CN117384027A - Method for preparing isooctanoic acid by self-condensation and oxidation of n-butyraldehyde - Google Patents
Method for preparing isooctanoic acid by self-condensation and oxidation of n-butyraldehyde Download PDFInfo
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000009833 condensation Methods 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 33
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 31
- 239000011949 solid catalyst Substances 0.000 claims abstract description 31
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- -1 fluorine ions Chemical class 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 52
- 238000003756 stirring Methods 0.000 description 40
- 239000007868 Raney catalyst Substances 0.000 description 26
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 26
- 229910000564 Raney nickel Inorganic materials 0.000 description 26
- 239000002585 base Substances 0.000 description 26
- 238000005984 hydrogenation reaction Methods 0.000 description 26
- 238000001816 cooling Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 230000003197 catalytic effect Effects 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PYLMCYQHBRSDND-UHFFFAOYSA-N 2-ethyl-2-hexenal Chemical compound CCCC=C(CC)C=O PYLMCYQHBRSDND-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention belongs to the technical field of catalysts, and in particular relates to a method for preparing isooctanoic acid by self-condensation and oxidation of n-butyraldehyde, which adopts acid and alkaliThe solid catalyst and the n-butyraldehyde can be prepared according to the following ratio of 0.5-15: 100, reacting for 0.5-8 h at 20-200 ℃ in a protective atmosphere to separate out an acid-base bifunctional solid catalyst, then adding SBA-15 loaded heteropolyacid catalyst with 1-10% of the mass of n-butyraldehyde into the obtained reaction system for mixing, and introducing oxygen for oxidation to obtain isooctanoic acid, wherein the acid-base bifunctional solid catalyst is prepared by loading fluorine ions on Al 2 O 3 ‑TiO 2 The supported catalyst formed on the composite carrier is used for providing fluorine-containing substances of fluorine ions to be supported on Al in a weight percentage of 0.5-15% 2 O 3 ‑TiO 2 And (3) on a composite carrier.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a method for preparing isooctanoic acid by self-condensation and oxidation of n-butyraldehyde.
Background
Isooctanoic acid is an oily liquid, soluble in hot water, slightly soluble in cold water and ethanol, and is mainly used as a paint drier, an ink thickener, various unsaturated polyester resin accelerators, and some catalysts. In addition, the isooctanoate has wide application in metal processing, lubricating auxiliary agent protection, polyvinyl chloride processing auxiliary agent, oil additive and the like. Isooctanoic acid can also be used as an intermediate to synthesize various medicines, dyes, pesticides, fragrances and the like. In recent years, the isooctanoic acid demand in domestic and foreign markets is increasing, the productivity is insufficient, and the product supply is tension, so that the method has high economic benefit.
The industrial synthesis of isooctanoic acid mainly has two routes, namely an isooctanol oxidation method which has high selectivity, reliable raw material sources and simple operation, but has long process flow and is not easy for large-scale production; and secondly, taking n-butyraldehyde as a raw material, condensing and dehydrating to generate 2-ethyl hexenal, hydrogenating to obtain isooctyl aldehyde, and oxidizing to obtain isooctanoic acid. The aldehyde oxidation method has reliable sources of raw materials, is a continuous and totally-enclosed process, and is easy for large-scale production.
