CN112517075B - Isomerization catalyst, preparation method thereof and preparation method of beta-isophorone - Google Patents
Isomerization catalyst, preparation method thereof and preparation method of beta-isophorone Download PDFInfo
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- CN112517075B CN112517075B CN202011369912.8A CN202011369912A CN112517075B CN 112517075 B CN112517075 B CN 112517075B CN 202011369912 A CN202011369912 A CN 202011369912A CN 112517075 B CN112517075 B CN 112517075B
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- isophorone
- catalyst
- reaction
- acetate
- magnetic nanoparticles
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- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930192627 Naphthoquinone Natural products 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 150000002791 naphthoquinones Chemical class 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 26
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 18
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Chemical class 0.000 claims description 13
- 239000002184 metal Chemical class 0.000 claims description 13
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011258 core-shell material Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000006249 magnetic particle Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 claims description 2
- 229940105324 1,2-naphthoquinone Drugs 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-UHFFFAOYSA-N 0.000 claims description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 2
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- KQPYUDDGWXQXHS-UHFFFAOYSA-N juglone Chemical compound O=C1C=CC(=O)C2=C1C=CC=C2O KQPYUDDGWXQXHS-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 235000012711 vitamin K3 Nutrition 0.000 claims description 2
- 239000011652 vitamin K3 Substances 0.000 claims description 2
- 229940041603 vitamin k 3 Drugs 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 150000003335 secondary amines Chemical group 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HZNQSWJZTWOTKM-UHFFFAOYSA-N 2,3,4-trimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C(OC)=C1OC HZNQSWJZTWOTKM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ACYBVNYNIZTUIL-UHFFFAOYSA-N n'-benzylethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=C1 ACYBVNYNIZTUIL-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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Abstract
The invention discloses an isomerization catalyst and a preparation method thereof, and a preparation method of beta-isophorone. The isomerization catalyst, the structural formula of which is shown as:
Description
Technical Field
The invention relates to the field of catalysts and organic synthesis, in particular to an isomerization catalyst and a method for preparing beta-isophorone from alpha-isophorone.
Background
Beta-isophorone (3,5, 5-trimethylcyclohex-3-en-1-one) is an important intermediate for synthesizing vitamin E, carotenoids and various perfumes, especially an important raw material for preparing tea scented ketone (2,6, 6-trimethyl-2-cyclohexene-1, 4-dione, KIP).
The conventional preparation method of beta-isophorone is to take alpha-isophorone (3,5, 5-trimethylcyclohex-2-en-1-one) as a raw material and prepare the beta-isophorone through isomerization reaction under the action of a catalyst. The generation of the beta-isophorone relates to the equilibrium reaction of deconjugation, so the equilibrium concentration of the beta-isophorone is low, and the beta-isophorone needs to be continuously extracted by methods such as rectification and the like to promote the reaction to move towards the direction of generating the beta-isophorone.
Various methods have been reported for this isomerization reaction for a long time. The types of the used catalysts are mainly divided into acid catalysis and alkali catalysis, and the main process is as follows:
US patent US5907065A as Co3O4And metal oxides such as CaO and the like are used as catalysts, and the isomerization reaction is carried out by adopting a reduced pressure rectification mode. Although the purity of the obtained beta-isophorone can reach more than 97%, the reaction by-products are more, and the space-time yield is low.
In US4845303A, acetylacetone complexes of metals such as iron, cobalt, chromium, aluminum, etc. are used as catalysts to prepare beta-isophorone by reactive distillation. Although the reaction yield can reach 90-95%, the catalyst dosage is only 0.1-1 wt%. However, the space-time yield of the reaction is low, and the catalyst is dissolved in the reaction solution and is difficult to separate from the system, which is not favorable for industrial application.
US patent US4005145A discloses a process for carrying out an isomerisation reaction using acids. Acids used include adipic acid, trimethoxybenzoic acid, and the like. After reaction and rectification, the purity of the product can reach more than 91 percent, but the problems of more byproducts and serious equipment corrosion still exist.
Patents CN1288882A and CN1235954A disclose methods for preparing beta-isophorone by isomerization reaction using alkali metal compounds, including hydroxides and carbonates, as catalysts. Although the product obtained by the method has high purity, the catalyst has strong alkalinity and serious corrosion to equipment. And the catalyst is homogeneous and difficult to recycle.
