CN108440262A - A kind of method that solid-liquid biphasic catalysis oxidation of beta-isophorone prepares 4- ketoisophorones - Google Patents
A kind of method that solid-liquid biphasic catalysis oxidation of beta-isophorone prepares 4- ketoisophorones Download PDFInfo
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- CN108440262A CN108440262A CN201810322296.7A CN201810322296A CN108440262A CN 108440262 A CN108440262 A CN 108440262A CN 201810322296 A CN201810322296 A CN 201810322296A CN 108440262 A CN108440262 A CN 108440262A
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- catalyst
- isophorone
- ketoisophorones
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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 80
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 230000002051 biphasic effect Effects 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 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 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 239000003426 co-catalyst Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- VYBHLZOLHCQLHT-UHFFFAOYSA-N 1-(2-methylpropyl)-4,5-dihydroimidazole hydrochloride Chemical compound Cl.C(C(C)C)N1C=NCC1 VYBHLZOLHCQLHT-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- YDVJBLJCSLVMSY-UHFFFAOYSA-N carbamoyl cyanide Chemical compound NC(=O)C#N YDVJBLJCSLVMSY-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 58
- 239000002905 metal composite material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical class CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 abstract 2
- 125000006838 isophorone group Chemical class 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000013049 sediment Substances 0.000 description 12
- 239000003599 detergent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- -1 azo isobutyl cyano formamide Chemical compound 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010183 spectrum analysis Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 229910002445 Co(NO3)3·6H2O Inorganic materials 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010814 metallic waste Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 2
- 229930193351 phorone Natural products 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YWDWYOALXURQPZ-CYBMUJFWSA-N 2-methyl-n-[3-[(6s)-2,3,5,6-tetrahydroimidazo[2,1-b][1,3]thiazol-6-yl]phenyl]propanamide Chemical compound CC(C)C(=O)NC1=CC=CC([C@@H]2N=C3SCCN3C2)=C1 YWDWYOALXURQPZ-CYBMUJFWSA-N 0.000 description 1
- 235000005078 Chaenomeles speciosa Nutrition 0.000 description 1
- 240000000425 Chaenomeles speciosa Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229950000536 butamisole Drugs 0.000 description 1
- 238000001354 calcination Methods 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
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PSXRWZBTVAZNSF-UHFFFAOYSA-N hydron;quinoline;chloride Chemical compound Cl.N1=CC=CC2=CC=CC=C21 PSXRWZBTVAZNSF-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- SQZZGEUJERGRIN-UHFFFAOYSA-N manganese;pentane-2,4-dione Chemical compound [Mn].CC(=O)CC(C)=O SQZZGEUJERGRIN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- 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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods that solid-liquid biphasic catalysis oxidation of beta isophorone prepares 4 ketoisophorones.The method uses γ alundum (Al2O3) carried metal composite oxides (CuO Co2O3‑Fe2O3‑MgO/Al2O3) it is used as catalyst.It the described method comprises the following steps：β isophorones are in the presence of solvent, catalyst and hydrogen peroxide carries out oxidation reaction, and 4 ketoisophorones are made.The method reaction condition is mild, simple for process, product yield is high, environmentally protective, do not generate the waste liquid containing heavy metal element, can effectively solve the problem that the expendable problem of prior art preparation catalyst.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of solid-liquid biphasic catalysis oxidation of beta-isophorone preparation
The method of 4- ketoisophorones.
Background technology
4- ketoisophorones (abbreviation KIP) are a kind of important chemical intermediate products, can be used not only for cosmetics perfume
In material, it may also be used for the synthesis of carotenoid, vitamin.Due to importance of the 4- ketoisophorones in chemical products, close
It is always research hotspot for a long time at 4- ketoisophorones.
There are mainly two types of the methods of currently used synthesis KIP, is that β-isophorone (abbreviation β-IP) or α-is different respectively
Phorone (abbreviation α-IP) oxidative synthesis KIP.
Patent US4046813 describes one kind in the presence of pyridine, uses a kind of vanadium, iron, cobalt, manganese acetyl acetone complex
For the method that catalyst oxidation of beta-isophorone prepares KIP, although this method has about 100% conversion ratio, anti-
Should conversions of the β-IP to α-IP be had in the process, while have a large amount of high poly- by-product and generating so that the selectivity of the reaction
It is not high.