The n-butyraldehyde aldol condensation is a key for realizing carbon chain growth in the octanol production process, and a large number of catalysts are used in the industrial n-butyraldehyde aldol condensation preparation process nowadays, but a large amount of industrial waste alkaline water is brought by the traditional liquid base catalyst, and a large amount of acid liquor is needed for neutralization and washing, so that the environment pollution is caused, and the cost is increased. With the development of green chemistry, there is increasing emphasis on the development of new catalytic processes that are environmentally friendly. Solid catalysts have many advantages such as high activity, high selectivity, high stability, easy separation of products, and the like, and are attracting attention. However, the solid base catalyst has poor stability and is difficult to reuse. Compared with the traditional acid or base catalysis, the acid-base synergistic catalysis has more advantages, and meets the development requirement of green chemistry. Therefore, development of an acid-base bifunctional solid catalyst is one of the directions of research on the self-condensation reaction of n-butyraldehyde.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde, which comprises the steps of mixing an acid-base bifunctional solid catalyst with n-butyraldehyde according to the ratio of 0.5-15: 100, reacting for 0.5-8 h at 20-200 ℃ in protective atmosphere, separating out acid-base double-function solid catalyst, adding 1-10% SBA-15 supported heteropolyacid catalyst to the reaction system, introducing oxygen to oxidize to obtain isooctanoic acid,
wherein, the acid-base bifunctional solid catalyst is supported by fluorine ions on Al 2 O 3 -TiO 2 The supported catalyst formed on the composite carrier is used for providing fluorine-containing substances of fluorine ions to be supported on Al in a weight percentage of 0.5-15% 2 O 3 -TiO 2 And (3) on a composite carrier.
As preferable: the preparation method of the acid-base bifunctional solid catalyst comprises the steps of mixing NaAlO 2 Dissolved in TiCl 4 In the solution, the pH value of the obtained mixed system is regulated and the obtained precipitate is fully precipitated, the obtained precipitate is separated out and fully washed by deionized water, and then dried, and then baked to obtain Al 2 O 3 -TiO 2 Composite carrier, al 2 O 3 -TiO 2 And (3) soaking the composite carrier in the solution for adsorbing the fluorine-containing substances, drying, and calcining to obtain the acid-base bifunctional solid catalyst.
Further: tiCl 4 TiCl in the solution 4 The concentration is 0.1mol/L to 5mol/L.
Further: naAlO (NaAlO) 2 In solution, naAlO 2 The concentration is 0.1mol/L to 10mol/L.
Further: the pH value of the obtained mixed system is regulated to 7.0-11.0 by ammonia water.
Further: the drying temperature is 100-160 ℃, and the drying time is 1-10 h.
Further: the roasting temperature is 300-900 ℃ and the roasting time is 1-4 h.
Further: the fluorine-containing substance is KF or NaF.
Further: fluorine-containing material and Al 2 O 3 -TiO 2 The molar ratio of the composite carrier is 0.01-1: 1.
further: the calcination temperature is 200-300 ℃ and the calcination time is 3-5 h.
Further: tiCl 4 Solution and NaAlO 2 The solvent in the solution is one of water, methanol, ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-hexane, cyclohexane, toluene and p-xylene.
As preferable: the preparation method of the SBA-15 supported heteropoly acid catalyst comprises the steps of completely dissolving P123 in hydrochloric acid aqueous solution, adding Tetraethoxysilane (TEOS) into the solution, fully dispersing the solution, standing and crystallizing in a heat preservation state, separating out solid, washing the solid to be neutral, drying the solid, and roasting the solid in air to obtain the SBA-15 molecular sieve; the SBA-15 molecular sieve is fully mixed and dispersed in phosphotungstic heteropoly acid (H) 3 PW 12 O 40 ) After the water solution of (2) is kept warm for a period of time, the mixed system is filtered, and the obtained filter cake is dried and then calcined to obtain the SBA-15 supported heteropolyacid catalyst.
The beneficial effects of the invention are as follows: the proposal uses Al 2 O 3 -TiO 2 The acid-base double-function solid catalyst is a carrier, and can effectively promote the self-condensation reaction of the n-butyraldehyde due to the synergistic effect of the surface alkaline groups and the acid groups. In the organic synthesis reaction, al 2 O 3 Is a commonly used acid catalyst. It is generally considered that Al 2 O 3 The surface being co-located with Lewis acid sitesAcid position, wherein Lewis acid position is derived from surface-exposed Al atom, and +.>The acid position is formed by hydroxyl on Al atoms on the surface of the aluminum oxide tetrahedron; at the same time KF provides F in the reaction - Is the catalyst base center, F - After hydrogen bonding with alpha-H on the reactant n-butyraldehyde, alpha-C nucleophilicity is realizedEnhancement, also catalyzing the progress of the n-butyraldehyde self-condensation reaction; on the basis of which the catalyst is prepared by TiO 2 After further compounding, the relative strength and the relative position of the two acid-base active phases relative to the reactant n-butyraldehyde can be effectively regulated and controlled: may be based on Al 2 O 3 And TiO 2 The surface structure of the composite carrier formed by mixing and cohydrolysis is easier to combine with active H point positions on the n-butyraldehyde, thereby leading the catalytic alkali center F on the composite carrier to be - Is easier to combine with alpha-H on the n-butyraldehyde to generate positive carbon ions, and effectively improves the catalytic activity of the self-condensation reaction of the n-butyraldehyde.
