CN115286497B - Preparation method of 3, 5-trimethylcyclohexanone - Google Patents
Preparation method of 3, 5-trimethylcyclohexanone Download PDFInfo
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- CN115286497B CN115286497B CN202211060649.3A CN202211060649A CN115286497B CN 115286497 B CN115286497 B CN 115286497B CN 202211060649 A CN202211060649 A CN 202211060649A CN 115286497 B CN115286497 B CN 115286497B
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- trimethylcyclohexanone
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- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 248
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 128
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000001257 hydrogen Substances 0.000 claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 94
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 27
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 238000009423 ventilation Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 94
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 47
- 229910052763 palladium Inorganic materials 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 229910000510 noble metal Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- QTNLQPHXMVHGBA-UHFFFAOYSA-H hexachlororhodium Chemical compound Cl[Rh](Cl)(Cl)(Cl)(Cl)Cl QTNLQPHXMVHGBA-UHFFFAOYSA-H 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 15
- 239000012752 auxiliary agent Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 230000002829 reductive effect Effects 0.000 description 29
- 239000006227 byproduct Substances 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 26
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 description 21
- 229910052593 corundum Inorganic materials 0.000 description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000010453 quartz Substances 0.000 description 10
- 238000007086 side reaction Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010606 normalization Methods 0.000 description 6
- 238000011002 quantification Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000012937 correction Methods 0.000 description 5
- 238000006606 decarbonylation reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 230000006324 decarbonylation Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- -1 cyclic ketone compound Chemical class 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 238000005906 dihydroxylation reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- UENOQWSWMYJKIW-UHFFFAOYSA-N 1,2,2-trimethylcyclohexan-1-ol Chemical compound CC1(C)CCCCC1(C)O UENOQWSWMYJKIW-UHFFFAOYSA-N 0.000 description 1
- XPZBNIUWMDJFPW-UHFFFAOYSA-N 2,2,3-trimethylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1(C)C XPZBNIUWMDJFPW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- IJBHDAGZDSCZBP-UHFFFAOYSA-N azane rhodium Chemical compound N.[Rh] IJBHDAGZDSCZBP-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 3, 5-trimethylcyclohexanone, wherein isophorone is contacted with a hydrogenation catalyst in a hydrogen-containing atmosphere of 0-5 bar, and a selective hydrogenation reaction is carried out to prepare 3, 5-trimethylcyclohexanone; the production method of the hydrogenation catalyst comprises the following steps: (a) Providing a support comprising silica and alumina; (b) Impregnating the support with an aqueous solution of a noble metal-ammonia complex to obtain a catalyst; (c) Drying the catalyst obtained in step (b) by ventilation at a certain temperature; (d) Calcining the catalyst obtained in step (c) at a temperature; (e) activating the catalyst with hydrogen at a temperature. The preparation method of 3, 5-trimethylcyclohexanone realizes the continuous preparation of 3, 5-trimethylcyclohexanone with high selectivity and high yield, so as to solve the problems that the catalyst in the prior art cannot be recycled, the production and use costs are high, and the separation of products and auxiliary agents is difficult.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a preparation method of 3, 5-trimethylcyclohexanone.
Background
The 3, 5-trimethyl cyclohexanone is a colorless cyclic ketone compound with high boiling point and low viscosity, and is mainly used in a plurality of fields of medicine, pesticide, fine chemical industry and the like. For example, peroxides of 3, 5-trimethylcyclohexanone can be used for the production of vulcanizing agents in the rubber industry or polymerization initiators in the plastics industry; meanwhile, the solvent is an excellent solvent for substances such as nitrocellulose, low-molecular-weight polyvinyl chloride, alkyd resin and the like; in addition, the 3, 5-trimethyl cyclohexanone can also be used for manufacturing key medical intermediates, and the added value of the product is higher.
3, 5-Trimethylcyclohexanone is mainly prepared by hydrogenation of isophorone. The isophorone molecular structure contains a carbon-carbon double bond and a carbon-oxygen double bond, and a conjugated system is formed, so that the competitive hydrogenation reaction of the carbon-carbon double bond and the carbon-oxygen double bond is easy to occur. The conventional hydrogenation catalyst is extremely easy to hydrogenate carbon-oxygen double bonds at the same time of hydrogenizing carbon-carbon double bonds, so that a saturated hydrogenation product 3, 5-trimethylcyclohexanol is formed, and the situation is more obvious when high conversion rate of isophorone is pursued. Since the boiling points of the product and the byproduct are very close to each other (the normal pressure boiling point of 3, 5-trimethylcyclohexanone is 189 ℃, the normal pressure obtaining point of 3, 5-trimethylcyclohexanol is 191 ℃), and the product and the byproduct have an azeotropic phenomenon, the main product and the byproduct are difficult to effectively separate through conventional rectification operation. In addition, conventional hydrogenation catalysts generally adopt platinum group metals or nickel-based metals, and the metals and the used carrier have Lewis acidity, so that the byproduct 3, 5-trimethylcyclohexanol is easy to dehydroxylate and then is hydrogenated to form 3, 5-trimethylcyclohexane, and the difficulty of product separation is further increased.
According to the technology of the presently disclosed patent, the preparation of 3, 5-trimethylcyclohexanone by hydrogenation of isophorone mainly comprises two types of catalytic systems:
1. nickel-based catalytic system
Patent CN105061176B discloses that the selective hydrogenation of isophorone with Cr-modified supported Ni-based catalysts in a fixed bed reactor to prepare 3, 5-trimethylcyclohexanone only achieves a reaction selectivity of 95-97%. The addition amount of heavy metal Cr in the catalytic system is 10%, and the toxicity of Cr is larger, so that the environmental protection pressure of the process is higher. In addition, the reaction temperature of the method is 140-300 ℃, and the high temperature is more favorable for carrying out side reactions such as saturated hydrogenation, hydrogenation after dehydroxylation and the like, so that the reaction selectivity is low. The volume ratio of hydrogen to oil reported by the patent is 500-1500:1, and the molar ratio of the hydrogen to oil is 3.5-10:1, which shows that the method needs to use a larger amount of hydrogen based on the theoretical molar ratio of 1:1, so that the energy consumption, the production cost and the three-waste treatment cost of the process are high, and the method is extremely unfavorable for industrial production.
Patent CN110963901a discloses the preparation of 3, 5-trimethylcyclohexanone by catalytic selective hydrogenation of isophorone with an alkali metal modified supported Ni-based catalyst. The reaction system needs to add a certain amount of ammonium oxalate alcohol solution to inhibit the hydrogenation activity of the catalyst, so that higher conversion rate and reaction selectivity are obtained. However, the patent does not mention how to remove the ammonium oxalate auxiliary agent after the reaction, the molar ratio of the reacted hydrogen to the oil is up to 30:1, the hydrogen is used in a large amount, and the production cost is high. Furthermore, the patent does not disclose the influence of ammonia and carbon monoxide decomposed from ammonium oxalate for a long period of time on the activity and service life of the catalyst while suppressing the activity of the catalyst.
2. Noble metal catalytic system
Patent CN102718641B discloses the preparation of 3, 5-trimethylcyclohexanone by co-catalytic hydrogenation of isophorone in a batch mode using a Pd or Pt catalyst in a high pressure reactor, with the addition of zinc chloride as a cocatalyst. In order to improve the selectivity of the reaction, the addition amount of zinc chloride needs to be 1 to 1.3 times of the mass of the main catalyst, chloride ions have strong corrosiveness to reaction equipment and are difficult to completely remove, and the quality of downstream products is adversely affected. According to the disclosed embodiment, the method needs to add a solvent such as methylene dichloride and the like to participate in the reaction so as to improve the selectivity of the reaction from 76-78% to 92-98%, and the residual organic chloride is more difficult to remove than chloride ions. In addition, the noble metal catalyst adopted by the method has higher loading, so that the cost is higher; the method discloses batch reaction, has small treatment capacity and does not have industrial application prospect.