Patent CN101417936A describes the side that a kind of catalysis oxidation α-IP under no metal catalyst system prepare KIP
Method, but α-IP are difficult to aoxidize, and reaction conversion ratio highest only has 60%.
In the case that patent DE2526851 discloses addition molybdenum trioxide, the method that catalysis oxidation α-IP prepare KIP, but
In order to realize sufficiently high conversion ratio, the time of 72h or more and 80 DEG C or more of high temperature are needed, it under these conditions can be real
Existing yield only has within 50%.
Describe using phosphomolybdate as catalyst oxidation α-IP in patent EP0425976, reaction result with
DE2526851 is close.
In US4898985, using iron, copper, cobalt, the porphyrin of manganese or phthalocyanine complex as catalyst, while with three second
Amine or glycol dimethyl ether make solvent, and oxidation of beta-isophorone prepares KIP.Although this method has a very high yield, but porphyrin
Or phthalocyanines transition-metal catalyst is fairly expensive, and can be more easily damaged in reaction so that reaction process cost is higher.Separately
Outer diethylene glycol dimethyl ether and triethylamine are extremely dangerous in the operating condition, do not have realize industrialized condition at present.
Described in US6297404 it is a kind of doing catalysis system using n,N-Dimethylformamide and lithium acetate under conditions of urge
Change β-IP and aoxidize the method for preparing 4- ketoisophorones, the disadvantage of this method maximum is exactly to easy to produce ortho position oxidized byproduct
O-KIP, o-KIP are close with KIP in physical property, extremely difficult with the separation of KIP.
The above-mentioned method for preparing 4- ketoisophorones, both approach are each defective.It is KIP by α-IP direct oxidations,
The time needed is long, and conversion ratio is not high, and selectivity is low；And β-IP can be easy to be oxidized by oxygen to prepare KIP, but it is homogeneous
Catalyst oxidation, which has, largely to be generated containing metal waste liquid, and catalyst is difficult to recycle, and increases intractability and environmental protection
Cost pressure.
It is not mentioned in open source literature at present and uses γ-alundum (Al2O3) carried metal composite oxides as catalyst
The method that hydrogen peroxide oxidation β-isophorone prepares 4- ketoisophorones.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the object of the present invention is to provide a kind of solid-liquid biphasic catalysis oxidation of beta-is different
The method that phorone prepares 4- ketoisophorones.This method uses γ-alundum (Al2O3) carried metal composite oxides conduct
Catalyst hydrogen peroxide oxidation β-isophorone prepares 4- ketoisophorones.Reaction process is simple, reaction yield is high, tool
There is the advantages of catalyst recyclable recycling, and catalyst, after repeatedly applying mechanically, catalytic activity can keep stable.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of method that solid-liquid biphasic catalysis oxidation of beta-isophorone prepares 4- ketoisophorones, includes the following steps：
β-isophorone is in the presence of solvent, catalyst and hydrogen peroxide carries out oxidation reaction, and 4- ketoisophorones are made.
As a kind of specific embodiment, in a kettle, β-isophorone, solvent, catalyst is added, then to body
Hydrogen peroxide is added dropwise in system, carries out oxidation reaction, 4- ketoisophorones are made.
The reaction equation of the reaction is as follows：
Catalyst of the present invention is that composite oxide of metal is supported on (CuO-Co in γ-alundum (Al2O3) powder2O3-
Fe2O3-MgO/Al2O3), wherein the gross mass based on catalyst, copper oxide mass content is in 1%-10%, preferably 4%-5%；
Iron oxide mass content is in 0.5%-2%, preferably 1%-1.2%；Cobalt oxide mass content is in 0.5%-2%, preferably 1%-
1.2%；Magnesia mass content is in 0.5%-2%, preferably 1%-1.2%.Catalyst average grain diameter is 10-80 μm, preferably 30-
40μm。
As a kind of perferred technical scheme, β-isophorone is in the presence of solvent, catalyst, co-catalyst and hydrogen peroxide
Oxidation reaction is carried out, 4- ketoisophorones are made.It is different that the co-catalyst is selected from azo-bis-isobutyrate hydrochloride, azo two
It is one or more in Butamisole quinoline hydrochloride, azo isobutyl cyano formamide, preferred two isobutyl imidazoline hydrochloride of azo.