In summary, there is a need to develop a novel catalyst for the isomerization reaction of beta-isophorone, which can solve the disadvantages of the prior art and process.
Disclosure of Invention
The invention provides an isomerization catalyst and a preparation method thereof. The catalyst is simple to prepare, active groups are loaded on the carrier through chemical bonds, the catalyst is high in stability, and no obvious activity loss exists after the catalyst can be reused. Also provides a preparation method of the beta-isophorone, which has high selectivity and high yield for the reaction of generating the beta-isophorone by isomerizing the alpha-isophorone and a catalyst. The reaction process is simple, has no corrosion to equipment and has strong industrial applicability.
In order to achieve the purpose, the invention adopts the following technical scheme:
an isomerization catalyst having the formula:wherein R is-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、 preferably-CH2CH2-; m represents Cr, Mn, Fe, Co, Ni, Cu, Zn, preferably Zn; ac represents an acetoxy group;magnetic nanoparticles Fe representing a core-shell structure3O4@SiO2。
A method of preparing the isomerization catalyst of the present invention comprises the steps of:
1) 3-Chloropropyltriethoxysilane (CPTES) on magnetic nanoparticles Fe with core-shell structure3O4@SiO2(SMNP) to obtain an alkyl halideBase-modified magnetic nanoparticles (MN-Cl);
2) performing substitution reaction on the halogenated alkyl modified magnetic nanoparticles (MN-Cl) and primary diamine to obtain amino modified magnetic nanoparticles;
3) performing substitution reaction on the amino-modified magnetic nanoparticles and o-formylbenzoic acid to prepare o-formylbenzoic acid-modified magnetic nanoparticles;
4) coordinating the magnetic nano-particle modified by o-formylbenzoic acid with metal ions to obtain the magnetic nano-particle catalyst modified by secondary amino and metal complexes.
The catalyst preparation reaction equation is exemplified as follows:
in the step 1), the magnetic nanoparticles Fe with core-shell structure3O4@SiO2(SMNP), see literature "carboxylated core-shell magnetic Nano Fe3O4Preparation of adsorbent and counter Cu2+Adsorption Performance, Proc. of higher school chemistry 2012, 33(1): 107-.
As a preferred embodiment, in step 1) of the present invention, the reaction of 3-Chloropropyltriethoxysilane (CPTES) with SMNP is carried out in a solvent, wherein the solvent comprises one or more of methanol, ethanol, toluene, acetonitrile, dichloromethane, acetone, n-hexane, cyclohexane, etc., and toluene is preferred.
In the step 1) of the invention, the mass ratio of the SMNP to the CPTES is 1:0.5-5, preferably 1: 1-3.
The reaction temperature in step 1) of the present invention is 60-120 deg.C, preferably 80-110 deg.C. The reaction time is 8-30h, preferably 10-15 h.
In step 2), the primary diamine includes one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and 1, 4-cyclohexanediamine, preferably one or more of ethylenediamine, propylenediamine, butylenediamine, and hexylenediamine, and more preferably ethylenediamine.
As a preferred embodiment, in step 2) of the present invention, the reaction of MN — Cl with the primary diamine is performed in a solvent, and the solvent includes one or more of methanol, ethanol, toluene, acetonitrile, water, acetone, n-hexane, cyclohexane, etc., preferably ethanol.
In the step 2) of the invention, the mass ratio of MN-Cl to primary diamine is 1:2-10, preferably 1: 4-8.
The reaction temperature of the step 2) of the present invention is 0 to 50 ℃, preferably 20 to 40 ℃. The reaction time is 15-50h, preferably 20-40 h.
As a preferable scheme, the reaction of the amine-group modified magnetic nanoparticles and o-formylbenzoic acid in step 3) of the present invention is performed in a solvent. The solvent includes one or more of methanol, ethanol, tetrahydrofuran, acetonitrile, dichloromethane, acetone, n-hexane, cyclohexane, ethyl acetate, etc., preferably acetonitrile.
In the step 3), the mass ratio of the amino-modified magnetic nanoparticles to the o-formylbenzoic acid is 1:5-30, preferably 1: 8-15.