SBA-15 loaded heteropoly acid catalyst is easy to diffuse from isooctyl aldehyde to a catalyst pore canal because SBA-15 has ordered mesoporous structure and pore size, and meanwhile, the heteropoly acid is taken as an active center to improve an acidic site, so that the conversion rate of an intermediate product and the selectivity of isooctanoic acid can be effectively improved.
The two catalysts have the advantages of high selectivity, high catalytic activity, mild use condition, no corrosion to equipment, reusability and the like, meet the development requirements of green chemistry and have good industrial prospect.
Detailed Description
Preparation of the acid-base bifunctional solid catalyst used in the following examples:
1.08mol of NaAlO 2 Dissolved in 300mL TiCl with a concentration of 1.8mol/L 4 In water solution, after mixing thoroughly, regulating pH value of the obtained mixed system to 11 with ammonia water and precipitating thoroughly, filtering and separating the obtained precipitate, washing thoroughly with deionized water, oven drying at 120deg.C for 6 hr, and roasting at 600deg.C for 3 hr to obtain Al 2 O 3 -TiO 2 The composite carrier is prepared from the components of the composite carrier,
according to KF and Al 2 O 3 -TiO 2 The molar ratio of the composite carrier is 0.1:1 (molar ratio of F: al: ti is 0.1:2:1, the same applies below), and the entire KF aqueous solution is dropwise added to the Al obtained above 2 O 3 -TiO 2 After fully soaking and adsorbing on the composite carrier, the Al is added into the composite carrier 2 O 3 -TiO 2 Drying the composite carrier at 120deg.C for 2 hr, and air-drying at 300deg.CCalcining for 4h to obtain the acid-base bifunctional solid catalyst KF/Al 2 O 3 -TiO 2 。
Preparation of SBA-15 Supported heteropolyacid catalyst used in the examples below:
adding 2g of P123 into 80mL of hydrochloric acid aqueous solution with the concentration of 2mol/L, stirring for 3 hours at 50 ℃ in a constant-temperature electromagnetic oven water bath to completely dissolve, adding 4.5mL of Tetraethoxysilane (TEOS) into the mixture by a pipette, continuously stirring for 4 hours at 50 ℃ in the water bath, transferring the reaction system into a baking oven with the temperature of 100 ℃ to stand for 48 hours for crystallization, filtering out solid from the reaction system, washing the solid to be neutral by ammonia water, fully drying at room temperature (25 ℃, the same applies below), and roasting in static air for 6 hours at 550 ℃ to obtain the SBA-15 molecular sieve;
10mL of deionized water was weighed into a polytetrafluoroethylene-lined reactor, and 0.2632g of phosphotungstic heteropoly acid (H) 3 PW 12 O 40 ) After the SBA-15 molecular sieve is completely dissolved by light vibration, 5g of the SBA-15 molecular sieve is weighed and added, after the mixture is fully mixed and dispersed (at the moment, the mixture in the reactor is viscous), the mixture is transferred into a 100 ℃ oven for 24 hours, then the mixture is filtered, the obtained filter cake is dried at 150 ℃ for 10 hours, and then the filter cake is baked in a muffle furnace at 550 ℃ for 4 hours to obtain the SBA-15 supported heteropolyacid catalyst.