Co-catalyst of the present invention is water-soluble azo class compound, and its role is to improve composite oxide of metal
The selectivity of the product 4- ketoisophorones of catalyst β-isophorone oxidation, is reacting with conventional azo compound
In effect it is different.When being not added with co-catalyst in reaction system, most of β-isophorone generates the different Buddhist of 4- hydroxyls by oxidation
That ketone, and the yield of 4- ketoisophorones is relatively low.When, there are when co-catalyst, 4- hydroxy isophorones can be more in reaction system
Easily continue to be aoxidized and generate 4- ketoisophorones, to improve the selectivity of principal product.
The catalyst that the present invention uses has cellular structure, reaches nanoscale in reaction site, can effectively urge
Change β-IP and oxidation reaction occurs.Reaction process is divided into four-stage：Hydrogen peroxide generates hydrogen in catalyst activity component surface catalysis
Oxygen radical, hydroxyl free radical oxidation of beta-isophorone generate 4- hydroxy isophorones, hydroxyl free radical aoxidizes the different Buddhist of 4- hydroxyls
That ketogenesis 4,4- dihydroxy isophorone, the dehydration of 4,4- dihydroxy isophorones generate 4- ketoisophorones.Above four
Stage occurs simultaneously in reaction process.
Heretofore described composite oxide of metal is supported on the preparation method of γ-alundum (Al2O3) powder catalyst,
Include the following steps：
(1) proportionally, dissolving metal salts are configured to standard solution in water, in sodium carbonate and/or potassium carbonate standard
It is co-precipitated in solution；
(2) step (1) products therefrom is aged, dried, roasted；
Wherein, the metal salt is the soluble-salt of copper, cobalt, iron, magnesium and aluminium, preferably nitrate or chloride；It is described
Co-precipitation temperature in step (1) is 60-80 DEG C, preferably 70-75 DEG C.
Digestion time in the step (2) is 20-30 hours, preferably 22-26 hours.
Drying temperature in the step (2) is 80-100 DEG C, and preferably 90-95 DEG C, drying time is 18-36 hours, excellent
It selects 22-26 hours.
Calcination temperature in the step (2) is 300-500 DEG C, and preferably 375-425 DEG C, roasting time is 6-12 hours,
It is preferred that 7-9 hours.
In the present invention, the β-isophorone and catalyst quality ratio are 1:0.005-0.02, preferably 1:0.008-
0.012。
In the present invention, the solvent is selected from the one or more of methanol, ethyl alcohol, normal propyl alcohol and isopropanol, preferably methanol.
In the present invention, the mass ratio of the β-isophorone and solvent is 1:0.5-1, preferably 1:0.6-0.8.
In the present invention, the β-isophorone and co-catalyst mass ratio are 1:0.01-0.05, preferably 1:0.02-0.03.
As a kind of perferred technical scheme, oxidation reaction of the invention preferably carries out in the presence of an inorganic base.It is described
Inorganic base it is one or more in potassium carbonate, sodium carbonate, sodium phosphate, potassium phosphate, vulcanized sodium etc., preferably sodium carbonate or carbon
Sour potassium.It is advantageous to reacting under weakly alkaline environment, be conducive to the progress of final step dehydration.
In the present invention, the β-isophorone and inorganic base mass ratio are 1:0.001-0.005, preferably 1:0.002-
0.003。
In the present invention, the hydrogen peroxide concentration is selected from 30%-50%, preferably 35%-40%.
The mole amount ratio of β-isophorone and hydrogen peroxide of the present invention is 1:1-1.05 preferably 1:1.02-1.04.
In the present invention, the temperature of the oxidation reaction is 40-75 DEG C, and preferably 55-60 DEG C, the time of oxidation reaction is 4-
12h, preferably 7-9h.
This method compared with prior art, has the effect of following prominent：Using hydrogen peroxide as oxidant, technique letter
Single, operation is easy, and reaction condition is mild, process route environmental protection；Catalyst is cheap and easy to get recyclable, does not generate containing heavy metal
Waste liquid；Feed stock conversion can reach 99% or more, and the yield of product can reach 84-86%.Catalyst is by repeatedly applying mechanically
Afterwards, catalytic activity can be kept stable.
Specific implementation mode
Technical scheme of the present invention is further described below, however, it is not limited to this, every to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the range of technical solution of the present invention, should all cover the protection in the present invention
In range.