In the step 3) of the present invention, the reaction temperature is 20 to 120 ℃, preferably 60 to 90 ℃. The reaction time is 10-60h, preferably 30-50 h.
In the step 4), the obtained o-formylbenzoic acid modified magnetic particles and metal ions are subjected to coordination reaction in a corresponding metal acetate aqueous solution, wherein the metal acetate comprises one or more of chromium acetate, manganese acetate, iron acetate, cobalt acetate, nickel acetate, copper acetate, zinc acetate and the like, and preferably zinc acetate.
In the step 4), the mass ratio of the o-formylbenzoic acid modified magnetic nanoparticles to the metal acetate is 1:1-40, preferably 1: 10-20.
In the step 4) of the present invention, the reaction temperature is 10 to 100 ℃, preferably 60 to 80 ℃. The reaction time is 5-80h, preferably 40-50 h.
In the preparation method of the beta-isophorone, the alpha-isophorone is prepared by isomerization reaction in the presence of the isomerization catalyst and the auxiliary agent.
In the method for preparing the beta-isophorone, the isomerization catalyst is used in an amount of 0.1-10 wt% relative to alpha-isophorone, and preferably 0.5-2 wt%.
In the preparation method of the beta-isophorone, the auxiliary agent is one or more of benzoquinone and naphthoquinone substances, preferably comprises one or more of benzoquinone, tert-butyl p-benzoquinone, methyl benzoquinone, 2-chloro-1, 4-benzoquinone, 1, 2-naphthoquinone, 1, 4-naphthoquinone, 5-hydroxy p-naphthoquinone and menadione; preference is given to naphthoquinones, more preferably 1, 4-naphthoquinone.
In the preparation method of the beta-isophorone, the amount of the auxiliary agent is 0.05-5 wt% relative to the amount of the alpha-isophorone, and preferably 0.2-2 wt%.
In the preparation method of beta-isophorone, the reaction can be carried out in a reactor known in the art, preferably in a tower reactor by a reactive distillation process, the theoretical plate number of the reactor is 20-50, preferably 30-40; the reaction temperature is 100 ℃ to 300 ℃, preferably 210 ℃ to 250 ℃. The reflux ratio is 10-50:1, preferably 30-40: 1.
The technical scheme of the invention has the following advantages:
(1) magnetic nanoparticles Fe with core-shell structure3O4@SiO2The (SMNP) is used as a catalyst carrier, so that the supported catalyst has a nano-scale dispersion effect, the dispersibility of the supported catalyst is improved, and the utilization rate of the catalyst is improved. In addition, SiO is coated on the surface of the magnetic nano particles2The layer forms a core-shell structure, so that the metal core can be prevented from being corroded by an acidic medium, the agglomeration of the catalyst is effectively avoided, and the service life of the catalyst is prolonged.
(2) Secondary amine groups playing a main catalytic role can be introduced on the surface of the magnetic carrier through further modification of 3-Chloropropyltriethoxysilane (CPTES) and primary diamine. And different substituted secondary amine groups can be introduced by adjusting the use of different primary diamines, so that the best catalytic effect is obtained. In addition, when secondary amine group is introduced, the residual primary amine group can be further reacted with o-formylbenzoic acid to generate imine, imine bond and carboxyl can be reacted with goldThe metal ions are coordinated to obtain the magnetic nano particle catalyst modified by secondary amino and metal complexes, so that a carbanion intermediate generated in the process of alpha-isophorone isomerization reaction can be effectively stabilized, and Michael addition (the product structure is) And carbonyl condensation (product structure is) And side reactions are carried out, so that the reaction selectivity is improved, and the accumulation of heavy components in a tower kettle in the reaction rectification process is avoided. Meanwhile, the conversion of the product beta-isophorone to alpha-isophorone is avoided.
(3) The auxiliary agent contains a polyatomic conjugated system, and plays a stabilizing role in charged intermediates including ions, free radicals and the like through a delocalization effect. Therefore, the method can also play a role in avoiding the accumulation of heavy components and the conversion of the beta-isophorone to the alpha-isophorone and improve the reaction selectivity.