Example 1
Into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and the reaction was continued with stirring at a flow rate of 30mL/minIntroducing oxygen (O) 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Example 2
The amount of the acid-base bifunctional solid catalyst and the SBA-15 supported heteropolyacid catalyst relative to the n-butyraldehyde is reduced, and the rest conditions are the same as those of the example 1:
into a 100mL autoclave were charged 20g of deionized water, 2.5g of n-butyraldehyde, and 0.25g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.1g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Example 3
The temperature and time of the self-condensation reaction were reduced, and the other conditions were the same as in example 1:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 100 ℃ under stirring, reacting for 7 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; then 0.2g of Raney nickel hydrogenation catalyst is added into the reaction kettle, and the hydrogen in the kettle is replaced by hydrogenAfter the gas reaches 4Mpa, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring, stopping heating, releasing the pressure in the reaction kettle, and centrifugally separating a hydrogenation catalyst Raney nickel from the obtained reaction system after the reaction kettle is naturally cooled to room temperature; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Example 4
Deionized water without dispersant was used, and the other conditions were the same as in example 1:
into a 100mL autoclave were charged 5g of n-butyraldehyde and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Comparative example 1
Using Al 2 O 3 Instead of Al in example 1 2 O 3 -TiO 2 Preparation of acid-base double-function solid catalyst by composite carrier, and the other conditions are the same as in example 1:
preparation of an acid-base dual-function solid catalyst:
1.08mol of NaAlO 2 Dissolving in 300mL deionized water, mixing thoroughly, regulating pH to 11 with ammonia water, precipitating thoroughly, filtering the precipitate, washing thoroughly with deionized water, oven drying at 120deg.C for 6 hr, and calcining at 600deg.C for 3 hr to obtain Al 2 O 3 The carrier is used for the preparation of the carrier,
according to KF and Al 2 O 3 The molar ratio of the carrier is 0.1:1, and the KF aqueous solution was completely added dropwise to the Al solution obtained above 2 O 3 After fully soaking and adsorbing on the carrier, the Al is added 2 O 3 Drying the carrier at 120 ℃ for 2 hours, and calcining the carrier in air at 300 ℃ for 4 hours to obtain the acid-base bifunctional solid catalyst KF/Al 2 O 3 。
Preparation of isooctanoic acid:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde and 0.75g of KF/Al prepared as described in this comparative example 2 O 3 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Comparative example 2
Using TiO 2 Instead of Al in example 1 2 O 3 -TiO 2 Preparation of acid-base double-function solid catalyst by composite carrier, and the other conditions are the same as in example 1:
preparation of an acid-base dual-function solid catalyst:
300mL of TiCl having a concentration of 1.8mol/L was introduced 4 The pH value of the aqueous solution is adjusted to 11 by ammonia water to ensure that the precipitate is fully precipitated, the obtained precipitate is filtered and separated, and is fully washed by deionized water, and then dried for 6 hours at 120 ℃, and roasted for 3 hours at 600 ℃ to obtain the TiO 2 The carrier is used for the preparation of the carrier,
according to KF and TiO 2 The molar ratio of the carrier is 0.1:1, and the KF aqueous solution is completely dripped into the obtained TiO 2 After fully soaking and adsorbing on the carrier, the TiO is prepared 2 Drying the carrier at 120 ℃ for 2 hours, and calcining the carrier in air at 300 ℃ for 4 hours to obtain the acid-base bifunctional solid catalyst KF/TiO 2 。
Preparation of isooctanoic acid:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde and 0.75g of KF/TiO prepared as described in this comparative example 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Comparative example 3
Using SiO 2 Instead of Al in example 1 2 O 3 -TiO 2 TiO in composite support 2 After that, an acid-base bifunctional solid catalyst was prepared, and the other conditions were the same as in example 1:
preparation of an acid-base dual-function solid catalyst:
1.08mol of NaAlO 2 Dispersing into 300mL ethyl orthosilicate ethanol solution with concentration of 1.8mol/L, mixing thoroughly, regulating pH of the obtained mixed system to 11 with ammonia water, precipitating thoroughly, filtering the precipitate, washing thoroughly with deionized water, oven drying at 120deg.C for 6 hr, and roasting at 600deg.C for 3 hr to obtain Al 2 O 3 -SiO 2 The composite carrier is prepared from the components of the composite carrier,
according to KF and Al 2 O 3 -SiO 2 The molar ratio of the composite carrier is 0.1:1, and the KF aqueous solution was completely added dropwise to the Al solution obtained above 2 O 3 -SiO 2 After fully soaking and adsorbing on the composite carrier, the Al is added into the composite carrier 2 O 3 -SiO 2 Drying the composite carrier at 120 ℃ for 2 hours, and calcining the composite carrier in air at 300 ℃ for 4 hours to obtain the acid-base bifunctional solid catalyst KF/Al 2 O 3 -SiO 2 。
Preparation of isooctanoic acid:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -SiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. After filtering out the SBA-15 supported heteropoly acid catalyst in the resultant reaction system, the composition of the filtrate was analyzed by gas chromatography as shown in Table 1.