Analytical conditions for gas chromatography：
Chromatography model：Agilent WAX:1701.42249
Carrier gas：High pure nitrogen
Sample introduction pattern：Autosampler
Nitrogen flow：64.5ml/min
Temperature of vaporization chamber：280℃
Split sampling, split ratio：1：40
Sample size：0.2μl
Column flow rate 1.5ml/min
Column temperature：First stage program temperature rise, 100 DEG C of initial temperature are kept for 2 minutes, then rise to 230 with the rate of 15 DEG C/min
DEG C, it is kept for 15 minutes；Operation total time is 25.67min
300 DEG C of detector temperature
Select quantified by external standard method.
ICP element spectrum analysis instruments producer：Jiangsu wuxi outstanding person Boke skill
ICP element spectrum analysis instrument models：JB-750 types
Portion of reagent specification and source in embodiment
Embodiment 1
Prepare catalyst：
Take a certain amount of Cu (NO3)2·H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O、Co(NO3)3·6H2O、Mg
(NO3)2·6H2O, anhydrous Na2CO3After being dissolved in water, it is configured to the standard aqueous solution of 1mol/L respectively.Weigh 970mLNa2CO3Water
Solution heats to 70 DEG C in thermostat water bath, by 623mL aluminum nitrate aqueous solutions and 19mL copper nitrates, 6.3mL cobalt nitrates,
After 2.1mL ferric nitrates, the mixing of 2.5mL magnesium nitrate aqueous solutions, it is slowly dropped to Na2CO3In solution.Process control temp is added dropwise to exist
70 ± 5 DEG C, continues constant temperature after completion of dropwise addition and stir 40min, then sediment is poured into beaker, is aged at ambient temperature
24h.After sediment is filtered, Ion Cleaning sediment is spent until cleaning solution is in neutrality.Then the sediment that will be obtained by filtration
It is 24 hours dry under the conditions of 90 DEG C, then roasted 8 hours under 400 DEG C of high temperature.After being cooled to room temperature, catalyst is taken out, with pressure
Piece machine tabletting, then fully crushed with pulverizer and obtain 33.3g CuO-Co2O3-Fe2O3-MgO/Al2O31# catalyst.By XDR
Show that 1# catalyst average grain diameters are 35.4 μm after scanning；It is 4.55% to measure CuO contents by ICP element spectrum analysis,
Co2O3Content is 1.2%, Fe2O3Content is 0.51%, content of MgO 1.81%.
Prepare 4- ketoisophorones：
To install the reaction kettle of six leaf turbine high-speed stirred paddles as reactor.β-isophorone is sequentially added into reaction kettle
1380g, methanol 970g, sodium carbonate 3.45g, 1# catalyst 13.8g, two isobutyl imidazoline hydrochloride 34.5g of azo；Electricity is opened to add
Heat and mechanical agitation, 60 DEG C are warming up to by reacting liquid temperature, and the hydrogen peroxide solution of 2267g30% is added dropwise, and 6h is added dropwise, continues to keep the temperature
2h.After reaction, gas chromatographic analysis, it is 99.71% to measure raw material β-isophorone conversion ratio, and filtering reacting liquid is used in combination
Methanol washing catalyst, catalyst detergent liquid merge with reaction solution.After solvent Rotary Evaporators are deviate from, theoretical tray is used
The packed tower that number is 16 rectifying under the conditions of 1KPa removes the reaction solution after solvent, reflux ratio 3:1, collect 83-86 DEG C of tower top
Fraction, obtain 4- ketoisophorones, yield 85.61%.
Embodiment 2
Prepare 4- ketoisophorones：
By natural air drying after the catalyst detergent obtained in embodiment 1, the catalyst as embodiment 2.
To install the reaction kettle of six leaf turbine high-speed stirred paddles as reactor.β-isophorone is sequentially added into reaction kettle
1380g, ethyl alcohol 970g, sodium carbonate 1.38g, 1# catalyst 13.8g, two isobutyl imidazoline hydrochloride 13.8g of azo；Electricity is opened to add
Heat and mechanical agitation, 75 DEG C are warming up to by reacting liquid temperature, and the hydrogen peroxide solution of 2289g30% is added dropwise, and 6h is added dropwise, continues to keep the temperature
2h.After reaction, gas chromatographic analysis, it is 99.33% to measure raw material β-isophorone conversion ratio, and filtering reacting liquid is used in combination
Ethyl alcohol washing catalyst, catalyst detergent liquid merge with reaction solution.After solvent Rotary Evaporators are deviate from, theoretical tray is used
The packed tower that number is 16 rectifying under the conditions of 1KPa removes the reaction solution after solvent, reflux ratio 3:1, collect 83-86 DEG C of tower top
Fraction, obtain 4- ketoisophorones, yield 86.04%.