(4) In addition, secondary amino and metal ions in the catalyst are connected to the catalyst carrier through chemical bonds, and the bonding effect is stronger than that of the common adsorption force, so that the stability of the catalyst in cyclic application can be improved, and the loss of active components of the catalyst is avoided. The catalyst can be used for 20 times, and the reaction conversion rate, the product selectivity and the product purity are not obviously reduced.
(5) Secondary amine groups with catalytic activity and metal ions are introduced on the surfaces of the magnetic particles through chemical modification, so that the defects that the catalyst is dissolved in a system, corrodes equipment and is difficult to recycle when organic base or inorganic base is singly used for catalysis are avoided. The catalyst is applied to the preparation of the beta-isophorone, has high catalytic efficiency and specificity, and is green and environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the invention.
Gas chromatography conditions: agilent gas chromatography, column HP-5 inPerforming line measurement, namely performing second-order temperature programming, wherein the initial temperature is 50 ℃, keeping the temperature for 1min, and then increasing the temperature to 80 ℃ at the speed of 5 ℃/min; then the temperature is increased to 250 ℃ at the speed of 10 ℃/min. Carrier gas high purity N2The split ratio is 100: 1. the temperature of the gasification chamber is 250 ℃, the temperature of the detector is FID, and the temperature of the detector is 250 ℃.
An infrared testing instrument: vetex-70 Fourier transform infrared spectrometer (Bruker, Germany).
Example 1
60g of magnetic nanoparticles (SMNP) with a core-shell structure are dispersed in 1.5L of toluene, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed. 60g of CPTES was added with mechanical stirring, followed by N2Reacting for 12h at 110 ℃ under the atmosphere. And after the reaction is finished, cooling to room temperature, carrying out magnetic separation on the solid, washing with absolute ethyl alcohol, and drying to obtain the magnetic nanoparticles (MN-Cl) with the surface modified by halogenated alkyl. IR: 2923cm-1,2852cm-1(methylene vibration), 680cm-1(C-Cl bond).
60g of MN-Cl is taken and dispersed in 1.5L of ethanol, 300g of ethylenediamine is added, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed. Then at N2Reacting for 24 hours at 25 ℃ under the atmosphere. And after the reaction is finished, carrying out magnetic separation on the solid, washing the solid with absolute ethyl alcohol, and drying to obtain the amino modified magnetic nanoparticles. IR: 2922cm-1,2852cm-1(methylene vibration), 1590cm-1(primary amine linkage).
60g of amino modified magnetic nanoparticles are dispersed in 1.5L of acetonitrile, 600g of o-formylbenzoic acid is added, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed. Then at N2Reacting for 30h at 70 ℃ under the atmosphere. And after the reaction is finished, carrying out magnetic separation on the solid, washing with acetonitrile, and drying to obtain the o-formylbenzoic acid modified magnetic nanoparticles. IR: 2924cm-1,2851cm-1(methylene vibration), 1642cm-1(imine bond), 1700cm-1(carboxyl group).
60g of the o-formylbenzoic acid modified magnetic nanoparticles are dispersed in 1.5L of deionized water, and 600g of zinc acetate is added. And performing ultrasonic treatment for 30min to uniformly disperse the particles. Then at N2Reacting for 48h at 60 ℃ under the atmosphere. After the reaction is finished, magnetically separating the solid, washing the solid with deionized water, and drying the washed solid to obtain secondary amino and goldBelongs to a complex modified magnetic nanoparticle catalyst (catalyst a). IR: 2922cm-1,2852cm-1(methylene vibration), 1640cm-1(imine bond), 560cm-1(metal coordinate bond).
1000g of alpha-isophorone containing 1.0 wt% of catalyst a and 0.5 wt% of 1, 4-naphthoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 98.2 percent, the selectivity of the beta-isophorone is 99.95 percent, the selectivity of heavy components is 0.05 percent, and the purity of the product beta-isophorone is 94.0 percent.
Example 2
1000g of alpha-isophorone containing 1.0 wt% of catalyst a and 0.5 wt% of benzoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 40: 1. The conversion rate of the alpha-isophorone is 97.8 percent, the selectivity of the beta-isophorone is 95.89 percent, the selectivity of heavy components is 4.11 percent, and the purity of the product beta-isophorone is 88.9 percent.