Patent CN105107495B and CN105111053B disclose that the eggshell type supported Pd/Al 2O3 catalyst acts on isophorone under the higher pressure of more than 10bar to prepare 3, 5-trimethylcyclohexanone, and the reaction conversion rate and the selectivity are higher. However, the preparation process of the catalyst is relatively complicated, and the catalyst carrier needs to be calcined at a temperature of 700-1000 ℃, resulting in higher production cost of the catalyst. In addition, the patent does not disclose the catalytic activity performance of the catalyst during long cycle life evaluation, which is critical for control of catalyst cost and future industrial applications.
Patent CN103880619a reports that the alumina supported Pd-Ni bimetallic catalyst is used for the selective hydrogenation of isophorone to prepare 3, 5-trimethylcyclohexanone, and the reaction selectivity is not high. The Pd content in the catalyst used in the method is as high as 6-9%, the cost of the catalyst is high due to the large noble metal consumption, and the patent does not disclose the preparation process of the catalyst. In addition, the method discloses batch or semi-continuous kettle type reaction operation, the treatment capacity is small, and the technical advantage is not obvious.
According to the disclosed patent technology, the following technical difficulties exist in the preparation of 3, 5-trimethylcyclohexanone by selective hydrogenation of isophorone: ① Reaction complexity: the carbon-carbon double bond and carbon-oxygen double bond in the conjugated system in isophorone molecule have competitive hydrogenation reaction, high-selectivity hydrogenation is difficult to realize by a general catalyst, and the byproduct 3, 5-trimethylcyclohexanol of saturated hydrogenation is further dehydroxylated under the action of Lewis acid metal and a carrier and then hydrogenated to generate 3, 5-trimethylcyclohexane. If the hydrogenation reaction of the carbon-carbon double bond of isophorone is advantageous, the further hydrogenation side reaction of the carbon-oxygen double bond is prevented, and the technical difficulty is effectively realized by regulating the hydrogenation activity of the catalyst and controlling the reaction process. ② Difficulty of separation of reaction: the boiling points of the carbon-carbon selective hydrogenation product 3, 5-trimethylcyclohexanone and the saturated hydrogenation byproduct 3, 5-trimethylcyclohexanol are close, and the two products have an azeotropic phenomenon, so that the main byproduct is difficult to effectively separate through conventional rectification operation, the byproduct 3, 5-trimethylcyclohexanol is dehydroxylated and then hydrogenated to generate 3, 5-trimethylcyclohexane, and related auxiliary agents for inhibiting the activity of the catalyst are added in the reaction process, so that the difficulty of separating the product is further increased. Therefore, how to effectively regulate the catalytic activity of the catalyst under the condition of avoiding using other auxiliary agents, thereby realizing the continuous preparation of 3, 5-trimethylcyclohexanone with high selectivity and high yield, and further avoiding the subsequent separation of the 3, 5-trimethylcyclohexanone from byproducts so as to reduce the separation energy consumption is a key premise.
Disclosure of Invention
In view of this, the present invention aims to propose a selective hydrogenation catalyst for the hydrogenation of isophorone to 3, 5-trimethylcyclohexanone. The high-selectivity and high-yield continuous preparation of the 3, 5-trimethylcyclohexanone is realized through the regulation and control of the catalyst activity and the control of the process conditions, so that the problems that the catalyst cannot be recycled, the production and use costs are high, the separation of a product and an auxiliary agent is difficult and the like in the prior art are solved.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
The invention provides a preparation method of 3, 5-trimethylcyclohexanone, which is characterized in that isophorone is contacted with a hydrogenation catalyst in a hydrogen-containing atmosphere to carry out selective hydrogenation reaction to prepare 3, 5-trimethylcyclohexanone. The production method of the hydrogenation catalyst comprises the following steps:
(a) Providing a carrier comprising 65 to 100wt% of silica and 0 to 35wt% of alumina;
(b) Impregnating the support with an aqueous solution of a noble metal-ammonia complex to obtain a catalyst;
(c) Drying the catalyst by ventilation at a temperature below 80 ℃;
(d) Calcining the catalyst at a temperature below 200 ℃;
(e) The catalyst is activated with hydrogen at a temperature below 150 ℃.
Further, the noble metal of the active component used in the hydrogenation catalyst is selected from one or more of palladium, platinum or rhodium, preferably palladium or platinum, particularly preferably palladium. The noble metal-ammonia complex is selected from one or more of palladium tetra ammine dichloride, platinum tetra diammine dichloride, platinum dinitroso diammine dichloride and rhodium hexachloride, preferably palladium tetra ammine dichloride and platinum tetra diammine dichloride, particularly preferably palladium tetra ammine dichloride. The content of noble metal in the hydrogenation catalyst is 0.1-5 wt% of the carrier, preferably 0.3-3 wt% of the carrier, and particularly preferably 0.5-2 wt% of the carrier.
In general, supported noble metal catalysts have higher hydrogenation activity and poorer selectivity for carbon-carbon double bonds and carbon-oxygen double bonds. The hydrogenation catalyst adopts a noble metal-ammonia compound as a catalyst precursor, and has the following functions relative to other precursor salts: ① In the case of palladium tetra-ammine dichloride, the molecular structure of palladium dichloride or palladium nitrate has an amino structure, and a small amount of ammonia gas starts to be decomposed slowly at about 80 ℃ to generate palladium dichloro-diammine. After palladium is combined with amino, the palladium is difficult to be completely reduced into zero-valent palladium in the hydrogen reduction process, and the palladium exists in a form of a part of ionic palladium, so that the hydrogenation activity of palladium is reduced, further hydrogenation of carbon-oxygen double bonds by palladium is further inhibited, and the selectivity of 3, 5-trimethylcyclohexanone is improved. ② In the reaction process, trace ammonia released by slow decomposition of the catalyst and dichloro diammine palladium with certain alkalinity can reduce the acidity of the surface of the catalyst, so that on one hand, the desorption of 3, 5-trimethyl cyclohexanone can be accelerated, the probability of saturated hydrogenation can be further reduced, and on the other hand, the generation of a byproduct 3, 5-trimethyl cyclohexane caused by hydrogenolysis can be inhibited.
Further, in the production method of the hydrogenation catalyst, in the step (b), the carrier used is impregnated with an aqueous solution of a noble metal-ammonia complex. Preferably, the solution is obtained by dissolving ammonia in a noble metal salt solution, or directly using a commercially available noble metal-ammonia complex in water. Preferably, the impregnation of the support is carried out for 2 to 48 hours, preferably 8 to 24 hours. During impregnation, the support is preferably stirred. Alternatively, the support is provided as a fixed bed and the impregnating solution is passed through the bed from below upwards or from above downwards.
Further, the drying step (c) is carried out at a temperature of 20 to 80 ℃, preferably 30 to 70 ℃, particularly preferably 45 to 65 ℃. The drying step may be performed for 5 to 48 hours, and is completed when the moisture in the catalyst is completely removed.
Further, the hydrogenation catalyst production process wherein the calcination step (d) is carried out under aeration conditions and/or at a temperature of 80 to 200 ℃, preferably at a temperature of 100 to 190 ℃, particularly preferably at a temperature of 120 to 180 ℃.