Embodiment 3
Prepare 4- ketoisophorones：
By natural air drying after the catalyst detergent obtained in embodiment 2, the catalyst as embodiment 3.
To install the reaction kettle of six leaf turbine high-speed stirred paddles as reactor.β-isophorone is sequentially added into reaction kettle
1380g, methanol 690g, potassium carbonate 3.45g, 1# catalyst 13.8g, two isobutyl imidazoline hydrochloride 34.5g of azo；Electricity is opened to add
Heat and mechanical agitation, 60 DEG C are warming up to by reacting liquid temperature, and the hydrogen peroxide solution of 1387g50% is added dropwise, and 6h is added dropwise, continues to keep the temperature
2h.After reaction, gas chromatographic analysis, it is 99.25% to measure raw material β-isophorone conversion ratio, and filtering reacting liquid is used in combination
Methanol washing catalyst, catalyst detergent liquid merge with reaction solution.After solvent Rotary Evaporators are deviate from, theoretical tray is used
The packed tower that number is 16 rectifying under the conditions of 1KPa removes the reaction solution after solvent, reflux ratio 3:1, collect 83-86 DEG C of tower top
Fraction, obtain 4- ketoisophorones, yield 85.13%.
Embodiment 4-8
By natural air drying after the catalyst detergent obtained in embodiment 3, repeat catalyst according to the condition of embodiment 3
Experiment is applied mechanically, it is as a result as follows：
| Embodiment | Catalyst applies mechanically number | Feed stock conversion | Reaction yield |
| 4 | 4 | 99.15% | 84.69% |
| 5 | 5 | 99.23% | 85.62% |
| 6 | 6 | 99.06% | 85.33% |
| 7 | 7 | 99.24% | 85.10% |
| 8 | 8 | 99.18% | 84.98% |
Catalyst is stablized in continuous procedural nature of applying mechanically, and continuously applies mechanically 8 times, feed stock conversion is more than 99%, reaction yield
Between 84%-86%.
Embodiment 9
Prepare catalyst：
Take a certain amount of Cu (NO3)2·H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O、Co(NO3)3·6H2O、Mg
(NO3)2·6H2O, anhydrous Na2CO3After being dissolved in water, it is configured to the standard aqueous solution of 1mol/L respectively.Weigh 985mLNa2CO3Water
Solution heats to 60 DEG C in thermostat water bath, by 645mL aluminum nitrate aqueous solutions and 5.7mL copper nitrates, 7.6mL nitric acid
After cobalt, 5.0mL ferric nitrates, the mixing of 2.2mL magnesium nitrate aqueous solutions, it is slowly dropped to Na2CO3In solution.Process control temp is added dropwise
Continue constant temperature at 60 ± 5 DEG C, after completion of dropwise addition and stir 40min, then sediment is poured into beaker, is aged at ambient temperature
20h.After sediment is filtered, Ion Cleaning sediment is spent until cleaning solution is in neutrality.Then the sediment that will be obtained by filtration
It is 18 hours dry under the conditions of 100 DEG C, then roasted 12 hours under 300 DEG C of high temperature.After being cooled to room temperature, catalyst is taken out, is used
Tabletting machine, then fully crushed with pulverizer and obtain 34.1g CuO-Co2O3-Fe2O3-MgO/Al2O32# catalyst.By
Show that 2# catalyst average grain diameters are 11.6 μm after XDR scannings；It is 1.35% to measure CuO contents by ICP element spectrum analysis,
Co2O3Content is 1.79%, Fe2O3Content is 1.14%, content of MgO 0.53%.
