CN1793099A - Process for preparing cyclohexone by catalyzing oxidating cyclohexol - Google Patents
Process for preparing cyclohexone by catalyzing oxidating cyclohexol Download PDFInfo
- Publication number
- CN1793099A CN1793099A CNA2005100623022A CN200510062302A CN1793099A CN 1793099 A CN1793099 A CN 1793099A CN A2005100623022 A CNA2005100623022 A CN A2005100623022A CN 200510062302 A CN200510062302 A CN 200510062302A CN 1793099 A CN1793099 A CN 1793099A
- Authority
- CN
- China
- Prior art keywords
- phosphorus molybdenum
- cyclohexol
- cyclohexone
- oxidating
- catalyzing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 63
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 6
- 239000011964 heteropoly acid Substances 0.000 claims description 61
- 229910052720 vanadium Inorganic materials 0.000 claims description 44
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 44
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 claims description 43
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- OTGFEQJKSRFOED-UHFFFAOYSA-N [P].[V].[Mo] Chemical group [P].[V].[Mo] OTGFEQJKSRFOED-UHFFFAOYSA-N 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- -1 ester compound Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 4
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical class [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UCAHIIZBPCASHX-UHFFFAOYSA-N CC[N+](CC)(CC)CC1=CC=CC=C1.N Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1.N UCAHIIZBPCASHX-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 3
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 59
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 230000009466 transformation Effects 0.000 description 15
- 229960004830 cetylpyridinium Drugs 0.000 description 13
- 238000010907 mechanical stirring Methods 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical class [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a method to make cyclohexanone by catalytic oxidation cyclohexanol that includes H<SUB>2</SUB>O<SUB>2</SUB> as oxidant. The catalyst is Q<SUB>3+x</SUB>PMo<SUB>12-x</SUB>V<SUB>x</SUB>O<SUB>40</SUB>, of which x=1-3, Q represents quaternary ammonium positive ion or MH<SUB>4</SUB><SUP>+</SUP>. The invention avoids using noble metal as catalyst, has low reaction temperature, low reaction powder consumption. The invention almost has no pollution, and has good economic and social benefits.
Description
(1) technical field
The present invention relates to a kind of preparation method of pimelinketone, particularly a kind of with H
2O
2Be oxygenant, the phosphorus molybdenum vanadium heteropolyacid ammonium salt is the method that catalyst oxidation hexalin prepares pimelinketone.
(2) background technology
Pimelinketone is a kind of important organic chemical industry, medical material, and its most important applications is the raw material hexanolactam of preparation nylon-6, the raw material hexanodioic acid of nylon-66.Prepare in the process of pimelinketone in hexalin oxydehydrogenation, traditional catalyst multiselect apparatus has inorganic and organic oxidizing agent such as chromium trioxides such as the heavy metal oxide, salt of oxidisability, potassium permanganate, potassium bichromate etc., though this type of oxygenant oxidisability is very strong, can the various substrates of oxidation, but catalyzer has intensive corrodibility and toxicity, can cause a series of problems such as equipment corrosion, product aftertreatment difficulty and environmental pollution, brought white elephant to enterprise, also brought certain influence to environment.Therefore, seeking high effective green environmentally friendly type oxide catalyst attracted attention by the people.Industrial for hexalin oxydehydrogenation part zinc calcium, magnesium copper, copper zinc and the copper silicon series catalysts of adopting more, cooperate precious metal such as palladium and/or platinum or its metal oxide to carry out dehydrogenation reaction together simultaneously, this type of catalyzer all need be under comparatively high temps (200-450 ℃) and certain pressure the various alcohols of gaseous oxidation, therefore higher to equipment requirements.Simultaneously,, need under higher temperature, to carry out if hexalin will obtain high per pass conversion, but because the temperature of reaction height, the selectivity of pimelinketone is relatively poor.Therefore to be target developing be main low temperature catalyst with copper to improve selectivity, and general temperature is at 220-350 ℃, but the per pass conversion of hexalin obviously reduces.Introduced the catalyzer of a kind of CuO of containing, ZnO, MgO, CaO and micro-Na among the Chinese patent CN 1056067A " multi component cyclohexanol dehydrogenation catalyst ", but in order to reach higher per pass conversion, have to adopt higher temperature of reaction, cause catalyst life to be affected.