The inventors have unexpectedly found during the course of the study that when the above-mentioned drying step and calcination step of the catalyst are carried out at a lower temperature, unexpected effects are brought about: in one comparative and preferred embodiment of the present invention, the hydrogenation activity of the catalyst is too high and the selectivity of 3, 5-trimethylcyclohexanone is significantly reduced when the catalyst is dried and calcined at a higher temperature; and when the catalyst is prepared by low-temperature drying and lower-temperature calcining as described above, the selective hydrogenation capability of the catalyst on carbon-carbon double bonds is greatly enhanced, and the selectivity of 3, 5-trimethylcyclohexanone is remarkably improved. These findings are surprising because the drying and calcining of the prior art are typically combined in one step, or the calcining step is typically carried out at a higher temperature. For example, patent CN105111053B discloses drying the catalyst at 120 ℃ followed by calcining the catalyst at 500 ℃.
When the drying step and the calcining step of the catalyst are carried out at a lower temperature, the tetraamminepalladium dichloride in the catalyst is decomposed into ammonia gas and diammine palladium dichloride. In the subsequent hydrogen activating and reducing process of the catalyst, the dichlorodiammine palladium in the catalyst is difficult to be completely reduced into zero-valent palladium, and exists in a form of a part of ionic palladium, so that the hydrogenation activity of palladium is reduced, further hydrogenation of carbon-oxygen double bonds by palladium is further inhibited, and the selectivity of 3, 5-trimethylcyclohexanone is improved. After drying and roasting at a higher temperature, the palladium dichloride in the catalyst can be completely decomposed to generate palladium oxide, almost all zero-valent palladium is obtained after subsequent hydrogen activation reduction, the hydrogenation capacity of the catalyst is greatly improved, and the catalyst is subjected to further saturated hydrogenation after hydrogenation of carbon-carbon double bonds, so that 3, 5-trimethylcyclohexanol byproducts are generated. Therefore, the decomposition degree of the noble metal precursor in the catalyst is controlled through the drying and calcining temperatures, and the decomposition and the stay of the noble metal precursor in the dichloro diammine palladium stage containing amino groups are controlled, so that the catalyst is very beneficial to regulating the hydrogenation activity of palladium and inhibiting the occurrence of saturated hydrogenation side reactions.
Further, the hydrogenation catalyst production process wherein the activation step (e) is carried out at a temperature of 80 to 150 ℃, preferably at a temperature of 90 to 140 ℃, particularly preferably at a temperature of 100 to 120 ℃ in a hydrogen atmosphere. An excessively high activation reduction temperature tends to cause that the palladium tetramine dichloride or the decomposed palladium diammine dichloride in the catalyst is completely reduced to obtain zero-valent palladium, so that the hydrogenation capacity of the catalyst is excessively high, and further saturated hydrogenation is carried out after hydrogenation of carbon-carbon double bonds, so that 3, 5-trimethylcyclohexanol byproducts are generated, and the reduction activation of the catalyst is preferably carried out in a temperature range of 30-50 ℃ higher than the reaction temperature.
Further, the hydrogenation catalyst production method wherein the carrier used in step (a) contains silica, and optionally contains a part of alumina. In a particular embodiment, the catalyst is comprised of silica. In a preferred embodiment, the catalyst support is comprised of 65 to 100wt% silica and 0 to 35wt% alumina. The catalyst may contain less than 5wt%, less than 1wt% or less than 0.5wt% of other components, such as impurities. Preferably, the silica is silica and the alumina is alumina. The catalyst may be obtained by preparing a mixed oxide of silica and alumina, preferably by a sol/gel process. Such carrier materials are well known in the art and commercially available. In addition, the catalyst may have a specific crystalline structure, such as aluminum silicate or zeolite. The specific surface area of the support is at least 100m 2/g, preferably from 100 to 700m 2/g, particularly preferably from 200 to 500m 2/g.
In the process of the present invention, the carrier is preferably neutralized with ammonia prior to the impregnation step (b), and the ammonia is bound to the acidic sites on the surface of the carrier to reduce the acidity of the surface, thereby accelerating the desorption of the product and suppressing the occurrence of hydrogenolysis side reactions, which is very advantageous for improving the selectivity and yield of 3, 5-trimethylcyclohexanone.
The hydrogenation catalyst is used for preparing 3, 5-trimethylcyclohexanone by selectively hydrogenating isophorone in a hydrogen-containing atmosphere.
Further, in the preparation method of the 3, 5-trimethylcyclohexanone, isophorone is contacted with a hydrogenation catalyst in a hydrogen-containing atmosphere of 0-5 bar, and the reaction pressure is preferably 0.1-1 bar.
The inventors found during the course of the study that an excessive hydrogen pressure easily resulted in several adverse effects: ① The higher hydrogen pressure can enable the hydrogenation activity of the catalyst to be at a higher level, so that the carbon-carbon double bond of isophorone is easier to be continuously hydrogenated with carbon-oxygen double bond to generate saturated 3, 5-trimethylcyclohexanol byproducts after hydrogenation, and the selectivity of the main product 3, 5-trimethylcyclohexanone is reduced; ② The carbonyl of 3, 5-trimethylcyclohexanone can be decarbonylated to generate a small amount of carbon monoxide under the action of a catalyst or a carrier with Lewis acidity, and the carbon monoxide can be subjected to hydroformylation with 3, 5-trimethylcyclohexene generated after the dehydroxylation of the 3, 5-trimethylcyclohexanol by-product and hydrogen to generate 3, 5-trimethylcyclohexyl-1-methanol on the one hand, so that the difficulty of later separation is further increased, and on the other hand, the carbon monoxide can gradually poison the catalyst, so that the catalyst is slowly deactivated. The higher reaction pressure can cause that carbon monoxide is difficult to desorb and leave on the surface of the catalyst, and further accelerates the poisoning and deactivation of the catalyst. Therefore, the hydrogen pressure of not more than 5bar is adopted, so that the hydrogenation activity of the catalyst is at a lower level, the selectivity and the yield of 3, 5-trimethylcyclohexanone are improved, simultaneously, carbon monoxide generated by decarbonylation of a main product can be quickly desorbed from the surface of the catalyst under a low pressure condition, the catalyst is prevented from being gradually poisoned and deactivated by carbon monoxide under a long-term operation condition, the service life of the catalyst is prolonged, and the use cost of the catalyst is reduced. In a preferred embodiment of the invention, the catalyst is capable of maintaining stable catalytic performance during long periods of operation up to 2000 hours. In addition, due to the lower hydrogen pressure, the equipment investment and the complexity level of technical operation can be further reduced compared with the prior art.
Further, the preparation method of the 3, 5-trimethylcyclohexanone is characterized in that the hydrogenation reaction is carried out in a hydrogen-containing gas atmosphere. The hydrogen-containing gas can be a pure hydrogen atmosphere or a hydrogen atmosphere containing a certain volume of nitrogen, wherein the ratio of hydrogen to nitrogen is 99:1-1:99, the preferable ratio is 95:5-50:50, and the particularly preferable ratio is 90:10-60:40.
The catalyst generally has higher catalytic activity under the pure hydrogen atmosphere, and the too high hydrogen flow can lead to too short residence time of isophorone raw material in a catalyst bed layer and insufficient conversion, and can lead to too strong hydrogen adsorption and dissociation capability of the catalyst, so that the hydrogenation reaction rate is too high, the side reaction rate of saturated hydrogenation is accelerated, the reaction selectivity of 3, 5-trimethylcyclohexanone is reduced, and the subsequent separation and purification are not facilitated. The hydrogen flow is too low, the activity of the catalyst is low, and the reaction conversion rate and the selectivity are both adversely affected. Therefore, in the preferred embodiment of the invention, the hydrogenation activity of the catalyst is controlled by adjusting the ratio of hydrogen to nitrogen, and a plurality of regulation and control mechanisms for the hydrogenation activity of the catalyst are realized by matching with the properties and characteristics of the catalyst, so that the synergistic effect is generated to the maximum extent, the selectivity of the product is improved, and the occurrence of side reactions is avoided.