Example 3
60g of MN-Cl prepared in example 1 was dispersed in 1.5L of ethanol, 300g of hexamethylenediamine was added, and the mixture was dispersed uniformly by sonication for 30 min. Then at N2Reacting for 24 hours at 25 ℃ under the atmosphere. And after the reaction is finished, magnetically separating the solid, washing the solid with absolute ethyl alcohol, and drying to obtain the hexamethylene diamine modified magnetic nanoparticles.
Otherwise, referring to example 1, magnetic nanoparticles (catalyst b) modified with secondary amino groups and metal complex were obtained
1000g of alpha-isophorone containing 1.0 wt% of catalyst b and 0.5 wt% of 1, 4-naphthoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of alpha-isophorone is 93.2%, the selectivity of beta-isophorone is 99.91%, the selectivity of heavy components is 0.09%, and the purity of product beta-isophorone is 93.7%.
Example 4
60g of the o-formylbenzoic acid-modified magnetic nanoparticles prepared in example 1 were dispersed in 1.5L of deionized water, and 600g of nickel acetate was added. And performing ultrasonic treatment for 30min to uniformly disperse the particles. Then at N2Reacting for 48h at 60 ℃ under the atmosphere. And after the reaction is finished, magnetically separating the solid, washing the solid with deionized water, and drying to obtain the magnetic nanoparticle catalyst (catalyst c) modified by the secondary amino and the metal complex.
1000g of alpha-isophorone containing 1.0 wt% of catalyst c and 0.5 wt% of 1, 4-naphthoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 98.0 percent, the selectivity of the beta-isophorone is 96.02 percent, the selectivity of heavy components is 3.98 percent, and the purity of the product beta-isophorone is 90.7 percent.
After the end of the catalyst reaction in example 1, the catalyst was magnetically separated and washed with ethanol. After drying, the catalyst is mechanically applied according to the conditions of the reaction rectification in the example 1, and the experimental data are shown in the following table 1:
TABLE 1 catalyst a application data
Comparative example 1
1000g of alpha-isophorone containing 1.0 wt% of catalyst a is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 97.5 percent, the selectivity of the beta-isophorone is 92.42 percent, the selectivity of heavy components is 7.58 percent, and the purity of the product beta-isophorone is 84.8 percent.
Comparative example 2
1000g of o-formylbenzoic acid-modified magnetic nanoparticles prepared in example 1 and 0.5 wt% of 1, 4-naphthoquinone-containing α -isophorone were added to a tray-type tower reactor having 35 trays, and a rectification reaction was carried out at an absolute pressure of 0.1MPa, a reflux ratio of 30:1 at 220 ℃. The conversion rate of the alpha-isophorone is 97.7 percent, the selectivity of the beta-isophorone is 93.20 percent, the selectivity of heavy components is 6.80 percent, and the purity of the product beta-isophorone is 83.9 percent.
Comparative example 3
Comparative catalyst 1 was prepared by substituting o-formylbenzoic acid with glyoxylic acid and otherwise referring to example 1.
1000g of alpha-isophorone containing 1.0 wt% of a comparative catalyst 1 and 0.5 wt% of 1, 4-naphthoquinone was added to the bottom of a plate-type tower reactor having 35 plates, and a rectification reaction was carried out at an absolute pressure of 0.1MPa, a reflux ratio of 220 ℃ and a reflux ratio of 30: 1. The conversion rate of the alpha-isophorone is 97.3 percent, the selectivity of the beta-isophorone is 93.80 percent, the selectivity of heavy components is 6.20 percent, and the purity of the product beta-isophorone is 85.3 percent.
Comparative example 4
Comparative catalyst 2, which was prepared without reactive secondary amine groups, was prepared by substituting ethylenediamine for N-benzylethylenediamine and the remaining conditions refer to example 1.
1000g of alpha-isophorone containing 1.0 wt% of a comparative catalyst 2 and 0.5 wt% of 1, 4-naphthoquinone was added to the column bottom of a plate-type column reactor having 35 plates, and a rectification reaction was carried out at an absolute pressure of 0.1MPa, a reflux ratio of 220 ℃ and a reflux ratio of 30: 1. The conversion rate of the alpha-isophorone is 45.6 percent, the selectivity of the beta-isophorone is 80.75 percent, the selectivity of heavy components is 19.25 percent, and the purity of the product beta-isophorone is 40.36 percent.