Preparing the reaction process of pimelinketone from the hexalin oxydehydrogenation of existing report at present, mainly is under gas phase condition, at 1.0-3.5MPa, is that catalyzer carries out cyclohexanol dehydrogenation and prepares pimelinketone with the mixture of each quasi-metal oxides under 220-450 ℃; Simultaneously, because it is the reaction that volume increases that the hexalin gas-phase dehydrogenation prepares pimelinketone, adopt in (CN1207383A) at Chinese patent " improvement of cyclohexanol dehydrogenation method " and in dehydrogenation reactor, to add the not water vapour of chloride ion-containing continuously, to improve the per pass conversion of hexalin, but dividing potential drop reduction effect is limited, can not obviously increase the hexalin per pass conversion, and energy consumption increases.Therefore, this type of is reflected under the gas phase condition and carries out, and conversion unit is had relatively high expectations, and needs in time to reduce the pressure in the reactor.
In recent years, along with molecule " is cut out " technology rapid development, new catalytic material emerges in an endless stream, more and more cause people's attention with heteropolyacid and salt thereof as the catalyzer of oxidative dehydrogenation, come its catalytic performance of modulation by the molecular composition and the structure that change heteropolyacid, to satisfy specific catalytic process requirement.Phosphorus molybdenum vanadium heteropolyacid has been subjected to people's common concern as a kind of outstanding oxidation catalyst, think according to reversible electric charge transition criterion, the redox processes of vanadium is a reversibility single electron transfer process preferably, vanadium in the phosphorus molybdenum vanadium heteropolyacid is stronger than the oxidisability of molybdenum, therefore can improve the oxidation-reduction quality of catalyzer greatly.The refined ripples of well etc. are with the oxidation-reduction quality of cyclic voltammetry research phosphorus molybdenum vanadium heteropolyacid, the introducing that the result shows vanadium has a significant impact the redox peak position of molybdenum, reduced the oxidation-reduction quality [Jilin University's journal (version of science), 2003:41 (4), 534-537] of molybdenum.Simultaneously, in heteropolyacid, introduce the quaternary ammonium cation of macromolecule, can not only increase its stability, can improve its specific surface area simultaneously; Quaternary ammonium cation can also effectively shift Sauerstoffatom between water and organic phase, thereby makes oxidizing reaction effectively be carried out, and can improve the transformation efficiency of speed of reaction and substrate greatly.
(3) summary of the invention
Adopt in the existing pimelinketone technology of preparing for overcoming that to have intensive corrodibility and toxic metal oxide etc. be catalyzer, very easily cause a series of problems such as equipment corrosion, product aftertreatment difficulty and environmental pollution, the invention provides a kind of method of preparing cyclohexone by catalyzing oxidating cyclohexol, with H
2O
2Be oxygenant, the phosphorus molybdenum vanadium heteropolyacid ammonium salt is that catalyst oxidation hexalin prepares pimelinketone.
The method of preparing cyclohexone by catalyzing oxidating cyclohexol of the present invention comprises with H
2O
2Be oxygenant, preparing cyclohexone by catalyzing oxidating cyclohexol in organic solvent, described catalyzer are phosphorus molybdenum vanadium heteropolyacid ammonium salt Q
3+xPMo
12-xV
xO
40, x=1~3, Q represents quaternary ammonium cation or NH
4 +
It is one of following that described phosphorus molybdenum vanadium heteropolyacid ammonium salt can be selected from: phosphorus molybdenum one vanadium ammonium heteropoly acids, phosphorus molybdenum one vanadium heteropolyacid tetraethyl-ammonium salt, phosphorus molybdenum one vanadium heteropolyacid 4-butyl ammonium, phosphorus molybdenum one vanadium heteropolyacid benzyl triethyl ammonium ammonium salt, phosphorus molybdenum one vanadium heteropolyacid dodecyl trimethyl ammonium salt, phosphorus molybdenum one vanadium heteropolyacid cetyltrimethyl ammonium salt, phosphorus molybdenum one vanadium heteropolyacid malachite green salt, phosphorus molybdenum two vanadium heteropolyacid cetyl pyridinium salt, phosphorus molybdenum three vanadium heteropolyacid cetyl pyridinium salt, phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium salt is preferably phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium salt.