Further, in the preparation method of the 3, 5-trimethylcyclohexanone, the molar ratio of the hydrogen to the isophorone is 1.5:1-10:1, preferably the molar ratio is 1.8:1-6:1, and particularly preferably the molar ratio is 2:1-5:1. The amount of hydrogen used in the present invention is significantly less than in the prior art, which is significantly advantageous for control of production costs and safe production.
Further, in the preparation method of the 3, 5-trimethylcyclohexanone, the reaction temperature of hydrogenation is 50-150 ℃, preferably 60-100 ℃; the mass space velocity is 0.05-5 h -1, preferably 0.2-2 h -1. The reaction temperature is too high, so that the hydrogenation activity of the catalyst is easily improved, the hydrogenation side reaction rate of carbon-oxygen double bonds is improved, and the reaction selectivity of 3, 5-trimethylcyclohexanone is reduced; the reaction temperature is too low, the catalytic hydrogenation activity is too low, and the raw material isophorone is difficult to be completely converted.
Further, in the preparation method of the 3, 5-trimethylcyclohexanone, the hydrogenation reaction is carried out in a batch or continuous mode, and the continuous operation is preferred; the hydrogenation reactor used is a loop reactor, a fixed bed reactor, a reaction kettle or a fluidized bed reactor, preferably a loop reactor or a fixed bed reactor.
Further, in the method for preparing 3, 5-trimethylcyclohexanone, the hydrogenation reaction is carried out in the presence or absence of an external solvent, preferably without adding an external solvent. When conducted in the presence of an added solvent, solvents that are inert under the hydrogenation conditions are preferred.
Further, in the preparation method of the 3, 5-trimethylcyclohexanone, the crude product of the hydrogenation reaction is subjected to purification measures including rectification, chromatography or comprehensive measures. The rectification apparatus used for purification includes optionally equipped rectification columns, bubble cap columns, tray columns or evaporators such as thin film evaporators, falling film evaporators, forced circulation evaporators, wiped film evaporators and combinations thereof.
Compared with the prior art, the preparation method of the 3, 5-trimethylcyclohexanone has the following beneficial effects:
1. The catalyst for preparing 3, 5-trimethylcyclohexanone by selectively hydrogenating isophorone adopts the noble metal-ammonia compound as a precursor, and is matched with drying and calcining at a lower temperature, and the decomposition degree of the noble metal precursor is controlled to stay at the stage of still containing the amino noble metal-ammonia compound, so that the catalyst is difficult to be completely reduced into zero-valence active metal in the hydrogen activating process, but exists in the form of a part of ionic active metal, thereby reducing the hydrogenation activity of the active metal, further inhibiting the further hydrogenation of carbon-oxygen double bonds and improving the selectivity of 3, 5-trimethylcyclohexanone. In addition, trace ammonia released by slow decomposition of the catalyst and a noble metal-ammonia compound with certain alkalinity in the reaction process can reduce the acidity of the surface of the catalyst, accelerate the desorption of 3, 5-trimethylcyclohexanone and reduce the probability of saturated hydrogenation, and simultaneously effectively inhibit the generation of byproduct 3, 5-trimethylcyclohexane caused by hydrogenolysis. The hydrogenation catalyst provided by the invention has mild preparation conditions, and solves the problems of complex preparation process, severe conditions, pollution in the preparation process and the like of the traditional catalyst. Can efficiently catalyze isophorone to 3, 5-trimethylcyclohexanone without adding other auxiliary agents. The addition amount of the active noble metal is small, long-period continuous stable operation can be realized, the catalytic life exceeds 2000h, the selectivity of 3, 5-trimethylcyclohexanone is stabilized at 99.1-99.8%, and the conversion rate of isophorone is stabilized at 99.4-99.9%. The catalyst has lower manufacturing cost and use cost, and also reduces the production cost of the 3, 5-trimethyl cyclohexanone.
2. The method for preparing 3, 5-trimethylcyclohexanone adopts the hydrogen pressure of not more than 5 bar. The hydrogenation activity of the catalyst can be at a lower level under low pressure, the selectivity and the yield of 3, 5-trimethylcyclohexanone are improved, simultaneously, carbon monoxide generated by decarbonylation of a main product can be quickly desorbed from the surface of the catalyst under low pressure, the catalyst is prevented from being deactivated by gradual poisoning of the carbon monoxide under long-term operation conditions, the service life of the catalyst is prolonged, and the use cost of the catalyst is reduced. Meanwhile, the hydrogenation activity of the catalyst is controlled by adjusting the ratio of hydrogen to nitrogen in the hydrogen-containing atmosphere, and the properties and the characteristics of the catalyst are matched, so that the hydrogenation activity of the catalyst is regulated and controlled by various means and mechanisms, a synergistic effect is generated to the greatest extent, the selectivity of the product is improved, and side reactions are avoided.
3. The method for preparing 3, 5-trimethylcyclohexanone effectively inhibits the generation of various byproducts such as 3, 5-trimethylcyclohexanol, 3, 5-trimethylcyclohexane, 3, 5-trimethylcyclohexyl-1-methanol and the like, the problem that 3, 5-trimethylcyclohexanone is difficult to separate and purify after the byproducts and the auxiliary agent are added is avoided, the separation operation difficulty and the separation energy consumption are greatly reduced, and the continuous preparation of 3, 5-trimethylcyclohexanone with high selectivity and high yield is realized.
4. The method for preparing 3, 5-trimethylcyclohexanone disclosed by the invention has the advantages that solvents and other auxiliary agents are not required to be added in the reaction process, the energy consumption required by the reaction is low, the emission of three wastes is almost avoided, and the method is suitable for industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows the results of catalyst B for the hydrogenation of isophorone to 3, 5-trimethylcyclohexanone (sample points on the abscissa, 2000h total continuous evaluation);
FIG. 2 is a preparation flow chart of a preparation method of 3, 5-trimethylcyclohexanone in the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
In the following examples, analysis of each component in the reaction system was performed by gas chromatography, quantification was performed by a calibration normalization method, and the conversion of the reactants, the selectivity of the products and the yield were calculated on the basis of the above-described results, which were all performed with reference to the prior art. The gas chromatographic analysis conditions were as follows:
Chromatographic column: agilent DB-Wax (30 m 0.32mm 0.25 mm); sample inlet temperature: 300 ℃; split ratio: 30:1; column flow rate: 1.5mL/min; column temperature: 100 ℃ for 0.5min; heating program: raising the temperature to 300 ℃ at 15 ℃/min, and keeping for 8min; detector temperature: 300 ℃, hydrogen flow: 35mL/min, air flow: 350mL/min.
Preparation of hydrogenation catalyst
Example 1: preparation of catalyst A (0.5% Pd/SiO 2-Al2O3,Al2O3: 13 wt%)
100G of SiO 2-Al2O3 support (Al 2O3 content 13% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 2ml/min for 1h. 1.15g of palladium tetra-chloride Pd (NH 3)4Cl2 (Pd content: 0.5 g)) was dissolved in 100mL of desalted water to complete dissolution, the pretreated support was added to the above palladium-ammonia complex aqueous solution, impregnation was carried out for 5 hours, and then the catalyst was washed 3 times with desalted water, dried with air at 60℃until most of the water was removed from the catalyst, after drying, the catalyst was calcined with air at about 130℃for about 10 hours, and the resulting catalyst was reduced under a hydrogen atmosphere at 120℃for 4 hours to obtain catalyst A.
