CN114149301B - 一种氢化柠檬醛制备香茅醇的方法 - Google Patents
一种氢化柠檬醛制备香茅醇的方法 Download PDFInfo
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- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 title claims abstract description 42
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229940043350 citral Drugs 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 23
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 title claims abstract description 22
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 235000000484 citronellol Nutrition 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000008139 complexing agent Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000007868 Raney catalyst Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- -1 aluminum ions Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DGGBNSXAFVNQJU-SECBINFHSA-N (3r)-3,7-dimethyloctanoic acid Chemical compound CC(C)CCC[C@@H](C)CC(O)=O DGGBNSXAFVNQJU-SECBINFHSA-N 0.000 description 1
- VZUZJYDKCIVBDN-UHFFFAOYSA-N 5-(3,3-dimethyloxiran-2-yl)-3-methylpent-2-enal Chemical compound O=CC=C(C)CCC1OC1(C)C VZUZJYDKCIVBDN-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 125000000300 citronellol group Chemical group 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种氢化柠檬醛制备香茅醇的方法,该方法包含:提供柠檬醛原料,在催化剂的催化下对柠檬醛进行加氢,高选择性的得到香茅醇,通过控制柠檬醛原料中金属离子的质量含量为10ppm—100ppm之间,能够显著提高香茅醇的选择性,并且解决了随着催化剂套用次数增加催化剂寿命减短的问题。
Description
技术领域
本发明涉及氢化柠檬醛制备领域,具体涉及一种氢化柠檬醛制备香茅醇的方法。
背景技术
香茅醇是一种重要的香料原料,具有甜的花香气味,类似于玫瑰花的气味,常用于玫瑰香、柑橘香的香精,并可作为制造二氢香茅醇、羟基二氢香茅醛的原料。香茅醇也可用于食用香料,如软饮、烘烤食品、糖果、果冻布丁等,属于大宗香原料之一。
柠檬醛分子中含有可加氢的孤立C=C双键、C=O键以及与羰基共轭的C=C双键,加氢后可能生成的产物比较复杂。随着催化剂和反应条件的不同,加氢反应可能发生在不同部位,随着反应时间的延长,过度加氢产物会随之增多。
专利文献CN1247182A,介绍了一种使用负载氧化铝上的钴活性催化剂气相催化氢化制备香茅醇的方法。该发明的优点在于可连续操作,常压反应、设备投资少。该方法的问题在于转化率与选择性较低(最高为93%),原料柠檬醛与产品香茅醇沸点相近而使难以精馏分离得到香茅醇。
专利US4029709介绍了一种由柠檬醛或者香茅醛选择性氢化获取香茅醇的方法。该方法选择一种使用铬离子改性的雷尼镍催化剂作为反应催化剂,选择一种或数种饱和低级醇作为反应溶剂。该方法所提及的直接选择性最高92%。该方法使用的催化剂不涉及贵金属离子,催化剂成本也相对低廉。
CN102295531A通过对催化剂的改进,提高反应转化率和反应选择性,然而该效果的实现依赖于特定的催化剂种类,普通催化剂不能达到相当的效果,且反应的选择性有待于进一步的提高。