Comparative example 5
1000g of alpha-isophorone containing 1.0 wt% of catalyst a and 0.5 wt% of cyclohexanone is added into a tower kettle of a plate tower reactor with 35 plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 97.3 percent, the selectivity of the beta-isophorone is 92.82 percent, the selectivity of heavy components is 7.18 percent, and the purity of the product beta-isophorone is 85.0 percent.
The above embodiments are not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention fall within the scope of the present invention.
Claims (14)
2. A process for preparing the isomerization catalyst of claim 1 comprising the steps of:
1) magnetic nano particle Fe with core-shell structure by using 3-chloropropyltriethoxysilane3O4@SiO2Modifying to obtain halogenated alkyl modified magnetic nanoparticles;
2) carrying out substitution reaction on the halogenated alkyl modified magnetic nanoparticles and primary diamine to obtain amino modified magnetic nanoparticles;
3) performing substitution reaction on the amino-modified magnetic nanoparticles and o-formylbenzoic acid to prepare o-formylbenzoic acid-modified magnetic nanoparticles;
4) coordinating the magnetic nanoparticles modified by o-formylbenzoic acid with metal ions to obtain a magnetic nanoparticle catalyst modified by secondary amino and metal complexes;
in the step 4), the obtained o-formylbenzoic acid modified magnetic particles and metal ions are subjected to coordination reaction in a corresponding metal acetate aqueous solution, wherein the metal acetate is selected from one or more of chromium acetate, manganese acetate, iron acetate, cobalt acetate, nickel acetate, copper acetate and zinc acetate.
3. The method of claim 2, wherein step 1 is performed by a computer) In, Fe3O4@SiO2The mass ratio of the 3-chloropropyltriethoxysilane to the reaction product is 1: 0.5-5.
4. The method according to claim 2, wherein in step 1), Fe3O4@SiO2The mass ratio of the silane to 3-chloropropyltriethoxysilane is 1: 1-3.
5. The method according to claim 2, wherein in step 2), the primary diamine is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and 1, 4-cyclohexanediamine.
6. The method as claimed in claim 2, wherein the mass ratio of the haloalkyl modified magnetic nanoparticles to the primary diamine in step 2) is 1: 2-10.
7. The method as claimed in claim 2, wherein the mass ratio of the haloalkyl modified magnetic nanoparticles to the primary diamine in step 2) is 1: 4-8.
8. The method according to claim 2, wherein in the step 3), the mass ratio of the amine-modified magnetic nanoparticles to the o-formylbenzoic acid is 1: 5-30.
9. The method as claimed in claim 2, wherein the mass ratio of the amine-group modified magnetic nanoparticles to the o-formylbenzoic acid in the step 3) is 1: 8-15.
10. The method as claimed in claim 2, wherein the mass ratio of the o-formylbenzoic acid modified magnetic nanoparticle to the metal acetate in the step 4) is 1: 1-40.
11. The method as claimed in claim 2, wherein in the step 4), the mass ratio of the o-formylbenzoic acid modified magnetic nanoparticle to the metal acetate is 1: 10-20.
12. A preparation method of beta-isophorone comprises the following steps: alpha-isophorone is prepared by an isomerization reaction in the presence of an isomerization catalyst as described in claim 1 or a catalyst prepared by a process as described in any one of claims 2 to 11 and auxiliaries.
13. The method according to claim 12, wherein the auxiliary agent is one or more of benzoquinone and naphthoquinone; and/or the dosage of the auxiliary agent is 0.05-5 wt% relative to the dosage of the alpha-isophorone.
14. The method of claim 12, wherein the auxiliary agent is one or more of benzoquinone, t-butyl-p-benzoquinone, methylbenzoquinone, 2-chloro-1, 4-benzoquinone, 1, 2-naphthoquinone, 1, 4-naphthoquinone, 5-hydroxy-p-naphthoquinone, and menadione; and/or the dosage of the auxiliary agent is 0.2-2 wt% relative to the dosage of the alpha-isophorone.
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CN111215138B (en) * | 2020-03-10 | 2022-11-08 | 万华化学集团股份有限公司 | Catalyst, preparation method and application of catalyst in preparation of beta-isophorone |
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