Example 2: preparation of catalyst B (0.8% Pd/SiO 2-Al2O3,Al2O3:15 wt%)
100G of SiO 2-Al2O3 support (Al 2O3 content 15% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 2ml/min for 1h. 1.33g of palladium chloride PdCl 2 (Pd content is 0.8 g) was added to 100mL of an aqueous ammonia solution of 0.32mol/L and stirred at 80℃for 0.5h, and palladium tetra-ammine dichloride Pd (NH 3)4Cl2 solution (Pd content is 0.8 g)) was obtained after cooling, the pretreated carrier was added to the above aqueous palladium-ammonia complex solution, impregnation and adsorption were carried out for 8h, and then washed 3 times with desalted water, the catalyst was dried with air at 50℃until most of the water was removed from the catalyst, after drying, the catalyst was calcined with air at about 120℃for about 18h, and the obtained catalyst was reduced under a hydrogen atmosphere at 100℃for 6 h, to obtain catalyst B.
Example 3: preparation of catalyst C (0.2% Pd/SiO 2-Al2O3,Al2O3:35 wt.%)
100G of SiO 2-Al2O3 support (Al 2O3 content 35% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 2ml/min for 1h. 0.46g of palladium tetra-chloride Pd (NH 3)4Cl2 (Pd content 0.2 g) was dissolved in 100mL of desalted water to dissolve it completely, the above palladium-ammonia complex aqueous solution was pumped over the pretreated support bed and circulated for 12 hours, and finally washed 3 times with desalted water the catalyst was dried with air at 75 ℃ until most of the water was removed from the catalyst, after drying, the catalyst was calcined with air at about 180 ℃ for about 6 hours, and the resulting catalyst was reduced under a hydrogen atmosphere at 115 ℃ for 6 hours to produce catalyst C.
Example 4: preparation of catalyst D (1% Pt/SiO 2-Al2O3,Al2O3:35 wt%)
100G of SiO 2-Al2O3 support (Al 2O3 content 35% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 5ml/min for 0.5h. 1.89g of platinum tetrachloride Pt (NH 3)2Cl4 (Pt content: 1 g)) was dissolved in 100mL of desalted water to completely dissolve it, and the pretreated support was added to the above platinum-ammonia complex aqueous solution, impregnated and adsorbed for 10 hours, followed by washing with desalted water 3 times, drying the catalyst with air at 40℃until most of the water was removed from the catalyst, drying, calcining the catalyst with air at about 165℃for about 12 hours, and reducing the resulting catalyst under a hydrogen atmosphere at 140℃for 3 hours to obtain catalyst D.
Example 5: preparation of catalyst E (3% Pt/SiO 2-Al2O3,Al2O3:20 wt%)
100G of SiO 2-Al2O3 carrier (Al 2O3 content 20% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 5ml/min for 0.5h. 4.94g of dinitroso diammine platinum Pt (NH 3)2(NO2)2 (Pt content: 3 g)) was dissolved in 100mL of desalted water to dissolve it completely, the pretreated support was added to the above platinum-ammonia complex aqueous solution, impregnated and adsorbed for 24 hours, and then washed 3 times with desalted water, the catalyst was dried with air at 55 ℃ until most of the water was removed from the catalyst, after drying, the catalyst was calcined with air at about 195 ℃ for about 8 hours, and the resulting catalyst was reduced under a hydrogen atmosphere at 130 ℃ for 5 hours to obtain catalyst E.
Example 6: preparation of catalyst F (1.2% Rh/SiO 2-Al2O3,Al2O3:20 wt%)
100G of SiO 2-Al2O3 carrier (Al 2O3 content 20% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 5ml/min for 0.5h. After 4.31g of rhodium hexachloride Rh (NH 3)3Cl6 (Rh content: 1.2 g)) was dissolved in 100mL of desalted water to dissolve it completely, the pretreated support was added to the above rhodium-ammonia complex aqueous solution, impregnated and adsorbed for 12 hours, and then washed 3 times with desalted water, the catalyst was dried with air at 65℃until most of the water was removed from the catalyst, after drying, the catalyst was calcined with air at about 170℃for about 12 hours, and the resulting catalyst was reduced under a hydrogen atmosphere at 110℃for 8 hours to obtain catalyst F.
Example 7: preparation of catalyst G (2% Pd/ZSM-5, al 2O3:30 wt%)
100G of ZSM-5 carrier (Al 2O3 content 30 wt%) was placed in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 2ml/min for 1h. 4.62G of palladium tetra-chloride Pd (NH 3)4Cl2 (Pd content: 2G)) was dissolved in 100mL of desalted water to make it completely dissolved, the pretreated support was added to the above palladium-ammonia complex aqueous solution, impregnated and adsorbed for 24 hours, and then washed 3 times with desalted water, the catalyst was dried with air at 80 ℃ until most of the water was removed from the catalyst, after drying, the catalyst was calcined with air at about 150 ℃ for about 24 hours, and the resulting catalyst was reduced under a hydrogen atmosphere at 90 ℃ for 10 hours to prepare catalyst G.
Example 8: the hydrogenation catalyst is used for catalyzing isophorone to selectively hydrogenate to prepare 3, 5-trimethylcyclohexanone.
Catalysts A to G are respectively filled into a fixed bed reactor equipped with a heating and heat preserving device, the diameter of the reactor is 20mm, the length of the reactor is 1000mm, and the filling height of the catalyst is 200mm. The reactor was purged three times with nitrogen prior to the reaction. After the reaction starts, hydrogen and nitrogen are respectively introduced from the top of the reactor under the control of a gas flowmeter, raw isophorone is pumped into a preheater by a plunger pump, the preheating temperature is 50-60 ℃, and then the raw isophorone and hydrogen-nitrogen mixed gas are mixed and then are introduced into a fixed bed reactor from the top of the reactor in parallel flow. The flow rate of the hydrogen is controlled so that the mole ratio of isophorone to the hydrogen is 1.5:1-10:1, and the volume flow rate ratio of the hydrogen to the nitrogen is 95:5-50:50. The reaction temperature is controlled at 50-150 ℃, the system pressure is controlled at 0.1-5 bar, and the residence time is controlled at mass airspeed, namely, 0.05-5 g of raw material/g of catalytic active metal/hour. The equipment is operated continuously for 48 hours, the reaction liquid is extracted from the bottom of the reactor, and the crude product is obtained after cooling. The results of the isophorone hydrogenation reaction after detection by gas chromatography and quantification by correction normalization are shown in Table 1.
Table 1 hydrogenation catalyst for selective hydrogenation of isophorone IP to 3, 5-trimethylcyclohexanone
Note that: the ketone represents 3, 5-trimethylcyclohexanone; alcohol represents 3, 5-trimethylcyclohexanol; alkane represents 3, 5-trimethylcyclohexane; decarbonylmethanol represents 3, 5-trimethylcyclohexylmethanol
Comparative example 1: preparation of catalyst H
The catalyst precursor was changed from palladium tetra-ammine dichloride Pd (NH 3)4Cl2 to palladium chloride PdCl 2) and the other preparation process was the same as in example 1.
