in Chinese patent document (application No. CN 96115489.6), a one-step method for synthesizing 2,5-dimethyl-2,4-hexadiene reaction catalyst and an application thereof are disclosed, wherein 2,5-dimethyl-2,5-hexadiene is prepared by simultaneously carrying out dehydration and isomerization reactions of 2,5-dimethyl-2,5-hexanediol under the action of an alkali-treated zeolite molecular sieve or a zeolite molecular sieve catalyst added with proper amount of Fe (III) and Cu (II) and carrying out one-step preparation of 2,5-dimethyl-2,4-hexadiene. The reaction is carried out under the conditions of normal pressure and 180-250 ℃ by adopting the catalytic system. Although high selectivity can be obtained, the current main production method of 2, 5-dimethyl-2, 5-hexanediol is to produce 2, 5-dimethyl-2, 4-hexadiene by acetylene acetone method and then 2, 5-dimethyl-2, 5-hexanediol through dehydration and isomerization, but the process is complex, has a lot of byproducts, is highly corrosive to equipment and pollutes the environment. The experiment adopts a reaction system taking isobutene and isobutyraldehyde as raw materials, and the system has simple process, no corrosion to equipment and little environmental pollution, and is increasingly valued by people.
Further, as disclosed in chinese patent document (application No. CN 202111064454.1), a preparation method of 2, 5-dimethyl-2, 4-hexadiene from isobutyraldehyde comprises using palladium-doped ZSM-5 as a catalyst, and using a fixed bed reaction apparatus to perform a condensation reaction between tert-butanol and isobutyraldehyde, wherein the yield is more than 80%. However, the synthesis process of the catalyst is complex, the crystallization time is long, and the synthesized catalyst has low repeatability and utilization rate. The catalyst of the invention has simple preparation process and high reusability.
At present, niobic acid is mainly used as a catalyst in industry, and the research on the catalytic synthesis of 2, 5-dimethyl-2, 4-hexadiene published by Chenjunqin and the like (Master's academic paper of Huadong university of science) is carried out under the conditions that the reaction pressure is 5-7MPa, the reaction temperature is 240 ℃, and the reaction temperature is 4:1, mass space velocity of 5h -1 The yield of the 2, 5-dimethyl-2, 4-hexadiene can reach more than 60 percent. However, the catalyst must be reacted under high pressure, otherwise temperatures of up to 300 ℃ are required to achieve the higher temperaturesYield, while at high temperature the catalyst is easily deactivated by carbon deposition and is not reproducible. The feed ratio has higher catalytic activity, but the surface acid amount of the niobic acid is less, the activity cannot meet the industrial requirement, the required reaction pressure on equipment is higher, and the catalyst has the problems of high price, complex preparation method, difficult regeneration after inactivation and the like. The reaction at high temperature puts higher requirements on reaction equipment, and is not beneficial to safe production. On the basis, the invention can obtain the catalyst with higher yield and anti-carbon deposition performance under normal pressure so as to reduce the requirement of the reaction on industrial equipment.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides a method for synthesizing 2, 5-dimethyl-2, 4-hexadiene by a Prins condensation reaction based on heteropoly acid catalysis, and the used catalyst has the characteristics of low price, high conversion rate, simple preparation scheme, easier separation of a product 2, 5-dimethyl-2, 4-hexadiene and good economic and industrial values. The invention passes through SiO 2 -Al 2 O 3 The supported heteropolyacid catalyst, silica supported heteropolyacid is a promising catalyst.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on a Prins condensation reaction catalyzed by heteropoly acid comprises the following steps: taking isobutyraldehyde as a raw material, introducing isobutene into a fixed bed at a certain flow rate, filling a heteropoly acid catalyst into the fixed bed reactor, and carrying out synthetic reaction through the fixed bed reactor; the reaction pressure is the self pressure of the reaction system or the inert gas is filled into the reaction system for pressure stabilization, the reaction temperature is carried out at 260 to 350 ℃, and the mass space velocity is 2 to 5 hours -1 The mol ratio of isobutyraldehyde to isobutene is 1: 2-1: 4, the amount of the catalyst is 0.7 to 1.2g, and the reaction product 2, 5-dimethyl-2, 4-hexadiene is separated out by a separator.
