CN110372555A - A kind of method that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin - Google Patents
A kind of method that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin Download PDFInfo
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- CN110372555A CN110372555A CN201910762538.9A CN201910762538A CN110372555A CN 110372555 A CN110372555 A CN 110372555A CN 201910762538 A CN201910762538 A CN 201910762538A CN 110372555 A CN110372555 A CN 110372555A
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- FDSDTBUPSURDBL-LOFNIBRQSA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)CCC1(C)C FDSDTBUPSURDBL-LOFNIBRQSA-N 0.000 title claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 235000012682 canthaxanthin Nutrition 0.000 title claims abstract description 36
- OOUTWVMJGMVRQF-DOYZGLONSA-N Phoenicoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)C(=O)CCC2(C)C OOUTWVMJGMVRQF-DOYZGLONSA-N 0.000 title claims abstract description 34
- 239000001659 canthaxanthin Substances 0.000 title claims abstract description 34
- 229940008033 canthaxanthin Drugs 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 claims abstract description 41
- 235000013734 beta-carotene Nutrition 0.000 claims abstract description 41
- 239000011648 beta-carotene Substances 0.000 claims abstract description 41
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 claims abstract description 41
- 229960002747 betacarotene Drugs 0.000 claims abstract description 41
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 claims abstract description 41
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000036647 reaction Effects 0.000 claims abstract description 5
- 230000005611 electricity Effects 0.000 claims description 41
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000008246 gaseous mixture Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 238000012856 packing Methods 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 238000010183 spectrum analysis Methods 0.000 description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000026030 halogenation Effects 0.000 description 6
- 238000005658 halogenation reaction Methods 0.000 description 6
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 5
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 5
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 2
- 101150019148 Slc7a3 gene Proteins 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal chlorate Chemical class 0.000 description 2
- FDSDTBUPSURDBL-DKLMTRRASA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)C(=O)CCC1(C)C FDSDTBUPSURDBL-DKLMTRRASA-N 0.000 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 150000001747 carotenoids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- DSPXASHHKFVPCL-UHFFFAOYSA-N 1-isocyanocyclohexene Chemical compound [C-]#[N+]C1=CCCCC1 DSPXASHHKFVPCL-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000623906 Lytta vesicatoria Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- UVCQMCCIAHQDAF-GYOQZRFSSA-N alpha-Bacterioruberin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C=C(C)/C=C/C(CCC(C)(C)O)C(C)(C)O)C=CC=C(/C)C=CC=C(/C)C=CC(CCC(C)(C)O)C(C)(C)O UVCQMCCIAHQDAF-GYOQZRFSSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UVCQMCCIAHQDAF-RNTVPSGKSA-N bacterioruberin Chemical compound CC(O)(C)CC[C@H](C(C)(C)O)/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(\C)/C=C/C=C(\C)/C=C/C=C(\C)/C=C/[C@H](CCC(C)(C)O)C(C)(C)O UVCQMCCIAHQDAF-RNTVPSGKSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- NNYBQONXHNTVIJ-UHFFFAOYSA-N etodolac Chemical compound C1COC(CC)(CC(O)=O)C2=C1C(C=CC=C1CC)=C1N2 NNYBQONXHNTVIJ-UHFFFAOYSA-N 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940063718 lodine Drugs 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin.Raw material beta carotene is dissolved in organic solvent, using gas oxygen source as oxidant, cell reaction one-step synthesis is carried out in the electrocatalysis oxidation apparatus for being filled with catalyst and obtains canthaxanthin.The invention has the advantages that reaction condition is mild, reaction process is easily controllable, environmentally protective, is suitble to industrialized production, and canthaxanthin yield is higher than 95%.
Description
Technical field
The invention belongs to nutrient chemistry product fields, and in particular to a kind of electro-catalysis oxygen oxidation of beta-carrotene preparation angle is yellow
The method of element.
Background technique
Canthaxanthin (canthaxanthin, β, β-Carotene-4,4'-dione) also known as Chinese blister beetle flavine, apricot bacterioruberin,
Canthaxanthin, cantaxanthin, edible orange 8, are a kind of orange-red carotenoid pigments of band, and a kind of anti-oxidant
Agent.Canthaxanthin is naturally present in many foods, such as mushroom, shellfish, fish and eggs.This pigment can also be used
Manual method manufacture, is mainly used in animal feed.
1980, Joachim Paust (US4212827) et al. reported the side that oxidation beta carotene prepares canthaxanthin
Method.This method is to aoxidize beta carotene with chlorate or bromate in the presence of a catalyst, the disadvantage is that the reaction time is too long,
Initiation is more difficult, and technique is unstable, uses more iodide.