100G of SiO 2-Al2O3 support (Al 2O3 content 13% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 2ml/min for 1h. 0.83g of palladium chloride PdCl 2 (Pd content 0.5 g) was dissolved in 100mL of desalted water to dissolve it completely. The pretreated carrier is added into the aqueous solution of palladium chloride, impregnated and adsorbed for 5 hours, and then washed with desalted water for 3 times. The catalyst was dried with air at 60 ℃ until most of the water was removed from the catalyst. After drying, the catalyst was calcined with air at about 130 ℃ for about 10 hours. The resulting catalyst was reduced at 120℃for 4 hours under a hydrogen atmosphere to prepare catalyst H.
Comparative example 2: preparation of catalyst I
The drying and calcining temperatures of the catalyst were increased and the other preparation processes were the same as in example 1.
100G of SiO 2-Al2O3 support (Al 2O3 content 13% by weight) were taken in a quartz tube filled with a nitrogen stream. The dried ammonia gas was passed through the support sample at a flow rate of 2ml/min for 1h. 0.83g of palladium chloride PdCl 2 (Pd content 0.5 g) was dissolved in 100mL of desalted water to dissolve it completely. The pretreated carrier is added into the aqueous solution of palladium chloride, impregnated and adsorbed for 5 hours, and then washed with desalted water for 3 times. The catalyst was dried with air at 150 ℃ until most of the water was removed from the catalyst. After drying, the catalyst was calcined with air at about 500 ℃ for about 10 hours. The catalyst was reduced at 120℃for 4 hours under a hydrogen atmosphere to obtain catalyst I.
Comparative example 3: preparation of catalyst J (Prior Art)
100G of SiO 2-Al2O3 support (Al 2O3 content 13% by weight) were taken in a quartz tube filled with a nitrogen stream. 0.83g of palladium chloride PdCl 2 (Pd content 0.5 g) was dissolved in 100mL of desalted water to dissolve it completely. The pretreated carrier is added into the aqueous solution of palladium chloride, impregnated and adsorbed for 5 hours, and then washed with desalted water for 3 times. The catalyst was dried with air at 150 ℃ until most of the water was removed from the catalyst. After drying, the catalyst was calcined with air at about 500 ℃ for about 10 hours. The obtained catalyst was reduced at 120℃for 4 hours under a hydrogen atmosphere to prepare catalyst J.
Comparative example 4: hydrogenation catalysts H, I and J are used for catalyzing isophorone to selectively hydrogenate to prepare 3, 5-trimethylcyclohexanone.
Catalysts A, H, I and J were respectively packed into a fixed bed reactor equipped with a heating and heat-preserving device, the diameter of the reactor was 20mm, the length of the tube was 1000mm, and the packed height of the catalyst was 200mm. The reactor was purged three times with nitrogen prior to the reaction. After the reaction starts, hydrogen and nitrogen are respectively introduced from the top of the reactor under the control of a gas flowmeter, raw isophorone is pumped into a preheater by a plunger pump, the preheating temperature is 50-60 ℃, and then the raw isophorone and hydrogen-nitrogen mixed gas are mixed and then are introduced into a fixed bed reactor from the top of the reactor in parallel flow. The hydrogen flow rate was controlled so that the molar ratio of isophorone to hydrogen was 2.5:1, while the volumetric flow rate ratio of hydrogen to nitrogen was 80:20. The reaction temperature was controlled at 80℃and the system pressure at 1bar and the residence time at a mass space velocity, i.e.at 1.25 g of starting material per g of catalytically active metal per hour. The equipment is operated continuously for 48 hours, the reaction liquid is extracted from the bottom of the reactor, and the crude product is obtained after cooling. The results of the isophorone hydrogenation reaction after detection by gas chromatography and quantification by correction normalization are shown in Table 2.
Table 2 comparative examples 1 to 3 hydrogenation catalysts for the preparation of 3, 5-trimethylcyclohexanone
Note that: the ketone represents 3, 5-trimethylcyclohexanone; alcohol represents 3, 5-trimethylcyclohexanol; alkane represents 3, 5-trimethylcyclohexane; decarbonylmethanol represents 3, 5-trimethylcyclohexylmethanol
As can be seen from Table 2, catalyst A obtained by drying and calcining at a lower temperature with the noble metal-ammonia complex as a precursor has significantly higher selectivity for 3, 5-trimethylcyclohexanone and other by-products such as alcohols, alkanes and decarbonylcohols suppressed at a very low level compared to other catalysts such as H, I and J. The noble metal-ammonia compound is adopted as a precursor, and the precursor is matched with drying and calcining at a lower temperature, so that the catalyst is difficult to be completely reduced into zero-valent active metal in the hydrogen activating process by controlling the decomposition degree of the noble metal precursor to stay at the stage of still containing the amino noble metal-ammonia compound, and exists in the form of a part of ionic active metal, thereby reducing the hydrogenation activity of the active metal, further inhibiting the further hydrogenation of carbon-oxygen double bonds, and further improving the selectivity of 3, 5-trimethylcyclohexanone. In addition, trace ammonia released by slow decomposition of the catalyst and a noble metal-ammonia compound with certain alkalinity in the reaction process can reduce the acidity of the surface of the catalyst, accelerate the desorption of 3, 5-trimethylcyclohexanone and reduce the probability of saturated hydrogenation, and simultaneously effectively inhibit the generation of byproduct 3, 5-trimethylcyclohexane caused by hydrogenolysis.
Comparative example 5: verifying that low pressure conditions promote preferential selective hydrogenation of isophorone carbon-carbon double bond
The catalyst B is used for catalyzing isophorone to prepare 3, 5-trimethylcyclohexanone by selective hydrogenation, and other conditions and operations are the same except for pressure adjustment of a reaction system.
The catalyst B was packed in a fixed bed reactor equipped with a heating and heat-preserving device, the diameter of the reactor was 20mm, the length of the tube was 1000mm, and the packed height of the catalyst was 200mm. The reactor was purged three times with nitrogen prior to the reaction. After the reaction starts, hydrogen and nitrogen are respectively introduced from the top of the reactor under the control of a gas flowmeter, raw isophorone is pumped into a preheater by a plunger pump, the preheating temperature is 50-60 ℃, and then the raw isophorone and hydrogen-nitrogen mixed gas are mixed and then are introduced into a fixed bed reactor from the top of the reactor in parallel flow. The hydrogen flow rate is controlled so that the molar ratio of isophorone to hydrogen is 2.1:1, and the volume flow rate ratio of hydrogen to nitrogen is 90:10. The reaction temperature is controlled at 90 ℃, the pressure of different reaction systems is regulated, and the residence time is controlled at a mass space velocity, namely, 1.08 g of raw material/g of catalytic active metal/hour. The equipment is operated continuously for 48 hours, the reaction liquid is extracted from the bottom of the reactor, and the crude product is obtained after cooling. The results of the isophorone hydrogenation reaction after detection by gas chromatography and quantification by correction normalization are shown in Table 3.