Described organic solvent can be selected from and be one of following or more than one arbitrary combination: (1) carbonatoms is the halohydrocarbon of 1-4; (2) carbonatoms is the ester compound of 1-7; (3) carbonatoms is the ketone compounds of 3-6; (4) carbonatoms is the ether compound of 2-6; (5) nitrogenous organic solvent is preferably the ketone compounds that carbonatoms is 3-6, is preferably acetone again.
Described catalytic oxidation temperature is generally 25~100 ℃, is preferably 60~80 ℃; Reaction times was generally 2~9 hours, was preferably 5~8 hours.
Described catalyst levels is generally 0.6~3.6wt% of hexalin quality, the H of employing
2O
2Concentration be generally 10~50%; Hexalin and H
2O
2The amount of substance ratio be generally 1: 1~6, be preferably 1: 1.5~5; Organic solvent is generally 0.5~2.5ml with respect to the consumption of every gram hexalin.
The method concrete steps of preparing cyclohexone by catalyzing oxidating cyclohexol provided by the present invention can be:
(1) is equipped with in the reactor of mechanical stirring, reflux exchanger etc. and adds hexalin, H
2O
2And organic solvent.
(2) heat temperature raising adds the agent of a certain amount of phosphorus molybdenum vanadium heteropolyacid ammonium salt in catalysis, stirring reaction again to certain temperature.
(3) after reaction reached setting-up time, catalyzer was removed in cooling, filtration, gets reaction solution.Reaction solution is through the vapor-phase chromatography separation determination.
Phosphorus molybdenum vanadium heteropolyacid ammonium salt in catalysis of the present invention agent can prepare according to following method:
Excessive inorganic ammonium salt or quaternary ammonium salt and phosphorus molybdenum vanadium heteropolyacid effect generate insoluble phosphorus molybdenum vanadium heteropolyacid ammonium salt, after filtration, washing, the drying, obtain phosphorus molybdenum vanadium heteropolyacid quaternary ammonium salt [Q
3+xPMo
12-xV
xO
40, x=1~3, Q represents quaternary ammonium cation or NH
4 +] catalyzer.
Described inorganic salt ammonium salt has: bicarbonate of ammonia, volatile salt, ammonium chloride, ammonium nitrate, ammonium acetate etc.
Described quaternary ammonium salt has: etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, cetyltriethylammonium bromide, bromohexadecane yl pyridines, benzyltriethylammoinium chloride, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, malachite green etc.
Described phosphorus molybdenum vanadium heteropolyacid has: H
4PMo
11VO
40, H
5PMo
10V
2O
40, H
6PMo
9V
3O
40
The present invention compares with the method that industrial cyclohexanol dehydrogenation prepares pimelinketone, and conversion unit requires lower, avoid using precious metal as promotor, and temperature of reaction is lower, and energy consumption of reaction is few.Use environmental type oxygenant H simultaneously
2O
2, the reaction back is H
2There is not " three wastes " pollution problem substantially in O, has certain practical value and tangible economical, societal benefits.
(4) embodiment
Below in conjunction with specific embodiment the present invention is further specified, but protection scope of the present invention is not limited to this.
Embodiment 1
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 6.8 gram (60mmol), 4.0ml acetone, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.1g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 47.6%, and the yield of pimelinketone is 100% (in the hexalin raw material of reaction).
Embodiment 2~5
Adopt the acetone consumption described in the different acetone consumption alternate embodiments 1, other condition is with embodiment 1, and its test-results is listed in table 1.