2000, gloomy pretty tree (CN1277191) et al. aoxidized beta carotene, addition with alkali metal chlorate or bromate
Catalyst be halogenation iodine, iodine or metal iodide.Halogenation iodine used includes lodine chloride, iodine trichloride, Iodide Bromide and tribromo
Change iodine, halogenation iodine can be used with single kind or is used in mixed way with a variety of.
2001, Quesnel (EP1253131) research report was with H2O2For oxidant, I2For catalyst, chloroform or chlorine are selected
Benzene is solvent, and at room temperature, canthaxanthin yield is up to 40%, although oxidant H2O2It is pollution-free, but this method yield is not
It is high.
Toshiki Mori (US6313352) et al. carried out on the basis of Joachim Paust (US4212827) compared with
Good improvement, the reaction time greatly shortens after improvement.Three steps of the preparation of canthaxanthin point: 1) beta carotene is dissolved in dichloromethane
The aqueous solution of chlorate or bromate is added in flask by alkane；2) add halogenation iodine or iodine；3) add potassium iodide or sodium iodide.Angle is yellow
Plain yield reaches 76%, the disadvantage is that the halogenation iodine used has special toxicity and volatility and yield lower and halogenation iodine
With unstability.
2003, it was with sulfurous acid, bisulfites or acid that GC, which applies the method for strangling Gadamer (CN1417207) invention,
The hypobromous acid that sulphite and bromate combine generation makees oxidant, so that canthaxanthin obtains good yield, while obvious
Ground shortens the reaction time.The disadvantages of the method are as follows the hypobromous acid generated is unstable, it is difficult to realize industrialized production.
2003, Dubner Frank (EP1371642) et al. reported that oxidant NaClO solution is suitble to beta carotene oxygen
Change prepares canthaxanthin, I2For catalyst, this method reaction yield is up to 71%.Wu Shilin (CN1793098) et al. invention is adjusted with acid
It is yellow to aoxidize beta carotene preparation angle under the conditions of the light-illuminating of 200~800W for the aqueous oxidizing agent solution that good pH value is 2~5
Element.
2008, Pi Shiqing (CN101633633) et al. report beta carotene oxidation prepare canthaxanthin method be with
H2O2For catalyst, using alkali metal chlorate or bromate as oxidant.This method canthaxanthin yield reaches 78%.
The above method exist to some extent reaction yield it is low, it is operational difference or environment it is unfriendly the problems such as.In view of existing
The deficiency of technology needs to develop a kind of novel method for preparing canthaxanthin, with the more efficient work for more safely realizing canthaxanthin
Industry metaplasia produces.
Summary of the invention
It is an object of the invention to propose a kind of method of a new step oxidative synthesis canthaxanthin.This method uses β-Hu
Radish element electrocatalytic oxidation prepares canthaxanthin, and this method reaction yield is high, environmental-friendly, and reaction condition is mild and reaction process
It is easily controllable, it is easy to accomplish industrialized production.
To reach the above goal of the invention, technical scheme is as follows:
A kind of method that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin, raw material beta carotene has been dissolved in
In solvent, using gas oxygen source as oxidant, one step of cell reaction is carried out in the electrocatalysis oxidation apparatus for being filled with catalyst
Synthesis obtains canthaxanthin, reacts as follows:
Organic solvent of the present invention be one of methylene chloride, dichloroethanes, chloroform, carbon tetrachloride or a variety of,
It is preferred that dichloroethanes；The quality dosage of organic solvent is 4~200 times, preferably 9~49 times of beta carotene quality.
Gas oxygen source of the present invention is the gaseous mixture (oxygen of air (oxygen purity 21%) or oxygen and nitrogen
Content is 10~75v%)；The preferred oxygen content of gas oxygen source is 15~40v%；Gas oxygen source flux is 0.08~0.8m3·h-1,
It is preferred that 0.2~0.6m3·h-1。
Current density is 10~800A/dm after cell reaction of the present invention is powered2, preferably 100~400A/dm2；Reaction
Temperature is 20~70 DEG C, preferably 30~60 DEG C；Reaction time is 2~20h, preferably 6~15h.
Catalyst of the present invention is Au-CuO/ white bole-graphene, and the catalyst includes active component, helps
Agent and carrier, the active component include Au and CuO, and the auxiliary agent is white bole, and the carrier is graphene, wherein to urge
It is counted on the basis of the weight of agent, the content of Au is 0.5~8wt%, preferably 2~6wt%；The content of CuO is 1~10wt%, excellent
Select 4~8wt%；Graphene content is 72~86wt%, preferably 75~82wt%；Remaining is white bole.On under power on condition
Catalyst and Interaction Law of Electric Current are stated, good synergy has been embodied.