上述专利中都无法避免过度加氢产物的生成,并且对于随着催化剂套用次数增加催化剂寿命减短的问题,也没有得到解决,严重影响产品收率和生产效率。
发明内容
金属离子钠、钾、铬、锰和镍来自于不锈钢等金属材质,无法去除,通过增加或减少金属离子的含量来控制原料指标,本发明的发明人惊讶地发现通过控制制备香茅醇的原料柠檬醛中金属离子的含量,能够显著提高香茅醇的选择性,并且解决了随着催化剂套用次数增加催化剂寿命减短的问题。
为了实现以上发明目的,本发明采用的技术方案如下:
一种氢化柠檬醛制备的香茅醇的方法,包括以下步骤:
提供柠檬醛原料,在催化剂的催化下对柠檬醛进行加氢,高选择性的得到香茅醇,所述柠檬醛原料中金属离子的质量含量为10ppm—100ppm之间,所述金属离子为钠、钾、铬、锰和镍离子。
在进行加氢之前,获取柠檬醛原料中金属离子的含量,并通过添加金属离子化合物或加入络合剂从而调整金属离子的含量为10ppm—100ppm,优选30—80ppm,当柠檬醛原料中金属离子化合物的含量在上述范围时,能够显著提高香茅醇的选择性以及催化剂的使用寿命。
优选地,金属离子的含量可以基于催化剂的转化数(TON)确定,当需要提高催化剂的转化数时,可降低金属离子的含量,如将金属离子的含量控制在10ppm-50ppm,当需要降低四氢香叶醇含量时,可提高金属离子的含量,如将金属离子的含量控制在50ppm-100ppm之间。
在一个具体的实施方案中,获取柠檬醛原料中金属离子钠、钾、铬、锰、镍的含量,当其含量小于10ppm时,向柠檬醛原料中添加金属离子化合物以提高金属离子的含量至10ppm-100ppm之间。
所述获取柠檬醛原料中金属离子的方法可以是现有技术中已知的方法,如电感耦合等离子体质谱法、流动注射分析法和电化学法等,优选电感耦合等离子质谱法。
所述金属离子化合物选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铬、硫酸铬、硝酸铬、氯化锰、硫酸锰、硝酸锰、氯化镍、硫酸镍、硝酸镍中的一种或多种,优选氯化钠、氯化钾、氯化铬、氯化锰、氯化镍。
所述金属离子化合物可以直接添加或者以溶液的形式计量添加。
在一个具体的实施方案中,获取柠檬醛原料中金属离子钠、钾、铬、锰、镍的含量,当其含量大于100ppm时,向柠檬醛原料中添加金属离子络合剂以减少金属离子的含量至10ppm-100ppm之间。
络合剂选自有机羧酸类络合剂、磷酸类络合剂中的一种或两种,具体选自乙二胺四乙酸、间苯二甲酸、三聚磷酸、磷酸二丁酯中的一种或多种。
所述加氢反应催化剂选自M2型金属合金固体催化剂、雷尼镍、雷尼钴、金属钌中的任一种;所述M2型金属合金固体催化剂由Co、Ni、Mo和Al四种金属依次经融合、冷却和粉碎,然后用煮沸的碱水溶液溶去铝离子,最后用清水洗净形成遍布孔洞的骨架状固体。
金属元素的质量百分含量为:Al占30-60%,Ni占25-50%,Mo占0.1-10%,Co占0.1-30%。
基于柠檬醛的质量,所述催化剂的用量为1wt%至2wt%,优选M2型金属合金固体催化剂的用量为1wt%至2wt%。
加氢反应的反应器选自釜式反应器、固定床反应器和流化床反应器中的一种,优选釜式反应器,加氢反应的反应压力为绝压1-8MPa,优选为2-5MPa;反应温度为20-80℃,优选为50-80℃,加氢反应的反应时间为2-24h,优选4-12h
加氢反应可以在无溶剂或溶剂存在下进行,加氢反应的溶剂没有限制,包括但不限于甲醇、乙醇、异丙醇、甲苯、正己烷。
本发明提供的技术方案具有如下有益效果:
氢化柠檬醛制备香茅醇,反应迅速,很容易产生过度加氢产物,本发明利用金属离子对催化活性的毒化作用,通过控制柠檬醛原料中金属离子的含量,避免金属离子对催化剂活性有累积的毒化、提高催化剂寿命,调节催化剂活性减少过度加氢产生,提高选择性,是一种高效、易于实现工业化制备香茅醇的方法。
具体实施方式
下面的实施例将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
原料:
柠檬醛99%购自BASF
氯化钠99.5wt%阿拉丁试剂有限公司;
磷酸二丁酯97wt%阿拉丁试剂有限公司;
钴粉 99.9wt%,阿拉丁试剂有限公司;
镍粉 99.5wt%,阿拉丁试剂有限公司;
钼粉 99.9wt%,阿拉丁试剂有限公司;
铝粉 99.95wt%,阿拉丁试剂有限公司;
RANEY镍淤浆催化剂格雷斯贸易(上海)有限公司:(催化剂B);
钌碳催化剂钌5wt%上海麦克林生化科技有限公司;(催化剂C)。
分析方法:
钠、钾、铬、锰、镍离子含量通过ICP-OES分析测定,等离子体流量13L/min,辅助流量0.2L/min,雾化器流量0.8L/min,射频功率1300W,试样流量0.5ml/min;