TABLE 3 catalyst B for the preparation of 3, 5-trimethylcyclohexanone at different hydrogenation pressures
Note that: the ketone represents 3, 5-trimethylcyclohexanone; alcohol represents 3, 5-trimethylcyclohexanol; alkane represents 3, 5-trimethylcyclohexane; decarbonylmethanol represents 3, 5-trimethylcyclohexylmethanol
As can be seen from table 3, the higher hydrogen pressure can make the hydrogenation activity of the catalyst at a higher level, so that the carbon-carbon double bond of isophorone is more easily hydrogenated with carbon-oxygen double bond to generate saturated 3, 5-trimethylcyclohexanol byproduct after hydrogenation, resulting in reduced selectivity of the main product 3, 5-trimethylcyclohexanone; meanwhile, carbonyl of 3, 5-trimethylcyclohexanone can generate decarbonylation reaction to generate a small amount of carbon monoxide under the action of a catalyst or carrier with Lewis acidity, and the carbon monoxide can carry out hydroformylation reaction with 3, 5-trimethylcyclohexene generated after the by-product of 3, 5-trimethylcyclohexanol is dehydroxylated and hydrogen to generate 3, 5-trimethylcyclohexyl-1-methanol on the one hand, so that the difficulty of later separation is further increased, and on the other hand, the catalyst is gradually poisoned by the carbon monoxide, so that the catalyst is slowly deactivated. In addition, the higher reaction pressure can cause that carbon monoxide is difficult to desorb and leave on the surface of the catalyst, so that the poisoning and deactivation of the catalyst are further accelerated. Therefore, the hydrogen pressure of not more than 5bar is adopted, so that the hydrogenation activity of the catalyst is at a lower level, the selectivity and the yield of 3, 5-trimethylcyclohexanone are improved, simultaneously, carbon monoxide produced by decarbonylation of a main product can be quickly desorbed from the surface of the catalyst under a low pressure condition, the catalyst is prevented from being gradually poisoned and deactivated by carbon monoxide under a long-term operation condition, the service life of the catalyst is prolonged, and the use cost of the catalyst is reduced.
Comparative example 6: verification of the Hydrogen/Nitrogen ratio to promote the advantageous Selective hydrogenation of isophorone carbon double bond
The catalyst B is used for catalyzing isophorone to prepare 3, 5-trimethylcyclohexanone by selective hydrogenation, and other conditions and operations are the same except that pure hydrogen is used for hydrogenation reaction.
The catalyst B was packed in a fixed bed reactor equipped with a heating and heat-preserving device, the diameter of the reactor was 20mm, the length of the tube was 1000mm, and the packed height of the catalyst was 200mm. The reactor was purged three times with nitrogen prior to the reaction. After the reaction starts, hydrogen is controlled by a gas flowmeter to be introduced from the top of the reactor, and raw isophorone is pumped into a preheater by a plunger pump, the preheating temperature is 50-60 ℃, and then the raw isophorone and the hydrogen are mixed and introduced into a fixed bed reactor from the top of the reactor in parallel flow. The hydrogen flow was controlled so that the molar ratio of isophorone to hydrogen was 2.1:1. The reaction temperature was controlled at 90℃and the reaction system pressure at 0.5bar, the residence time was controlled at a mass space velocity, i.e.at 1.08 g of starting material per g of catalytically active metal per hour. The equipment is operated continuously for 48 hours, the reaction liquid is extracted from the bottom of the reactor, and the crude product is obtained after cooling. The results of the isophorone hydrogenation reaction after detection by gas chromatography and quantification by correction normalization are shown in Table 4.
TABLE 4 catalyst B for the preparation of 3, 5-trimethylcyclohexanone under different hydrogen-to-nitrogen ratios
Note that: the ketone represents 3, 5-trimethylcyclohexanone; alcohol represents 3, 5-trimethylcyclohexanol; alkane represents 3, 5-trimethylcyclohexane; decarbonylmethanol represents 3, 5-trimethylcyclohexylmethanol
As can be seen from Table 4, the catalyst has higher catalytic hydrogenation activity under pure hydrogen atmosphere, and the catalyst has too strong hydrogen adsorption and dissociation capability, so that the hydrogenation reaction rate is too fast, the side reaction rate of saturated hydrogenation is increased, and the reaction selectivity of 3, 5-trimethylcyclohexanone is reduced. Therefore, the hydrogenation activity of the catalyst is controlled by adjusting the proportion of nitrogen and hydrogen, and a plurality of regulation and control mechanisms for the hydrogenation activity of the catalyst are realized by matching with the property of the catalyst, so that the synergistic effect is generated to the maximum extent, the selectivity of the product is improved, and the occurrence of side reactions is avoided.
Example 9: hydrogenation catalyst B for catalyzing isophorone to selectively hydrogenate to prepare 3, 5-trimethylcyclohexanone in long-period operation
The catalyst B was packed in a fixed bed reactor equipped with a heating and heat-preserving device, the diameter of the reactor was 20mm, the length of the tube was 1000mm, and the packed height of the catalyst was 200mm. The reactor was purged three times with nitrogen prior to the reaction. After the reaction starts, hydrogen and nitrogen are respectively introduced from the top of the reactor under the control of a gas flowmeter, raw isophorone is pumped into a preheater by a plunger pump, the preheating temperature is 50-60 ℃, and then the raw isophorone and hydrogen-nitrogen mixed gas are mixed and then are introduced into a fixed bed reactor from the top of the reactor in parallel flow. The hydrogen flow rate is controlled so that the molar ratio of isophorone to hydrogen is 2.1:1, and the volume flow rate ratio of hydrogen to nitrogen is 90:10. The reaction temperature was controlled at 90℃and the reaction system pressure at 0.5bar, the residence time was controlled at a mass space velocity, i.e.at 1.08 g of starting material per g of catalytically active metal per hour. The equipment is operated continuously every 24 hours, the reaction liquid is extracted from the bottom of the reactor, and the crude product is obtained after cooling. The results of the isophorone hydrogenation reaction after detection by gas chromatography and quantification by correction normalization are shown in FIG. 1.
The boiling points of the carbon-carbon selective hydrogenation product 3, 5-trimethylcyclohexanone and the saturated hydrogenation byproduct 3, 5-trimethylcyclohexanol are close, and the carbon-carbon selective hydrogenation product and the saturated hydrogenation byproduct 3, 5-trimethylcyclohexanol have an azeotropic phenomenon, so that the main byproduct is difficult to effectively separate through conventional rectification operation; if the activity of the catalyst for hydrogenation is too high, hydrogenolysis can occur to generate a byproduct 3, 5-trimethylcyclohexane, which increases the difficulty of separation and purification. The carbonyl of 3, 5-trimethylcyclohexanone can be decarbonylated to generate a small amount of carbon monoxide under the action of a catalyst or carrier with Lewis acidity, and the carbon monoxide can be subjected to hydroformylation with 3, 5-trimethylcyclohexene generated after the by-product of 3, 5-trimethylcyclohexanol is dehydroxylated and hydrogen to generate 3, 5-trimethylcyclohexyl-1-methanol, wherein the boiling point of the 3, 5-trimethylcyclohexyl-1-methanol is different from that of trimethylcyclohexanol or trimethylcyclohexanone by not more than 20 ℃, so that the later separation difficulty is further increased, and the carbon monoxide can gradually poison the catalyst to cause slow deactivation of the catalyst. The higher reaction pressure can cause that carbon monoxide is difficult to desorb and leave on the surface of the catalyst, and further accelerates the poisoning and deactivation of the catalyst.
The hydrogen pressure of not more than 5bar is adopted, so that the hydrogenation activity of the catalyst is at a lower level, the selectivity and the yield of 3, 5-trimethylcyclohexanone are improved, simultaneously, carbon monoxide generated by decarbonylation of a main product can be quickly desorbed from the surface of the catalyst under a low pressure condition, the catalyst is prevented from being gradually poisoned and deactivated by carbon monoxide under a long-term operation condition, the service life of the catalyst is prolonged, and the use cost of the catalyst is reduced. In a preferred embodiment of the invention, the catalyst is capable of maintaining stable catalytic performance during long periods of operation up to 2000 hours.