The preparation method of catalyst of the present invention comprises the steps of:
Step (1): graphene solid powder and white bole solid powder are added in low mass molecule alcohol and are ultrasonically treated
To being completely dispersed；
Step (2): the mixed system of step (1) is dry, it roasts, is obtained after Temperature fall white in inert gas atmosphere
Clay-graphene；
Step (3): gold chloride and copper nitrate are dissolved in the water, after step (2) obtained white bole-graphene is added
It is ultrasonically treated；
Step (4): the mixed system of step (3) is transferred in reaction kettle and carries out the bored kettle heat treatment of two-part；
Step (5): it after the drying of step (4) products therefrom, roasts in inert gas atmosphere, is made centainly with pelletizer
Au-CuO/ white bole-graphen catalyst of partial size.
In the present invention, the low mass molecule alcohol in the step (1) includes one of methanol, ethyl alcohol, normal propyl alcohol and isopropanol
Or a variety of, preferably methanol and/or ethyl alcohol, the dosage of low mass molecule alcohol are that well known can oxidize metal object solid powder and carrier is super
Fully decentralized dosage after sound, sonication treatment time are 3~13h, preferably 5~10h.
In the present invention, in the step (2) drying temperature be 65~100 DEG C, preferably 75~85 DEG C, drying time be 2~
8h, preferably 3~6h, maturing temperature be 850~1100 DEG C, preferably 900~1000 DEG C, calcining time be 3~10h, preferably 4~
8h。
In the present invention, the dosage of water is 5~35 times of gold chloride and copper nitrate gross mass in the step (3), preferably 10
~20 times, sonication treatment time is 3~13h, preferably 5~10h.
In the present invention, two-part bored kettle heat treatment in the step (4), first segment in 110~160 DEG C of bored kettles reactions 10~
50h, second segment react 10~50h in 160~260 DEG C of bored kettles.
In the present invention, in the step (5) drying temperature be 100~140 DEG C, preferably 110~130 DEG C, drying time 6
~for 24 hours, preferably 10~16h, maturing temperature is 850~1100 DEG C, and preferably 900~1000 DEG C, calcining time is 3~10h, preferably
4~8h, catalyst particle size are 0.3~1.25mm, preferably 0.6~1mm.
In the present invention, the electrocatalysis oxidation apparatus is as shown in the picture, includes microporous positive electricity pole plate a, porous negative electricity
Pole plate b, heating furnace c, loading catalyst d, thermocouple e, intelligent temperature controller f, DC power supply g, gas oxygen source h, pedestal i,
Gas chamber j, circulating pump k, liquid storage equipment l, inlet m, liquid outlet n, pressure reducing valve o, gas outlet p, reactor shell q.Wherein, micropore
Porous positive electricity pole plate a, porous negative electricity pole plate b are separately connected the electric contact of DC power supply g, and reactor shell q is embedded in heating furnace c
In, inlet m is located at reactor shell bottom and above microporous positive electricity pole plate a, and liquid outlet n is located at porous negative electricity pole plate
Above b, inlet m and liquid outlet n pass sequentially through pipeline and are connected to form circuit, and the mating thermocouple e of intelligent temperature controller f is to adding
Hot stove c is controlled.
The aperture of microporous positive electricity pole plate a of the present invention is 20~60 μm, preferably 30~50 μm；The porous negative electricity
The aperture of pole plate b is 0.1~1mm, preferably 0.3~0.7mm.
The filling ratio of height to diameter of catalyst is (1.5~5): 1, preferably (2~4) in electrocatalysis oxidation apparatus of the present invention:
1；The volume of organic solvent and the admission space ratio of catalyst are (0.5~100): 1, preferably (25~75): 1；The stream of circulating pump k
Speed is 1~50mL/min, preferably 15~35mL/min.
The positive effect of the present invention is:
(1) most clean reagent-electronics is used, it is completely nuisanceless, it is the important skill of current " green synthetic chemistry "
Art；
(2) carrying out beta carotene oxidative synthesis canthaxanthin as oxidant using air or oxygen gaseous mixture is green oxidation
Approach, and air or oxygen gaseous mixture abundance, it is easy to use, it is cheap and easy to get, it is more suitable for industrial production；
(3) reaction condition is mild and reaction process is easily controllable, therefore safer, efficient；Production operation difficulty is low, reaction
High income is higher than 95%, has industrial value.
Detailed description of the invention
Fig. 1 is the schematic device that electro-catalysis oxygen oxidation of beta-carrotene of the present invention prepares canthaxanthin.
In figure: a and b is respectively microporous positive electricity pole plate and porous negative electricity pole plate；C is heating furnace；D is filling catalysis
Agent；E is thermocouple；F is intelligent temperature controller；G is DC power supply；H is gas oxygen source；I is pedestal；J is gas chamber；K is to follow
Ring pump；L is liquid storage equipment；M is inlet；N is liquid outlet；O is pressure reducing valve；P is gas outlet；Q is reactor shell.