The heteropolyacid catalyst is Al-doped prepared by a sol-gel method 2 O 3 SiO of (2) 2 Microsphere (SiO for short) 2 -Al 2 O 3 Carrier) uniformly loaded with SiW, PW, siMo and PMoA heteropoly acid; siO 2 2 -Al 2 O 3 Al in carrier 2 O 3 With SiO 2 Is =0.1:1 to 1:1, siW: PW: siMo: PMo =0.1:0.1:1:1 to 1:1:1:1 (molar ratio).
Further, siO 2 -Al 2 O 3 The preparation method of the carrier comprises the following steps:
the amorphous SiO is prepared by taking tetraethyl orthosilicate and aluminum sec-butoxide as raw materials and adopting a sol-gel method 2 -Al 2 O 3 . Tetraethyl orthosilicate was initially heated to 75 ℃, and aluminum sec-butoxide was dissolved in ethanol. The first two solutions were then mixed under vigorous stirring. Then, a small amount of water was added to the mixture to obtain a transparent gel. Finally, after stirring for several hours, siO is obtained by filtration and drying 2 -Al 2 O 3 And (3) a carrier.
SiO is compared with silicon-aluminum zeolite molecular sieve 2 -Al 2 O 3 The acidity of the carrier is higher and the activity and selectivity of the reaction can be better improved.
Further, the method for supporting the heteropolyacid catalyst comprises the following steps: to dry SiO 2 -Al 2 O 3 Carrier dropping H 4 SiW 12 O 40 (SiW)、H 3 PW 12 O 40 (PW)、H 4 SiMo 12 O 40 (SiMo) and H 3 PMo 12 O 40 And (PMo) fully soaking and adsorbing the deionized water solution, drying, and calcining in air at 200-300 ℃ for 3-5 h to obtain the heteropoly acid catalyst.
The SiO 2 The specific preparation method of the supported heteropolyacid catalyst comprises the following steps:
(1) H is to be 4 SiW 12 O 40 (SiW)、H 3 PW 12 O 40 (PW)、H 4 SiMo 12 O 40 (SiMo) and H 3 PMo 12 O 40 (PMo) was added to deionized water to make solutions of different concentrations, where n (SiW): n (PW): n (SiMo): n (PMo) =0.1:0.1:1:1 to 1:1:1:1, the concentration of different solutions is 10-70wt%, and the solutions are divided into 7 types. In SiO 2 Middle doped with small amount of Al 2 O 3 Fully mixing to obtain SiO carrier 2 -Al 2 O 3 。
(2) Drying a certain amount of dried carrier which is SiO 2 -Al 2 O 3 And the drying condition is that the drying is carried out for 3 to 5 hours at the temperature of between 90 and 120 ℃.
(3) And (3) dripping the solutions with different concentrations in the step (1) into the carrier in the step (2), carrying out equal-volume impregnation, and standing for 5 hours.
(4) And (4) putting the solid obtained in the step (3) into an oven, and drying to obtain a catalyst precursor, wherein the drying condition is that the solid is dried for 5-8 h at 90-120 ℃.
(5) Calcining the catalyst precursor obtained in the step (4) in air, and calcining the catalyst precursor in air at 200-300 ℃ for 3-5 h to obtain samples under different loading amounts, namely xHPA, wherein x is the content of the impregnated heteropoly acid.