Table 1
The embodiment title | Solvent load (ml) | The transformation efficiency of hexalin (%) | The yield of pimelinketone (%) |
Embodiment 2 | 1.5 | 61.8 | 72.8 |
Embodiment 3 | 2.5 | 54.2 | 83.8 |
Embodiment 4 | 3.5 | 50.53 | 90.2 |
Embodiment 5 | 4.5 | 44.84 | 100 |
Embodiment 6
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), 2.5ml acetone, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.3g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 60.2%, and the yield of pimelinketone is 82.4% (in the hexalin raw material of reaction).
Embodiment 7
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), 2.5ml acetone, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.2g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 59.3%, and the yield of pimelinketone is 81.0% (in the hexalin raw material of reaction).
Embodiment 8
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 4.5 gram (40mmol), 3.5ml acetone, heat temperature raising to 70 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.1g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 25.9%, and the yield of pimelinketone is 100% (in the hexalin raw material of reaction).
Embodiment 9
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 4.5 gram (40mmol), 3.5ml acetone, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.1g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 8 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 54.5%, and the yield of pimelinketone is 95.6% (in the hexalin raw material of reaction).
Embodiment 10
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), 2.5ml acetone, heat temperature raising to 80 ℃ adds phosphorus one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 56.1%, and the yield of pimelinketone is 92.1% (in the hexalin raw material of reaction).
Embodiment 11
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), the 2.5ml butanone, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 71.2%, and the yield of pimelinketone is 56.7% (in the hexalin raw material of reaction).
Embodiment 12
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), the 2.5ml ethyl acetate, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 34.0%, and the yield of pimelinketone is 60.3% (in the hexalin raw material of reaction).
Embodiment 13
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), 2.5ml1, the 4-dioxane, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 62.3%, and the yield of pimelinketone is 45.3% (in the hexalin raw material of reaction).
Embodiment 14
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), 2.5ml N, dinethylformamide, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 49.3%, and the yield of pimelinketone is 57.5% (in the hexalin raw material of reaction).
Embodiment 15
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), 2.5ml1, the 2-ethylene dichloride, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 37.6%, and the yield of pimelinketone is 66.8% (in the hexalin raw material of reaction).
Embodiment 16
In the 50ml there-necked flask of mechanical stirring, reflux exchanger is housed, add hexalin 2 grams (20mmol), 30%H
2O
2Oxygenant 10 gram (88mmol), the 2.5ml acetonitrile, heat temperature raising to 80 ℃ adds phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C of 0.5g
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, stirring reaction 7 hours.Cool off, remove by filter catalyzer, reaction solution is through gas Chromatographic Determination, and the transformation efficiency of hexalin is 70.8%, and the yield of pimelinketone is 49.7% (in the hexalin raw material of reaction).
Embodiment 17~25
Adopt phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium the salt [(C in the various phosphorus molybdenum vanadium heteropolyacid quaternary ammonium salt catalyst alternate embodiments 7
16H
33C
5H
5N)
4PMo
11VO
40] catalyzer, other condition is with embodiment 7, and its test-results is listed in table 2.
Table 2
The embodiment title | Catalyzer | The transformation efficiency of hexalin, % | The yield of pimelinketone, % |
Embodiment 17 | Phosphorus molybdenum one vanadium ammonium heteropoly acids (NH 4) 4Mo 11VO 40 | 73.6 | 44.0 |
Embodiment 18 | Phosphorus molybdenum one vanadium heteropolyacid tetraethyl-ammonium salt (Et 4N) 4Mo 11VO 40 | 71.7 | 39.9 |
Embodiment 19 | Phosphorus molybdenum one vanadium heteropolyacid 4-butyl ammonium (Bu 4N) 4PMo 11VO 40 | 72.3 | 40.7 |
Embodiment 20 | Phosphorus molybdenum one vanadium heteropolyacid benzyl triethyl ammonium ammonium salt (C 6H 5CH 2(CH 3CH 2) 3N) 4PMo 11VO 40 | 68.1 | 33.5 |
Embodiment 21 | Phosphorus molybdenum one vanadium heteropolyacid dodecyl trimethyl ammonium salt (CH 3(CH 2) 11(CH 3) 3N) 4PMo 11VO 40 | 62.6 | 45.4 |
Embodiment 22 | Phosphorus molybdenum one vanadium heteropolyacid cetyltrimethyl ammonium salt (C 16H 33(CH 3) 3N) 4PMo 11VO 40 | 79.0 | 40.9 |
Embodiment 23 | Phosphorus molybdenum one vanadium heteropolyacid malachite green salt (C 23H 25N 2) 4PMo 11VO 40 | 67.8 | 32.7 |
Embodiment 24 | Phosphorus molybdenum two vanadium heteropolyacid cetyl pyridinium salt (C 16H 33C 5H 5N) 5PMo 10V 2O 40 | 62.5 | 64.0 |
Embodiment 25 | Phosphorus molybdenum three vanadium heteropolyacid cetyl pyridinium salt (C 16H 33C 5H 5N) 6PMo 9V 3O 40 | 63.7 | 57.9 |
Annotate: yield is in the hexalin raw material of reaction.