Specific embodiment
In order to which technical characteristic and content of the invention is understood in detail, portion of the invention is described in more detail below
Divide embodiment.Although describing some embodiments of the invention in embodiment, however, it is to be appreciated that can be in a variety of manners
Realize the present invention without that should be limited by the embodiments set forth herein.
Raw material (beta carotene) and gained target product (canthaxanthin) use standard by efficient liquid phase chromatographic analysis purity
Sample establishes external standard curve, and measured purity is all the purity of liquid phase external standard method.Analysis condition is as follows:
Liquid chromatogram instrument model Agilent 1260；Chromatographic column C30 column YMC carotenoid S-5um (4.6*
250mm)；Mobile phase is acetonitrile: isopropanol=9:1 (mass ratio)；Column temperature is 30 DEG C；Flow velocity is 2.0ml/min；Sample volume is
10.0 μ L, Detection wavelength 474nm.
Au-CuO/ white bole-graphen catalyst determines group by ICP element spectrum analysis instrument and infrared carbon sulfur analyzer
At content.ICP element spectrum analysis instrument model JB-750 type, jiangsu wuxi Jie Bo electric appliance Science and Technology Ltd.；Infrared Carbon-sulphur
Analyzer model CS996, jiangsu wuxi Jie Bo electric appliance Science and Technology Ltd..
Reagent and solvent used in embodiment and comparative example are purchased from Shanghai Mike's woods biochemical technology Co., Ltd:
| Reagent | Purity/% |
| Graphene | 99% |
| White bole | 99% |
| Gold chloride | 99.9% |
| Copper nitrate | 99% |
| Methanol | 99.9% |
| Ethyl alcohol | 99.8% |
| Normal propyl alcohol | 99.8% |
| Isopropanol | 99.5% |
| Methylene chloride | 99.9% |
| Dichloroethanes | 99% |
| Chloroform | 99% |
| Carbon tetrachloride | 99.5% |
| Beta carotene | 99% |
Embodiment 1
412g graphene solid powder and 100g white bole solid powder are added in 1536g methanol, 3h is ultrasonically treated
After obtain mixed system a.The filtered solid of mixed system a is dried into 2h at 65 DEG C, then in 850 DEG C of height in nitrogen atmosphere
The lower roasting 10h of temperature obtains white bole-graphene carrier.Weigh gold chloride and copper nitrate solid each 6g and 135g to be dissolved in 705g pure
In water, it is added after aforementioned gained white bole-graphene carrier after carrying out ultrasonic treatment 3h and obtains mixed system b.By mixed system b
Prior to 110 DEG C bored kettle reaction 10h are transferred in the autoclave of polytetrafluoro lining, react 10h then at 160 DEG C of bored kettles.Then
The dry 6h at 100 DEG C, then 10h is roasted under 850 DEG C of high temperature in nitrogen atmosphere, partial size finally, which is made, with pelletizer is
Au-CuO/ white bole-graphen catalyst Cat1 of 0.3mm.It measures Au through ICP element spectrum analysis and Infrared Carbon-sulphur analysis and contains
Amount is 0.52wt%, and CuO content is 10.01wt%, and graphene content is 72wt%.
Embodiment 2
688g graphene solid powder and 40g white bole solid powder are added in 2184g normal propyl alcohol, are ultrasonically treated
Mixed system a is obtained after 13h.By the filtered solid of mixed system a at 100 DEG C dry 8h, then in nitrogen atmosphere in
3h is roasted under 1100 DEG C of high temperature obtains white bole-graphene carrier.Weigh gold chloride and copper nitrate solid each 128g and 19g dissolution
In 5145g pure water, it is added after aforementioned gained white bole-graphene carrier after carrying out ultrasonic treatment 13h and obtains mixed system b.
Mixed system b is transferred in the autoclave of polytetrafluoro lining prior to 160 DEG C bored kettle reaction 50h, it is anti-then at 260 DEG C of bored kettles
Answer 50h.Then it is dried for 24 hours at 140 DEG C, then roasts 3h under 1100 DEG C of high temperature in nitrogen atmosphere, finally use granulation mechanism
Au-CuO/ white bole-graphen catalyst the Cat2 for being 1.25mm at partial size.Through ICP element spectrum analysis and Infrared C sulphur content
It is 8wt% that analysis, which measures Au content, and CuO content is 1.01wt%, and graphene content is 85.99wt%.