Compared with the prior art, the invention has the following technical advantages:
(1) The catalyst of the invention is made of SiO 2 -Al 2 O 3 As a carrier, wherein SiO 2 -Al 2 O 3 The carrier has the advantages of high thermal stability, moderate acidity and alkalinity, and the like. SiO 2 2 -Al 2 O 3 Bronsted acidity ratio SiO on a support 2 Is much higher and can obviously improve the activity and the selectivity of the Prins condensation reaction. SiO 2 2 And Al 2 O 3 SiO is the most commonly used catalyst support due to its high specific surface area, high thermal and mechanical stability 2 And Al 2 O 3 The chemical nature of the catalyst (e.g. affinity or acidity for metal ions) can be altered and the aluminium and silicon atoms become more positive and more negative, respectively, when they interact with the tungsten atom, indicating that there are some different inducing effects on the catalyst species depending on the chemical nature of the support. Compared with the amorphous SiO prepared conventionally 2 -Al 2 O 3 In contrast, the catalyst supports prepared by the methods of the present application have highly tunable synthesis routes that will allow for future material optimization; more comprehensive active area, and active site of acidThe distribution shifts to a stronger reactivity. Has better development prospect and application in the future.
(2) HPA has been widely used in acid and oxidation catalysts, which are believed to have a strong, pure Bronsted acidity, stronger than many mineral acids or traditional solid acids, H 3 PW 12 O 40 The catalyst has higher stability in the preparation process, and silicotungstic acid (SiW) is the most active and selective HPA and is strongly associated with inherent SiW proton
The acid site showed stronger activity in the prins reaction. However, catalyst selectivity and stability can be improved by optimizing the reaction temperature, the SiW loading, which should be high enough (within 45-65%) to achieve stable and efficient performance. SiO 2 2 -Al 2 O 3 The supported heteropoly acid is a promising catalyst, HPA has higher dispersity on the surface of silicon dioxide, siO 2 The microspheres load active centers, so that more active center sites are well exposed. Emphasis is given to elucidating the relationship between the properties of the HPA catalysts in the Prins condensation, their acidity and the nature of the carbonaceous deposits. Deposition of tungsten-based heteropoly acid on SiO 2 -Al 2 O 3 Can form highly dispersed HPA nanocrystals. As the HPA loading increases, the number of acid sites increases gradually, and the prins reaction carried out over the HPA catalyst tends to be complex with strong coking phenomena, which can alter the stability and selectivity of the catalyst, even providing additional active sites for the reaction. A challenge faced by future acid catalysts is to control the strength/character of the acid sites and their environment.
(3) The catalyst has no requirement on equipment, does not need strong acid and strong alkali environment, is very simple to separate, has high activity, and is more beneficial to the implementation of chemical production.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
Preparation of the catalyst: firstly, the sol-gel method is adopted to prepare amorphous SiO 2 -Al 2 O 3 The carrier is ready for use; 0.2gH 4 SiW 12 O 40 (SiW)、0.2gH 3 PW 12 O 40 (PW)、0.3gH 4 SiMo 12 O 40 (SiMo) and 0.3gH 3 PMo 12 O 40 (PMo) was added to 10ml of deionized water to obtain a 10wt% solution, the solution was allowed to stand for half an hour, and then solutions of different concentrations were dropped into the prepared SiO 2 -Al 2 O 3 Dipping, then placing for 3h at room temperature, then transferring into a 100 ℃ oven for drying for 5h to obtain a precursor of the catalyst, and calcining for 3h in air at 300 ℃ to obtain the catalyst with 10wt% of active components.
Weighing 1g of the catalyst and 6g of isobutyraldehyde, supplying gas isobutene at a constant flow rate of 15ml/min in a normal-pressure fixed bed reactor at an airspeed of 5h -1 The reaction temperature is raised from room temperature to 260 ℃ at 5 ℃/min, and finally the reaction product is taken out and analyzed by gas chromatography.
Example 2
Take 0.5gH 4 SiW 12 O 40 (SiW)、0.5gH 3 PW 12 O 40 (PW)、0.75gH 4 SiMo 12 O 40 (SiMo) and 0.75gH 3 PMo 12 O 40 (PMo) was added to 10ml of deionized water to obtain 20wt% solutions, respectively, and the other steps were the same as in example 1.
Example 3
Calcination in air at 300 deg.C for 3h was replaced with calcination in air at 200 deg.C for 3h, and the other steps were the same as in example 1.