Prepare 4- ketoisophorones：
To install the reaction kettle of six leaf turbine high-speed stirred paddles as reactor.β-isophorone is sequentially added into reaction kettle
1380g, isopropanol 970g, sodium phosphate 6.9g, 2# catalyst 27.6g, azo-bis-isobutyrate hydrochloride 69g；Open electrical heating with
Reacting liquid temperature is warming up to 40 DEG C, the hydrogen peroxide solution of 2001g 35% is added dropwise, 10h is added dropwise, continues to keep the temperature by mechanical agitation
2h.After reaction, gas chromatographic analysis, it is 99.54% to measure raw material β-isophorone conversion ratio, and filtering reacting liquid is used in combination
Isopropanol washing catalyst, catalyst detergent liquid merge with reaction solution.After solvent Rotary Evaporators are deviate from, theoretical tower is used
The packed tower that plate number is 16 rectifying under the conditions of 1KPa removes the reaction solution after solvent, reflux ratio 3:1, collect tower top 83-86
DEG C fraction, obtain 4- ketoisophorones, yield 84.12%.
Embodiment 10
Prepare 4- ketoisophorones：
By natural air drying after the catalyst detergent obtained in embodiment 9, the catalyst as embodiment 10.
To install the reaction kettle of six leaf turbine high-speed stirred paddles as reactor.β-isophorone is sequentially added into reaction kettle
1380g, ethyl alcohol 718g, potassium phosphate 6.9g, 2# catalyst 27.6g, azo-bis-isobutyrate hydrochloride 69g；Open electrical heating and machine
Tool stirs, and reacting liquid temperature is warming up to 40 DEG C, the hydrogen peroxide solution of 2357g 30% is added dropwise, 10h is added dropwise, and continues to keep the temperature 2h.
After reaction, gas chromatographic analysis, it is 99.18% to measure raw material β-isophorone conversion ratio, and isopropyl is used in combination in filtering reacting liquid
Alcohol washing catalyst, catalyst detergent liquid merge with reaction solution.After solvent Rotary Evaporators are deviate from, theoretical cam curve is used
For 16 packed tower under the conditions of 1KPa rectifying remove solvent after reaction solution, reflux ratio 3:1, collect 83-86 DEG C of tower top
Fraction obtains 4- ketoisophorones, yield 86.97%.
Embodiment 11
Prepare catalyst：
Take a certain amount of Cu (NO3)2·H2O、Al(NO3)3·9H2O、Fe(NO3)3·9H2O、Co(NO3)3·6H2O、Mg
(NO3)2·6H2O, anhydrous Na2CO3After being dissolved in water, it is configured to the standard aqueous solution of 1mol/L respectively.Weigh 985mLNa2CO3Water
Solution heats to 80 DEG C in thermostat water bath, by 595mL aluminum nitrate aqueous solutions and 38mL copper nitrates, 2.2mL cobalt nitrates,
After 8.3mL ferric nitrates, the mixing of 4.2mL magnesium nitrate aqueous solutions, it is slowly dropped to Na2CO3In solution.Process control temp is added dropwise to exist
60 ± 5 DEG C, continues constant temperature after completion of dropwise addition and stir 40min, then sediment is poured into beaker, is aged at ambient temperature
30h.After sediment is filtered, Ion Cleaning sediment is spent until cleaning solution is in neutrality.Then the sediment that will be obtained by filtration
It is 36 hours dry under the conditions of 80 DEG C, then roasted 6 hours under 500 DEG C of high temperature.After being cooled to room temperature, catalyst is taken out, with pressure
Piece machine tabletting, then fully crushed with pulverizer and obtain 32.9g CuO-Co2O3-Fe2O3-MgO/Al2O33# catalyst.By XDR
Show that 3# catalyst average grain diameters are 70.3 μm after scanning；It is 9.15% to measure CuO contents by ICP element spectrum analysis,
Co2O3Content is 0.54%, Fe2O3Content is 1.88%, content of MgO 1.07%.
Prepare 4- ketoisophorones：
To install the reaction kettle of six leaf turbine high-speed stirred paddles as reactor.β-isophorone is sequentially added into reaction kettle
1380g, normal propyl alcohol 970g, vulcanized sodium 3.45g, 3# catalyst 6.9g, azo isobutyl cyano formamide 34.5g；Open electrical heating
With mechanical agitation, reacting liquid temperature is warming up to 60 DEG C, the hydrogen peroxide solution of 1428g 50% is added dropwise, 3h is added dropwise, continues to keep the temperature
1h.After reaction, gas chromatographic analysis, it is 99.66% to measure raw material β-isophorone conversion ratio, and filtering reacting liquid is used in combination
Isopropanol washing catalyst, catalyst detergent liquid merge with reaction solution.After solvent Rotary Evaporators are deviate from, theoretical tower is used
The packed tower that plate number is 16 rectifying under the conditions of 1KPa removes the reaction solution after solvent, reflux ratio 3:1, collect tower top 83-86
DEG C fraction, obtain 4- ketoisophorones, yield 85.88%.