Embodiment 3
461g graphene solid powder and 85g white bole solid powder are added in 1638g methanol, after being ultrasonically treated 5h
Obtain mixed system a.The filtered solid of mixed system a is dried into 3h at 75 DEG C, then in 900 DEG C of high temperature in nitrogen atmosphere
Lower roasting 8h obtains white bole-graphene carrier.Weigh gold chloride and copper nitrate solid each 24g and 115g to be dissolved in 1390g pure
In water, it is added after aforementioned gained white bole-graphene carrier after carrying out ultrasonic treatment 5h and obtains mixed system b.By mixed system b
Prior to 120 DEG C bored kettle reaction 20h are transferred in the autoclave of polytetrafluoro lining, react 20h then at 180 DEG C of bored kettles.Then
The dry 10h at 110 DEG C, then 8h is roasted under 900 DEG C of high temperature in nitrogen atmosphere, partial size finally, which is made, with pelletizer is
Au-CuO/ white bole-graphen catalyst Cat3 of 0.6mm.It measures Au through ICP element spectrum analysis and Infrared Carbon-sulphur analysis and contains
Amount is 1.98wt%, and CuO content is 8.04wt%, and graphene content is 75.98wt%.
Embodiment 4
615g graphene solid powder and 60g white bole solid powder are added in 2025g isopropanol, are ultrasonically treated
Mixed system a is obtained after 10h.The filtered solid of mixed system a is dried into 6h at 85 DEG C, then in 1000 in nitrogen atmosphere
Roasting 4h obtains white bole-graphene carrier under DEG C high temperature.It weighs gold chloride and copper nitrate solid each 90g and 71g is dissolved in
In 3220g pure water, it is added after aforementioned gained white bole-graphene carrier after carrying out ultrasonic treatment 10h and obtains mixed system b.It will
Mixed system b is transferred in the autoclave of polytetrafluoro lining prior to 150 DEG C bored kettle reaction 40h, then at 240 DEG C of bored kettle reactions
40h.Then the dry 16h at 130 DEG C, then 4h is roasted under 1000 DEG C of high temperature in nitrogen atmosphere, finally it is made of pelletizer
Partial size is Au-CuO/ white bole-graphen catalyst Cat4 of 1mm.It is measured through ICP element spectrum analysis and Infrared Carbon-sulphur analysis
Au content is 6wt%, and CuO content is 4.01wt%, and graphene content is 81.99wt%.
Embodiment 5
520g graphene solid powder and 65g white bole solid powder are added in 1755g ethyl alcohol, after being ultrasonically treated 8h
Obtain mixed system a.The filtered solid of mixed system a is dried into 4.5h at 80 DEG C, then in 950 DEG C of height in nitrogen atmosphere
The lower roasting 6h of temperature obtains white bole-graphene carrier.Weigh gold chloride and copper nitrate solid each 53g and 91g to be dissolved in 2160g pure
In water, it is added after aforementioned gained white bole-graphene carrier after carrying out ultrasonic treatment 7.5h and obtains mixed system b.By mixture
It is that b is transferred in the autoclave of polytetrafluoro lining prior to 135 DEG C bored kettle reaction 30h, reacts 30h then at 210 DEG C of bored kettles.So
The dry 13h at 120 DEG C afterwards, then 6h is roasted under 950 DEG C of high temperature in nitrogen atmosphere, partial size finally, which is made, with pelletizer is
Au-CuO/ white bole-graphen catalyst Cat5 of 0.8mm.It measures Au through ICP element spectrum analysis and Infrared Carbon-sulphur analysis and contains
Amount is 4.08wt%, and CuO content is 5.94wt%, and graphene content is 79.99wt%.
Embodiment 6
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 20 μm, porous negative electrode
The aperture of plate b is 0.1mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
8.25cm, diameter are 5.5cm (ratio of height to diameter 1.5, volume 195.9mL), and Catalyst packing part is filled up with Cat1.
32.4g beta carotene is dissolved in 130g organic solvent dichloromethane (98mL) and is configured to beta carotene solution
(quality of organic solvent is 4 times of beta carotene quality, and the volume of organic solvent and the admission space ratio of catalyst are
0.5) it, and is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 1mL/min, and with 0.08m3·h-1Gas
Body flow leads to gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 10v%)；After liquid establishes circulation, pass through intelligent temperature
Spending controller f control temperature of reaction system is 20 DEG C；800A/dm is provided by DC power supply g2Electric current, electrocatalytic oxidation is anti-
After answering 2h, reaction solution is sampled and carries out efficient liquid phase chromatographic analysis, measuring raw material beta carotene conversion ratio is 97.39%, angle
Flavine yield is 95.28%.
Embodiment 7
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 60 μm, porous negative electrode
The aperture of plate b is 1mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
18.5cm, diameter are 3.7cm (ratio of height to diameter 5, volume 198.8mL), and Catalyst packing part is filled up with Cat2.