Example 4
0.7g of the catalyst prepared in example 1, 6g of isobutyraldehyde and gaseous isobutene were weighed out and supplied at a constant flow rate of 10ml/min in a fixed bed reactor at a space velocity of 5h -1 Reacting under normal pressure, raising the temperature from room temperature to 300 ℃ at the speed of 5 ℃/min, and finally taking out a reaction product for analysis by adopting gas chromatography. The other steps are the same as in example 1.
Example 5
The catalyst prepared in example 1 was weighed out1g of catalyst, 6g of isobutyraldehyde, gaseous isobutene were supplied at a constant flow rate of 10ml/min in a fixed bed reactor at a space velocity of 5h -1 Reacting at normal pressure, raising the temperature from room temperature to 350 ℃ at 5 ℃/min, and finally taking out a reaction product for analysis by adopting gas chromatography. The other steps are the same as in example 1.
Comparative example 1
Preparation of the catalyst: firstly, the sol-gel method is adopted to prepare amorphous SiO 2 -Al 2 O 3 The carrier is ready for use; 1gH is reacted with 4 SiW 12 O 40 (SiW) was added to 10ml of deionized water to obtain a 10wt% solution, the solution was allowed to stand for half an hour, and then solutions of different concentrations were dropped into the prepared SiO 2 -Al 2 O 3 Dipping, then placing for 3h at room temperature, then transferring into a 100 ℃ oven for drying for 5h to obtain a precursor of the catalyst, and calcining for 3h in air at 300 ℃ to obtain the catalyst with 10wt% of active components.
The other steps are the same as in example 1.
Comparative example 2
Preparation of the catalyst: firstly, the sol-gel method is adopted to prepare amorphous SiO 2 -Al 2 O 3 The carrier is ready for use; 1gH is reacted with 3 PW 12 O 40 (PW) adding 10ml of deionized water to obtain a 10wt% solution, standing the solution for half an hour, and then dropping the solutions with different concentrations into the prepared SiO 2 -Al 2 O 3 Dipping, then placing for 3h at room temperature, then transferring into a 100 ℃ oven for drying for 5h to obtain a precursor of the catalyst, and calcining for 5h in air at 300 ℃ to obtain the catalyst with 10wt% of active components.
The other steps are the same as in example 1.
Comparative example 3
Preparation of the catalyst: firstly, the sol-gel method is adopted to prepare amorphous SiO 2 -Al 2 O 3 A carrier is ready for use; 1gH is reacted with 4 SiMo 12 O 40 (Simo) was added to 10ml of deionized water to obtain a 10wt% solution, the solution was allowed to stand for half an hour, and then solutions of different concentrations were dropped into the prepared SiO 2 -Al 2 O 3 Dipping, then placing for 3h at room temperature, then transferring into a 100 ℃ oven for drying for 5h to obtain a precursor of the catalyst, and calcining for 5h in air at 300 ℃ to obtain the catalyst with 10wt% of active components.
The other steps are the same as in example 1.
Comparative example 4
Preparation of the catalyst: firstly, the sol-gel method is adopted to prepare amorphous SiO 2 -Al 2 O 3 A carrier is ready for use; 1gH is reacted with 3 PMo 12 O 40 (PMo) was added to 10ml of deionized water to obtain a 10wt% solution, the solution was allowed to stand for half an hour, and then solutions of different concentrations were dropped into the prepared SiO 2 -Al 2 O 3 Dipping, then placing for 3h at room temperature, then transferring into a 100 ℃ oven for drying for 5h to obtain a precursor of the catalyst, and calcining for 5h in air at 300 ℃ to obtain the catalyst with 10wt% of active components.
The other steps are the same as in example 1.
Comparative example 5
Preparation of the catalyst: first, siO is determined 2 Weighing 2gSiO 2g of water absorption of the microspheres 2 Drying at 100 deg.C to obtain carrier. 1gH is reacted with 4 SiW 12 O 40 (SiW) was added to 10ml of deionized water to obtain a 10wt% solution, the solution was allowed to stand for half an hour, and then solutions of different concentrations were dropped into the prepared SiO 2 Dipping, then placing for 3h at room temperature, then transferring into a 100 ℃ oven for drying for 5h to obtain a precursor of the catalyst, and calcining for 5h in air at 300 ℃ to obtain the catalyst with 10wt% of active components.