Claims (11)
1. a kind of method that solid-liquid biphasic catalysis oxidation of beta-isophorone prepares 4- ketoisophorones, includes the following steps：β-
Isophorone is in the presence of solvent, catalyst and hydrogen peroxide carries out oxidation reaction, and 4- ketoisophorones are made.
2. according to the method described in claim 1, it is characterized in that, the catalyst is CuO-Co2O3-Fe2O3-MgO/
Al2O3, wherein copper oxide mass content is in 1%-10%, preferably 4%-5%；Iron oxide mass content is in 0.5%-2%, preferably
1%-1.2%；Cobalt oxide mass content is in 0.5%-2%, preferably 1%-1.2%；Magnesia mass content in 0.5%-2%,
It is preferred that 1%-1.2%；Gross mass based on catalyst.
3. according to the method described in claim 2, it is characterized in that, the average grain diameter of the catalyst is 10-80 μm, preferably
30-40μm。
4. method according to any one of claim 1-3, which is characterized in that the oxidation reaction is deposited in co-catalyst
In lower progress, the co-catalyst is selected from azo-bis-isobutyrate hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo isobutyl
It is one or more in cyano formamide, preferred two isobutyl imidazoline hydrochloride of azo.
5. according to the described method of any one of claim 1-4, which is characterized in that the solvent is selected from methanol, ethyl alcohol, just
One or more, the preferred methanol of propyl alcohol and isopropanol；The mass ratio of the β-isophorone and solvent is 1:0.5-1, preferably
1:0.6-0.8。
6. method according to any one of claims 1-5, which is characterized in that the β-isophorone and catalyst quality
Than being 1:0.005-0.02, preferably 1:0.008-0.012.
7. according to the method described in claim 4, it is characterized in that, the β-isophorone and co-catalyst mass ratio are 1:
0.01-0.05, preferably 1:0.02-0.03.
8. according to claim 1-7 any one of them methods, which is characterized in that the oxidation reaction is in the presence of an inorganic base
It carries out, the inorganic base is one or more in potassium carbonate, sodium carbonate, sodium phosphate, potassium phosphate and vulcanized sodium, preferably carbon
Sour sodium.
9. according to the method described in claim 8, it is characterized in that, the mass ratio of the β-isophorone and inorganic base is 1:
0.001-0.005, preferably 1:0.002-0.003.
10. according to the method described in any one of claim 1-9, which is characterized in that the β-isophorone and hydrogen peroxide
Mole ratio is 1:2-2.1 preferably 1:2.04-2.08.
11. according to the method described in any one of claim 1-10, which is characterized in that the temperature of the oxidation reaction is 40-
The time of 75 DEG C, preferably 55-60 DEG C, oxidation reaction is 4-12h, preferably 7-9h.
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| CN110075894A (en) * | 2019-04-03 | 2019-08-02 | 万华化学集团股份有限公司 | A kind of metal/metal composite oxide/g-C3N4The preparation method of catalyst and 4- ketoisophorone |
| CN110721696A (en) * | 2019-10-01 | 2020-01-24 | 山东新和成维生素有限公司 | Method for catalytically synthesizing tea scented ketone by adopting perovskite type composite oxide |
| CN111777497A (en) * | 2020-07-08 | 2020-10-16 | 万华化学集团股份有限公司 | Method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone |
| CN117623891A (en) * | 2023-11-03 | 2024-03-01 | 广州健顺生物医药研究院有限公司 | A kind of high-purity nicotinone crystal and its preparation method and application |
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| CN110075894A (en) * | 2019-04-03 | 2019-08-02 | 万华化学集团股份有限公司 | A kind of metal/metal composite oxide/g-C3N4The preparation method of catalyst and 4- ketoisophorone |
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| CN111777497B (en) * | 2020-07-08 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone |
| CN117623891A (en) * | 2023-11-03 | 2024-03-01 | 广州健顺生物医药研究院有限公司 | A kind of high-purity nicotinone crystal and its preparation method and application |
| CN118530113A (en) * | 2024-07-19 | 2024-08-23 | 山东富宇石化有限公司 | Preparation method of 2,3,5-trimethylhydroquinone diester |
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