122.8g beta carotene is dissolved in 24553g organic solvent dichloroethanes (19881mL) and is configured to β-carrot
(quality of organic solvent is 200 times of beta carotene quality, the volume of organic solvent and the admission space of catalyst to plain solution
Than for 100), and it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 50mL/min, and with 0.8m3·h-1
Gas flow lead to gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 75v%)；After liquid establishes circulation, pass through intelligence
Energy temperature controller f control temperature of reaction system is 70 DEG C；10A/dm is provided by DC power supply g2Electric current, electrocatalytic oxidation
After reacting 20h, reaction solution is sampled and carries out efficient liquid phase chromatographic analysis, measuring raw material beta carotene conversion ratio is 96.14%,
Canthaxanthin yield is 95.62%.
Embodiment 8
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 30 μm, porous negative electrode
The aperture of plate b is 0.3mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
10cm, diameter are 5cm (ratio of height to diameter 2, volume 196.3mL), and Catalyst packing part is filled up with Cat3.
809g beta carotene is dissolved in 7281g organic solvents, chloroform (4906mL) and is configured to beta carotene solution
(quality of organic solvent is 9 times of beta carotene quality, the volume of organic solvent and the admission space ratio of catalyst be 25),
And it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 15mL/min, and with 0.2m3·h-1Gas flow
Logical gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 15v%)；After liquid establishes circulation, controlled by intelligent temperature
It is 30 DEG C that device f, which controls temperature of reaction system,；400A/dm is provided by DC power supply g2Electric current, after electrocatalysis oxidation reaction 6h,
Reaction solution is sampled and carries out efficient liquid phase chromatographic analysis, measuring raw material beta carotene conversion ratio is 97.51%, canthaxanthin yield
It is 96.55%.
Embodiment 9
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 50 μm, porous negative electrode
The aperture of plate b is 0.7mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
16cm, diameter are 4cm (ratio of height to diameter 4, volume 201mL), and Catalyst packing part is filled up with Cat4.
490.6g beta carotene is dissolved in 24040g organic solvent carbon tetrachloride (15072mL) and is configured to β-carrot
(quality of organic solvent is 49 times of beta carotene quality, the volume of organic solvent and the admission space of catalyst to plain solution
Than for 75), and it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 35mL/min, and with 0.6m3·h-1's
Gas flow leads to gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 40v%)；After liquid establishes circulation, pass through intelligence
It is 60 DEG C that temperature controller f, which controls temperature of reaction system,；100A/dm is provided by DC power supply g2Electric current, electrocatalytic oxidation
After reacting 15h, reaction solution is sampled and carries out efficient liquid phase chromatographic analysis, measuring raw material beta carotene conversion ratio is 97.95%,
Canthaxanthin yield is 96.75%.
Embodiment 10
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 40 μm, porous negative electrode
The aperture of plate b is 0.5mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
13.5cm, diameter are 4.5cm (ratio of height to diameter 3, volume 214.6mL), and Catalyst packing part is filled up with Cat5.
456.9g beta carotene is dissolved in 13252g organic solvent dichloroethanes (10730mL) and is configured to β-carrot
(quality of organic solvent is 29 times of beta carotene quality, the volume of organic solvent and the admission space of catalyst to plain solution
Than for 50), and it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 25mL/min, and with 0.4m3·h-1's
Gas flow leads to gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 27v%)；After liquid establishes circulation, pass through intelligence
It is 45 DEG C that temperature controller f, which controls temperature of reaction system,；250A/dm is provided by DC power supply g2Electric current, electrocatalytic oxidation
After reacting 8h, reaction solution is sampled and carries out efficient liquid phase chromatographic analysis, measuring raw material beta carotene conversion ratio is 98.93%,
Canthaxanthin yield is 98.45%.
Embodiment 11
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 40 μm, porous negative electrode
The aperture of plate b is 0.5mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
13.5cm, diameter are 4.5cm (ratio of height to diameter 3, volume 214.6mL), and Catalyst packing part is filled up with Cat5.
456.9g beta carotene is dissolved in 13252g organic solvent dichloroethanes (10730mL) and is configured to β-carrot
(quality of organic solvent is 29 times of beta carotene quality, the volume of organic solvent and the admission space of catalyst to plain solution
Than for 50), and it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 25mL/min, and with 0.4m3·h-1's
Gas flow blowing air (oxygen content 21v%)；After liquid establishes circulation, reactant is controlled by intelligent temperature controller f
Be temperature be 45 DEG C；250A/dm is provided by DC power supply g2Electric current, after electrocatalysis oxidation reaction 8h, reaction solution is sampled
Efficient liquid phase chromatographic analysis is carried out, measuring raw material beta carotene conversion ratio is 99.12%, and canthaxanthin yield is 97.41%.
Comparative example 1
This comparative example does not use electro-catalysis.
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 40 μm, porous negative electrode
The aperture of plate b is 0.5mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
13.5cm, diameter are 4.5cm (ratio of height to diameter 3, volume 214.6mL), and Catalyst packing part is filled up with Cat5.