The other steps are the same as in example 1.
The product properties under different process conditions in the above examples and comparative examples are shown in Table 1:
TABLE 1 comparison of product Properties under different Process conditions in the examples and comparative examples
| Serial number | Conversion ratio of raw Material (%) | Catalyst selectivity (%) |
| Example 1 | 100 | 65 |
| Example 2 | 98 | 71 |
| Example 3 | 97 | 64 |
| Example 4 | 99 | 68 |
| Example 5 | 98 | 63 |
| Comparative example 1 | 69 | 42 |
| Comparative example 2 | 72 | 46 |
| Comparative example 3 | 66 | 35 |
| Comparative example 4 | 68 | 37 |
| Comparative example 5 | 76 | 45 |
Table 1 shows that the acid active site catalyst loaded by the method has higher reaction activity for Prins condensation reaction of raw materials, the solid catalyst and the product are easy to separate, the equipment is not corroded, and the method is an environment-friendly green catalyst.
It will be appreciated that modifications and variations are possible to those skilled in the art in light of the above teachings and are intended to be included within the scope of the appended claims.
Claims (4)
1. A method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropoly acid is characterized by comprising the following steps: the method comprises the following steps: isobutyraldehyde is taken as a raw material, isobutene is introduced into a fixed bed at a certain flow rate, a heteropoly acid catalyst is filled in the fixed bed reactor, and the fixed bed reactor is used for synthesis reaction; the reaction pressure is the self pressure of the reaction system or the inert gas is filled into the reaction system for pressure stabilization, the reaction temperature is carried out at 260 to 350 ℃, and the mass space velocity is 2 to 5 hours -1 The mol ratio of isobutyraldehyde to isobutene is 1: 2-1: 4, the catalyst dosage is 0.7-1.2g, and the reaction product 2, 5-dimethyl-2, 4-hexadiene is separated out by a separator;
the heteropoly acid catalyst is SiO prepared by a sol-gel method 2 -Al 2 O 3 The microspheres uniformly load heteropoly acid consisting of SiW, PW, siMo and PMo; siO 2 2 -Al 2 O 3 Al in microspheres 2 O 3 With SiO 2 Is =0.1:1 to 1:1,SiW: PW: siMo: PMo =0.1:0.1:1:1 to 1:1:1:1 (molar ratio).
2. The method for the synthesis of 2, 5-dimethyl-2, 4-hexadiene based on a heteropoly acid catalyzed Prins condensation reaction according to claim 1, wherein: the method for supporting the heteropolyacid catalyst comprises: to dry SiO 2 -Al 2 O 3 Microsphere dropwise addition H 4 SiW 12 O 40 、H 3 PW 12 O 40 、H 4 SiMo 12 O 40 And H 3 PMo 12 O 40 The obtained deionized water solution is fully soaked and adsorbed, then dried and calcined in air at the temperature of 200-300 ℃ for 3-5 hours to obtain the heteropoly acid catalyst.
3. The process for the synthesis of 2, 5-dimethyl-2, 4-hexadiene based on a heteropoly acid catalyzed Prins condensation reaction according to claim 2, wherein: the concentration of the deionized water solution is 10-70wt%.
4. The method for the synthesis of 2, 5-dimethyl-2, 4-hexadiene based on a heteropoly acid catalyzed Prins condensation reaction according to claim 1, wherein: siO 2 2 -Al 2 O 3 The preparation method of the carrier comprises the following steps:
the amorphous SiO is prepared by taking tetraethyl orthosilicate and aluminum sec-butoxide as raw materials and adopting a sol-gel method 2 -Al 2 O 3 Tetraethyl orthosilicate is initially heated to 75 ℃, aluminum sec-butoxide is dissolved in ethanol, the first two solutions are mixed under vigorous stirring, then a small amount of water is added to the mixture to obtain a transparent gel, and finally, after stirring for several hours, siO is obtained by filtration and drying 2 -Al 2 O 3 And (3) a carrier.
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