Claims (10)
1, a kind of method of preparing cyclohexone by catalyzing oxidating cyclohexol comprises with H
2O
2Be oxygenant, hexalin catalyzed oxidation in organic solvent prepares pimelinketone, it is characterized in that described catalyzer is phosphorus molybdenum vanadium heteropolyacid ammonium salt Q
3+xPMo
12-xV
xO
40, x=1~3, Q represents quaternary ammonium cation or NH
4 +
2, the method of preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 1 is characterized in that described phosphorus molybdenum vanadium heteropolyacid ammonium salt is one of following: phosphorus molybdenum one vanadium ammonium heteropoly acids, phosphorus molybdenum one vanadium heteropolyacid tetraethyl-ammonium salt, phosphorus molybdenum one vanadium heteropolyacid 4-butyl ammonium, phosphorus molybdenum one vanadium heteropolyacid benzyl triethyl ammonium ammonium salt, phosphorus molybdenum one vanadium heteropolyacid dodecyl trimethyl ammonium salt, phosphorus molybdenum one vanadium heteropolyacid cetyltrimethyl ammonium salt, phosphorus molybdenum one vanadium heteropolyacid malachite green salt, phosphorus molybdenum two vanadium heteropolyacid cetyl pyridinium salt, phosphorus molybdenum three vanadium heteropolyacid cetyl pyridinium salt, phosphorus molybdenum one vanadium heteropolyacid cetyl pyridinium salt.
3, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 2 is characterized in that described phosphorus molybdenum vanadium heteropolyacid ammonium salt is phosphorus molybdenum one a vanadium heteropolyacid cetyl pyridinium salt.
4, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 1, it is characterized in that described organic solvent is one of following or more than one arbitrary combination: (1) carbonatoms is the halohydrocarbon of 1-4; (2) carbonatoms is the ester compound of 1-7; (3) carbonatoms is the ketone compounds of 3-6; (4) carbonatoms is the ether compound of 2-6; (5) nitrogenous organic solvent.
5, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 4 is characterized in that described organic solvent is that carbonatoms is the ketone compounds of 3-6.
6, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 5 is characterized in that described organic solvent is an acetone.
7, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 1 is characterized in that described catalytic oxidation temperature is 25~100 ℃, and the reaction times is 2~9 hours.
8, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 7 is characterized in that described catalytic oxidation temperature is 60~80 ℃, and the reaction times is 5~8 hours.
9,, it is characterized in that described catalyst levels is 0.6~3.6wt% of hexalin quality, the H of employing as the method for the described preparing cyclohexone by catalyzing oxidating cyclohexol of one of claim 1~8
2O
2Concentration be 10~50%, described hexalin and H
2O
2The amount of substance ratio be 1: 1~6, organic solvent is 0.5~2.5ml with respect to the consumption of every gram hexalin.
10, the method for preparing cyclohexone by catalyzing oxidating cyclohexol as claimed in claim 9 is characterized in that described hexalin and H
2O
2The amount of substance ratio be 1: 1.5~5.
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