456.9g beta carotene is dissolved in 13252g organic solvent dichloroethanes (10730mL) and is configured to β-carrot
(quality of organic solvent is 29 times of beta carotene quality, the volume of organic solvent and the admission space of catalyst to plain solution
Than for 50), and it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 25mL/min, and with 0.4m3·h-1's
Gas flow leads to gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 27v%)；After liquid establishes circulation, pass through intelligence
It is 45 DEG C that temperature controller f, which controls temperature of reaction system, samples after 8h to reaction solution and carries out efficient liquid phase chromatographic analysis, measures original
Expect that beta carotene conversion ratio is 41.11%, canthaxanthin yield is 33.41%.
Comparative example 2
This comparative example substitutes catalyst prepared by the present invention with graphene.
As shown in the picture, in electrocatalysis oxidation apparatus, the aperture of microporous positive electricity pole plate a is 40 μm, porous negative electrode
The aperture of plate b is 0.5mm, Catalyst packing part between microporous positive electricity pole plate a and porous negative electricity pole plate b it is a height of
13.5cm, diameter are 4.5cm (ratio of height to diameter 3, volume 214.6mL), and Catalyst packing part is filled up with graphene.
456.9g beta carotene is dissolved in 13252g organic solvent dichloroethanes (10730mL) and is configured to β-carrot
(quality of organic solvent is 29 times of beta carotene quality, the volume of organic solvent and the admission space of catalyst to plain solution
Than for 50), and it is transferred in liquid storage equipment l；Opening circulating pump k setting flow rate of liquid is 25mL/min, and with 0.4m3·h-1's
Gas flow leads to gaseous mixture (gaseous mixture of oxygen and nitrogen, oxygen content 27v%)；After liquid establishes circulation, pass through intelligence
It is 45 DEG C that temperature controller f, which controls temperature of reaction system,；250A/dm is provided by DC power supply g2Electric current, electrocatalytic oxidation
After reacting 8h, reaction solution is sampled and carries out efficient liquid phase chromatographic analysis, measuring raw material beta carotene conversion ratio is 60.23%,
Canthaxanthin yield is 47.89%.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of method that electro-catalysis oxygen oxidation of beta-carrotene prepares canthaxanthin, raw material beta carotene is dissolved in organic
In solvent, using gas oxygen source as oxidant, one step of cell reaction is carried out in the electrocatalysis oxidation apparatus for being filled with catalyst and is closed
At obtaining canthaxanthin.
2. the method according to claim 1, wherein the organic solvent is methylene chloride, dichloroethanes, chloroform
With one of carbon tetrachloride or a variety of, preferably dichloroethanes；The quality dosage of organic solvent be beta carotene quality 4~
200 times, preferably 9~49 times.
3. the method according to claim 1, wherein the gas oxygen source is that (oxygen purity is air
And/or the gaseous mixture of oxygen and nitrogen 21%) (oxygen content is 10~75v%)；The preferred oxygen content of gas oxygen source be 15~
40v%；Gas oxygen source flux is 0.08~0.8m3·h-1, preferably 0.2~0.6m3·h-1。
4. the method according to claim 1, wherein the cell reaction be powered after current density be 10~
800A/dm2, preferably 100~400A/dm2；Reaction temperature is 20~70 DEG C, preferably 30~60 DEG C；Reaction time is 2~20h, excellent
Select 6~15h.
5. being urged the method according to claim 1, wherein the catalyst is Au-CuO/ white bole-graphene
Agent includes active component, auxiliary agent and carrier, and the active component includes Au and CuO, and the auxiliary agent is white bole, the carrier
For graphene；Wherein, it is counted on the basis of the weight of catalyst, the content of Au is 0.5~8wt%, preferably 2~6wt%；CuO's
Content is 1~10wt%, preferably 4~8wt%；Graphene content is 72~86wt%, preferably 75~82wt%；Remaining is white pottery
Soil.
6. method according to any one of claims 1-5, which is characterized in that the preparation step of the catalyst are as follows:
Step (1): graphene solid powder and white bole solid powder are added in low mass molecule alcohol and are ultrasonically treated to complete
Full dispersion；
Step (2): the mixed system of step (1) is dry, it is roasted in inert gas atmosphere, white pottery is obtained after Temperature fall
Soil-graphene；
Step (3): gold chloride and copper nitrate are dissolved in the water, and are carried out after step (2) obtained white bole-graphene is added
Ultrasonic treatment；
Step (4): the mixed system of step (3) is transferred in reaction kettle and carries out the bored kettle heat treatment of two-part；
Step (5): it after the drying of step (4) products therefrom, is roasted in inert gas atmosphere, certain partial size is made with pelletizer
Au-CuO/ white bole-graphen catalyst.