Comparative example 4
MgO is used instead of Al in example 1 2 O 3 -TiO 2 TiO in composite support 2 After that, an acid-base bifunctional solid catalyst was prepared, and the other conditions were the same as in example 1:
preparation of an acid-base dual-function solid catalyst:
1.08mol of NaAlO 2 Dispersed in 300mL of MgCl with concentration of 1.8mol/L 2 Mixing in water solution, regulating pH to 11 with ammonia water to precipitate, filtering to separate precipitate, washing with deionized water, oven drying at 120deg.C for 6 hr, and calcining at 600deg.C for 3 hr to obtain Al 2 O 3 -a MgO composite carrier, which is composed of a matrix,
according to KF and Al 2 O 3 -the molar ratio of MgO composite carrier is 0.1:1, and the KF aqueous solution was completely added dropwise to the Al solution obtained above 2 O 3 On MgO composite carrier, after fully soaking and adsorbing, al is added 2 O 3 Drying the MgO composite carrier for 2 hours at 120 ℃, and calcining for 4 hours at 300 ℃ in air to obtain the acid-base bifunctional solid catalyst KF/Al 2 O 3 -MgO。
Preparation of isooctanoic acid:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 MgO catalyst, N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then 0.2g of the SBA-15 supported heteropolyacid catalyst prepared above was charged therein, and oxygen (O) was continuously introduced therein with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. Filtering out SBA-15 supported heteropolyacid catalyst in the obtained reaction system, using gas phase chromatographyThe filtrate composition was analyzed spectrally as in table 1.
TABLE 1
( Wherein the conversion of n-butyraldehyde is "1- (mass of n-butyraldehyde remaining in the filtrate/(mass of original n-butyraldehyde × 100%)", the same applies below; the yield of isooctanoic acid is "mol% of isooctanoic acid in filtrate. Times.2/(mol% of original n-butyraldehyde. Times.100%", as follows )
As shown in table 1: comparison of the catalytic reaction results of comparative example 1 and comparative example 2 shows that: tiO (titanium dioxide) 2 The catalytic acidity activity for the self-condensation of n-butyraldehyde should be significantly lower than that of Al 2 O 3 A kind of electronic device. On this basis, example 1, which represents the present scheme, corresponds to the incorporation of 50% by mole of TiO into the catalyst support on the basis of comparative example 1 2 The catalytic activity is not reduced but is obviously improved, possibly based on Al 2 O 3 And TiO 2 The surface structure of the composite carrier formed by mixing and cohydrolysis is easier to combine with active H point positions on the n-butyraldehyde, so that F - More readily binds to alpha-H on n-butyraldehyde, resulting in improved catalytic activity.
Comparative example 3, comparative example 4, 50 mol% SiO was introduced into the catalyst support based on comparative example 1 2 Or MgO, and does not exceed the pure Al of comparative example 1 in overall catalytic activity 2 O 3 The carrier is due to SiO 2 Or MgO and Al 2 O 3 The surface structure of the composite support produced by cohydrolysis was different from that of example 1.