The invention suppresses the generation of various byproducts such as 3, 5-trimethylcyclohexanol, 3, 5-trimethylcyclohexane, 3, 5-trimethylcyclohexyl-1-methanol, and the like, avoids the problems that 3, 5-trimethylcyclohexanone is difficult to separate and purify from the byproducts and the addition of auxiliary agents, greatly reduces the operation difficulty and the separation energy consumption of separation, and ensures the product purity of 3, 5-trimethylcyclohexanone (the purity of the winning product is required to be more than 98.5 percent, and the impurity content of 3, 5-trimethylcyclohexanol and the like is lower than 1.5 percent).
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (27)
1. A preparation method of 3, 5-trimethylcyclohexanone is characterized in that: isophorone is contacted with a hydrogenation catalyst in a hydrogen-containing atmosphere of 0.1-1 bar, and a selective hydrogenation reaction is carried out to prepare 3, 5-trimethylcyclohexanone;
the production method of the hydrogenation catalyst comprises the following steps:
(a) Providing a support comprising silica and alumina;
(b) Impregnating the support with an aqueous solution of a noble metal-ammonia complex to obtain a catalyst;
(c) Drying the catalyst obtained in step (b) by ventilation at a certain temperature;
(d) Calcining the catalyst obtained in step (c) at a temperature;
(e) Activating the catalyst with hydrogen at a temperature;
The noble metal-ammonia complex in the step (b) comprises one or more than two of palladium dichloride, platinum dinitroso diammine and rhodium hexachloride;
step (c) air drying the catalyst at a temperature below 80 ℃;
calcining step (d) is calcining the catalyst at a temperature of less than 200 ℃ under aeration conditions;
Step (e) activating the catalyst with hydrogen at a temperature below 150 ℃;
The mass space velocity of the isophorone contacted with the hydrogenation catalyst in the hydrogen-containing atmosphere is 0.05-5 h -1.
2. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the noble metal used in the hydrogenation catalyst is one or more selected from palladium, platinum or rhodium, and the content of the noble metal in the hydrogenation catalyst is 0.1-5 wt% of the carrier.
3. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the noble metal used in the hydrogenation catalyst is palladium or platinum.
4. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the noble metal used in the hydrogenation catalyst is palladium.
5. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the content of noble metal used in the hydrogenation catalyst is 0.3-3 wt% of the carrier.
6. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the content of noble metal used in the hydrogenation catalyst is 0.5-2 wt% of the carrier.
7. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the carrier in the step (a) comprises 65-100 wt% of silicon oxide and 0-35 wt% of aluminum oxide.
8. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the noble metals in the step (b) are palladium tetramine dichloride and platinum diammine dichloride.
9. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the noble metal in the step (b) is palladium tetra-ammine dichloride.
10. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: step (c) air drying the catalyst at a temperature of 20-80 ℃.
11. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: step (c) is carried out at a temperature of 30 to 70 ℃.
12. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: step (c) is carried out at a temperature of 45 to 65 ℃.
13. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: calcination step (d) is calcining the catalyst at a temperature of 80 to 200 ℃ under aeration.
14. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: calcination step (d) is calcining the catalyst at a temperature of 100 to 190 ℃ under aeration.
15. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: calcination step (d) is calcining the catalyst at a temperature of 120-180 ℃ under aeration.
16. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: step (e) activating the catalyst with hydrogen at a temperature of 80 to 150 ℃.
17. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: step (e) activating the catalyst with hydrogen at a temperature of 90-140 ℃.
18. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: step (e) activating the catalyst with hydrogen at a temperature of 100 to 120 ℃.
19. The method for preparing 3, 5-trimethylcyclohexanone according to claim 1, wherein: the hydrogenation reaction is carried out in a hydrogen-containing gas atmosphere, the hydrogen-containing gas can be a pure hydrogen atmosphere or a hydrogen atmosphere containing a certain volume of nitrogen, wherein the ratio of hydrogen to nitrogen is 99:1-1:99, and the molar ratio of hydrogen to isophorone is 1.5:1-10:1.
20. The method for preparing 3, 5-trimethylcyclohexanone according to claim 19, wherein: the ratio of the hydrogen to the nitrogen is 95:5-50:50.
21. The method for preparing 3, 5-trimethylcyclohexanone according to claim 19, wherein: the ratio of the hydrogen to the nitrogen is 90:10-60:40.
22. The method for preparing 3, 5-trimethylcyclohexanone according to claim 19, wherein: the molar ratio of the hydrogen to the isophorone is 1.8:1-6:1.
23. The method for preparing 3, 5-trimethylcyclohexanone according to claim 19, wherein: the molar ratio of the hydrogen to the isophorone is 2:1-5:1.
24. A process for the preparation of 3, 5-trimethylcyclohexanone as claimed in claim 1, wherein: the reaction temperature of the hydrogenation reaction is 60-100 ℃; the mass airspeed is 0.2-2 h -1.
25. A process for the preparation of 3, 5-trimethylcyclohexanone as claimed in claim 1, wherein:
the hydrogenation reaction is carried out in a batch or continuous mode;
the hydrogenation reactor used comprises a loop reactor, a fixed bed reactor, a reaction kettle or a fluidized bed reactor.
26. A process for the preparation of 3, 5-trimethylcyclohexanone as claimed in claim 1, wherein: the hydrogenation reaction adopts continuous operation.
27. A process for the preparation of 3, 5-trimethylcyclohexanone as claimed in claim 1, wherein:
The hydrogenation reactor is one of a loop reactor or a fixed bed reactor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03127752A (en) * | 1989-10-11 | 1991-05-30 | New Japan Chem Co Ltd | Production of methylcyclohexanone |
| CN102718641A (en) * | 2012-07-03 | 2012-10-10 | 北京化工大学 | Method for preparing 3,3,5-trimethyl-cyclohexanone by selectively hydrogenating isophorone |
| CN105061176A (en) * | 2015-07-22 | 2015-11-18 | 黄河三角洲京博化工研究院有限公司 | Fixed-bed synthetic method for 3,3,5-trimethylcyclohexanone |
| CN110201680A (en) * | 2019-07-04 | 2019-09-06 | 山西师范大学 | It is a kind of for alpha, beta-unsaturated aldehyde/ketone selective hydrogenation catalyst, preparation method and catalysis process |
| CN110963901A (en) * | 2019-11-28 | 2020-04-07 | 万华化学集团股份有限公司 | Preparation method of 3,3, 5-trimethylcyclohexanone |
-
2022
- 2022-08-31 CN CN202211060649.3A patent/CN115286497B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03127752A (en) * | 1989-10-11 | 1991-05-30 | New Japan Chem Co Ltd | Production of methylcyclohexanone |
| CN102718641A (en) * | 2012-07-03 | 2012-10-10 | 北京化工大学 | Method for preparing 3,3,5-trimethyl-cyclohexanone by selectively hydrogenating isophorone |
| CN105061176A (en) * | 2015-07-22 | 2015-11-18 | 黄河三角洲京博化工研究院有限公司 | Fixed-bed synthetic method for 3,3,5-trimethylcyclohexanone |
| CN110201680A (en) * | 2019-07-04 | 2019-09-06 | 山西师范大学 | It is a kind of for alpha, beta-unsaturated aldehyde/ketone selective hydrogenation catalyst, preparation method and catalysis process |
| CN110963901A (en) * | 2019-11-28 | 2020-04-07 | 万华化学集团股份有限公司 | Preparation method of 3,3, 5-trimethylcyclohexanone |
Non-Patent Citations (1)
| Title |
|---|
| Nagendiran, Anuja等.Mild and Selective Catalytic Hydrogenation of the C=C Bond in α,β-Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles.Chemistry - A European Journal.2016,第22卷(第21期),7184-7189. * |
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