7. according to the method described in claim 6, it is characterized in that, in the step (1) low mass molecule alcohol include methanol, ethyl alcohol,
One of normal propyl alcohol and isopropanol are a variety of, preferably methanol and/or ethyl alcohol；Sonication treatment time be 3~13h, preferably 5~
10h；
Drying temperature is 65~100 DEG C in the step (2), and preferably 75~85 DEG C, drying time is 2~8h, preferably 3~6h；
Maturing temperature is 850~1100 DEG C, and preferably 900~1000 DEG C, calcining time is 3~10h, preferably 4~8h；
The dosage of water is 5~35 times of gold chloride and copper nitrate gross mass in the step (3), preferably 10~20 times；At ultrasound
The reason time is 3~13h, preferably 5~10h；
Two-part bored kettle heat treatment in the step (4), first segment react 10~50h in 110~160 DEG C of bored kettles, second segment in
160~260 DEG C of bored kettles react 10~50h；
In the step (5) drying temperature be 100~140 DEG C, preferably 110~130 DEG C, drying time be 6~for 24 hours, preferably 10
~16h；Maturing temperature is 850~1100 DEG C, and preferably 900~1000 DEG C, calcining time is 3~10h, preferably 4~8h；Catalyst
Partial size is 0.3~1.25mm, preferably 0.6~1mm.
8. the method according to claim 1, wherein the electrocatalysis oxidation apparatus includes microporous positive electrode
Plate a, porous negative electricity pole plate b, heating furnace c, loading catalyst d, thermocouple e, intelligent temperature controller f, DC power supply g, gas
Oxygen source h, pedestal i, gas chamber j, circulating pump k, liquid storage equipment l, inlet m, liquid outlet n, pressure reducing valve o, gas outlet p, reactor enclosure
Body q；
Wherein, microporous positive electricity pole plate a, porous negative electricity pole plate b are separately connected the electric contact of DC power supply g, reactor shell q
In heating furnace c, inlet m is located at reactor shell bottom and above microporous positive electricity pole plate a, and liquid outlet n is located at
Above porous negative electricity pole plate b, inlet m and liquid outlet n pass sequentially through pipeline and are connected to form circuit, and intelligent temperature controller f matches
Set thermocouple e controls heating furnace c.
9. method according to claim 1 to 8, which is characterized in that the hole of the microporous positive electricity pole plate a
Diameter is 20~60 μm, preferably 30~50 μm；The aperture of the porous negative electricity pole plate b is 0.1~1mm, preferably 0.3~0.7mm.
10. method according to claim 1 to 9, which is characterized in that be catalyzed in the electrocatalysis oxidation apparatus
The filling ratio of height to diameter of agent is (1.5~5): 1, preferably (2~4): 1；The volume of organic solvent and the admission space ratio of catalyst are
(0.5~100): 1, preferably (25~75): 1；The flow velocity of circulating pump k is 1~50mL/min, preferably 15~35mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910762538.9A CN110372555B (en) | 2019-08-19 | 2019-08-19 | Method for preparing canthaxanthin by oxidizing beta-carotene through electrocatalytic oxygen |
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| CN201910762538.9A CN110372555B (en) | 2019-08-19 | 2019-08-19 | Method for preparing canthaxanthin by oxidizing beta-carotene through electrocatalytic oxygen |
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| CN111302925A (en) * | 2020-03-16 | 2020-06-19 | 万华化学集团股份有限公司 | Method for preparing cyclic α -unsaturated ketone |
| CN111423349A (en) * | 2020-04-02 | 2020-07-17 | 万华化学集团股份有限公司 | Synthetic method of canthaxanthin |
| CN113416968A (en) * | 2021-06-08 | 2021-09-21 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin by electrochemical catalysis without oxidant |
| CN115057805A (en) * | 2022-05-16 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin crystal with high all-trans isomer stability |
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| CN111302925A (en) * | 2020-03-16 | 2020-06-19 | 万华化学集团股份有限公司 | Method for preparing cyclic α -unsaturated ketone |
| CN111302925B (en) * | 2020-03-16 | 2023-05-30 | 万华化学集团股份有限公司 | Method for preparing cyclic alpha, beta-unsaturated ketone |
| CN111423349A (en) * | 2020-04-02 | 2020-07-17 | 万华化学集团股份有限公司 | Synthetic method of canthaxanthin |
| CN111423349B (en) * | 2020-04-02 | 2022-02-15 | 万华化学集团股份有限公司 | Synthetic method of canthaxanthin |
| CN113416968A (en) * | 2021-06-08 | 2021-09-21 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin by electrochemical catalysis without oxidant |
| CN113416968B (en) * | 2021-06-08 | 2022-11-08 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin by electrochemical catalysis without oxidant |
| CN115057805A (en) * | 2022-05-16 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin crystal with high all-trans isomer stability |
| CN115057805B (en) * | 2022-05-16 | 2024-10-18 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin crystals with high all-trans isomer stability |
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