Comparative examples 5 to 9
Based on example 1, only oxygen (O 2 ) The catalyst used in the oxidation reaction was replaced with the catalyst used in the self-condensation reaction of n-butyraldehyde in example 1 and comparative examples 1, 2, 3 and 4 in this order, and the rest of the procedure was the same as in example 1:
comparative example 5
KF/Al 2 O 3 -TiO 2 Catalytic oxidation:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then, 0.2g of the same KF/Al prepared as described above was added thereto 2 O 3 -TiO 2 Continuously introducing oxygen (O) into the catalyst at a flow rate of 30mL/min under stirring 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. Filtering KF/Al from the obtained reaction system 2 O 3 -TiO 2 After the catalyst, the filtrate composition was analyzed by gas chromatography as in table 2.
Comparative example 6
KF/Al 2 O 3 Catalytic oxidation:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then, 0.2g of KF/Al prepared in comparative example 1 was charged thereinto 2 O 3 Continuously introducing oxygen into the catalyst at a flow rate of 30mL/min under stirringGas (O) 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. Filtering KF/Al from the obtained reaction system 2 O 3 After the catalyst, the filtrate composition was analyzed by gas chromatography as in table 2.
Comparative example 7
KF/TiO 2 Catalytic oxidation:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then, 0.2g of KF/TiO prepared in comparative example 2 was charged thereinto 2 Continuously introducing oxygen (O) into the catalyst at a flow rate of 30mL/min under stirring 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. Filtering KF/TiO in the obtained reaction system 2 After the catalyst, the filtrate composition was analyzed by gas chromatography as in table 2.
Comparative example 8
KF/Al 2 O 3 -SiO 2 Catalytic oxidation:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; then 0.2g of hydrogenation catalyst Raney nickel is put into the reaction kettle, hydrogen is used for replacing the gas in the kettle, after the hydrogen in the kettle reaches 4Mpa, the temperature and pressure are kept for 6 hours at 200 ℃ under stirring, the heating is stopped, the pressure in the kettle is released, and the reaction is carried outNaturally cooling the kettle to room temperature, and centrifugally separating a hydrogenation catalyst Raney nickel in the obtained reaction system; then, 0.2g of KF/Al prepared in comparative example 3 was added thereto 2 O 3 -SiO 2 Continuously introducing oxygen (O) into the catalyst at a flow rate of 30mL/min under stirring 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. Filtering KF/Al from the obtained reaction system 2 O 3 -SiO 2 After the catalyst, the filtrate composition was analyzed by gas chromatography as in table 2.
Comparative example 9
KF/Al 2 O 3 -MgO catalytic oxidation:
into a 100mL autoclave were charged 20g of deionized water, 5g of n-butyraldehyde, and 0.75g of KF/Al prepared as described above 2 O 3 -TiO 2 Catalyst, using N 2 After the air in the reaction kettle is replaced, heating to 180 ℃ under stirring, reacting for 8 hours, stopping heating, naturally cooling the reaction kettle to room temperature, and centrifugally separating the catalyst in the obtained reaction system; adding 0.2g of hydrogenation catalyst Raney nickel into the reaction kettle, replacing the gas in the kettle with hydrogen, keeping the temperature and pressure for 6 hours at 200 ℃ under stirring after the hydrogen in the kettle reaches 4Mpa, stopping heating, releasing the pressure in the kettle, naturally cooling the reaction kettle to room temperature, and centrifugally separating the hydrogenation catalyst Raney nickel in the obtained reaction system; then, 0.2g of KF/Al prepared in comparative example 3 was added thereto 2 O 3 MgO catalyst, into which oxygen (O) was continuously introduced with stirring at a flow rate of 30mL/min 2 ) And heating to 120 ℃, preserving heat for 8 hours, and oxidizing to obtain the isooctanoic acid. Filtering KF/Al from the obtained reaction system 2 O 3 After the MgO catalyst, the filtrate composition was analyzed by gas chromatography as shown in Table 2.