仪器:Thermo Scientific ICAP 7200ICP-OES;
柠檬醛转化率和柠檬醛氧化物的含量使用气相色谱分析;
气相色谱仪:Agilent7820A,色谱柱HP-5(30m×320μm×0.25μm),进样口温度:150℃;分流比50:1;载气流量:1.5ml/min;升温程序:40℃保持1min,以10℃/min升温至90℃,保持0min,然后以5℃/min升温至160℃,保持0min,然后以30℃/min升温至280℃,保持6min。检测器温度:280℃。
反应选择性根据以下公式计算:
反应选择性=香茅醇产率/柠檬醛转化率*100%。
外购柠檬醛99%(样品0)金属离子含量的确定
经ICP-OES检测钠、钾、铬、锰和镍离子含量为2ppm。
不同金属离子含量的柠檬醛原料的制备
向上述制备获取的柠檬醛中添加金属离子化合物并搅拌均匀以获取不同金属离子含量的柠檬醛原料样品A、样品B、样品C和样品D,向样品B中添加络合剂乙二胺四乙酸以降低柠檬醛中的金属离子含量,试验结果如下。
M2型金属合金固体催化剂(催化剂A)制备例
将金属钴、镍、钼、铝分别按照25%、30%、5%、40%的质量比例进行高温融合,将合金冷却至室温,粉碎,筛选50-400目的合金颗粒。配置20%浓度的氢氧化钠溶液500g,煮沸,缓慢加入合金颗粒100g,继续煮沸4小时,冷却。倾倒灰色的上层浊液,加入清水常温下反复洗涤3次,待静置后液层清晰透明,pH值小于10即可。制备好的M2型催化剂经ICP检测钴含量为31%,镍含量为37%,保存在水封液面之下,备用。
实施例
取一定量的催化剂与柠檬醛转移至高压釜中,使用氮气置换釜内气体三次后,使用氢气置换釜内氮气,调节氢气压力为3MPaA后开启搅拌,升温至50℃反应5小时,使用气相色谱测得柠檬醛转化率,过滤去除催化剂后得到香茅醇产品。
由以上实施例和对比例可以看出,当控制柠檬醛原料中的金属离子含量在10ppm—100ppm范围时,能够调节催化剂活性减少过度加氢产生,提高选择性。
催化剂套用实例
重复实施例2、实施例4、对比例1和对比例2的条件,过滤回收催化剂进行套用,反应结果如下:
由以上实施例和对比例可以看出,通过控制柠檬醛原料中金属离子的含量,避免金属离子对催化剂活性有累积的毒化、提高催化剂寿命。
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应被认为是对本发明的限制。本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (8)
1.一种氢化柠檬醛制备香茅醇的方法,其特征在于,包含如下步骤:提供柠檬醛原料,在催化剂的催化下对柠檬醛进行加氢,选择性的得到香茅醇,所述柠檬醛原料中金属离子的含量为10ppm—100ppm之间,所述金属离子为钠、钾、铬、锰和镍离子,所述催化剂选自M2型金属合金固体催化剂、雷尼镍、金属钌中的任一种,所述M2型金属合金固体催化剂由Co、Ni、Mo和Al四种金属依次经融合、冷却和粉碎,然后用煮沸的碱水溶液溶去铝离子,最后用清水洗净形成具有孔洞的骨架状固体。
2.如权利要求1所述的方法,其特征在于,在进行加氢之前,获取柠檬醛原料中金属离子的含量,并通过添加金属离子化合物或络合剂调整柠檬醛原料中金属离子的含量为10ppm—100ppm。
3.如权利要求2所述的方法,其特征在于,所述金属离子化合物选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铬、硫酸铬、硝酸铬、氯化锰、硫酸锰、硝酸锰、氯化镍、硫酸镍、硝酸镍中的一种或多种。
4.如权利要求2-3任一项所述的方法,其特征在于,所述络合剂选自有机羧酸类络合剂、磷酸类络合剂中的一种或两种。
5.如权利要求4所述的方法,其特征在于,所述络合剂具体选自乙二胺四乙酸、间苯二甲酸、三聚磷酸、磷酸二丁酯中的一种或多种。
6.如权利要求1-3任一项所述的方法,其特征在于,以柠檬醛的质量为100%计,所述催化剂的用量为1wt%至2wt%。
7.如权利要求1-3任一项所述的方法,其特征在于,所述加氢反应的反应器选自釜式反应器、固定床反应器和流化床反应器中的一种;和/或,所述加氢反应的反应压力为绝压1-8MPa;和/或,所述加氢反应的反应温度为20-80℃,和/或,所述加氢反应的反应时间为2-24h。
8.如权利要求7所述的方法,其特征在于,所述加氢反应的反应器选自釜式反应器;和/或,所述加氢反应的反应压力为2-5MPa;和/或,所述加氢反应的反应温度为50-80℃,和/或,所述加氢反应的反应时间为4-12h。
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