TABLE 2
As shown in table 2: the same KF/Al 2 O 3 -TiO 2 When the catalyst is used for catalytic oxidation reaction, KF/Al 2 O 3 -TiO 2 The catalyst does not show advantages over the same type of catalyst. This should be due to KF/Al after the reactants and reaction types are changed compared to Table 1 above 2 O 3 -TiO 2 The surface structure of the composite carrier of the catalyst can not be effectively combined with the corresponding active point on the molecular structure of the isooctyl aldehyde reactant, thereby leading the catalytic alkali center F - And not so easily bonded to that location. The composite catalyst has certain selectivity to reactants when fully exerting catalytic activity.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for preparing isooctanoic acid by self-condensation and oxidation of n-butyraldehyde is characterized by comprising the following steps: the preparation method comprises the steps of mixing an acid-base bifunctional solid catalyst with n-butyraldehyde according to the proportion of 0.5-15: 100, reacting for 0.5-8 h at 20-200 ℃ in a protective atmosphere, separating the acid-base bifunctional solid catalyst, then adding 1-10% of SBA-15 supported heteropoly acid catalyst by mass of n-butyraldehyde into the obtained reaction system for mixing after addition reaction in a hydrogen atmosphere, introducing oxygen for oxidation to obtain isooctanoic acid,
wherein the acid-base bifunctional solid catalyst is prepared by loading fluorine ions on Al 2 O 3 -TiO 2 The supported catalyst formed on the composite carrier is used for providing fluorine-containing substances of fluoride ions to be supported on the Al in a weight percentage of 0.5-15% 2 O 3 -TiO 2 And (3) on a composite carrier.
2. As claimed inThe method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde according to claim 1, wherein the method comprises the following steps: the preparation method of the acid-base bifunctional solid catalyst comprises the steps of mixing NaAlO 2 Dissolved in TiCl 4 In the solution, the pH value of the obtained mixed system is regulated and the obtained precipitate is fully precipitated, the obtained precipitate is separated out and fully washed by deionized water, and then the mixture is dried and baked to obtain the Al 2 O 3 -TiO 2 Composite carrier, said Al 2 O 3 -TiO 2 And (3) infiltrating the solution for adsorbing the fluorine-containing substances by the composite carrier, drying and calcining to obtain the acid-base bifunctional solid catalyst.
3. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the pH value of the obtained mixed system is regulated to 7.0-11.0 by ammonia water.
4. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the drying temperature is 100-160 ℃, and the drying time is 1-10 h.
5. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the roasting temperature is 300-900 ℃ and the roasting time is 1-4 h.
6. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the fluorine-containing substance is KF or NaF.
7. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the fluorine-containing material and the Al 2 O 3 -TiO 2 The molar ratio of the composite carrier is 0.01-1: 1.
8. the method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the calcination temperature is 200-300 ℃ and the calcination time is 3-5 h.
9. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 2, wherein: the TiCl is 4 Solution and NaAlO 2 The solvent in the solution is one of water, methanol, ethanol, propanol, n-butanol, isobutanol, n-hexanol, n-hexane, cyclohexane, toluene and p-xylene.
10. The method for preparing isooctanoic acid by self-condensing and oxidizing n-butyraldehyde as claimed in claim 1, wherein: the preparation method of the SBA-15 supported heteropoly acid catalyst comprises the steps of completely dissolving P123 in hydrochloric acid aqueous solution, adding tetraethoxysilane into the solution, fully dispersing the solution, standing and crystallizing in a heat preservation state, separating out solid, washing the solid to be neutral, drying, and roasting in air to obtain the SBA-15 molecular sieve; and (3) fully mixing and dispersing the obtained SBA-15 molecular sieve in the aqueous solution of the phosphotungstic heteropoly acid, preserving heat for a period of time, filtering the mixed system, drying the obtained filter cake, and calcining to obtain the SBA-15 supported heteropoly acid catalyst.
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