CN102807481A - Method for preparing methyl ethyl ketone by oxidizing normal butane - Google Patents
Method for preparing methyl ethyl ketone by oxidizing normal butane Download PDFInfo
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- CN102807481A CN102807481A CN2012103018366A CN201210301836A CN102807481A CN 102807481 A CN102807481 A CN 102807481A CN 2012103018366 A CN2012103018366 A CN 2012103018366A CN 201210301836 A CN201210301836 A CN 201210301836A CN 102807481 A CN102807481 A CN 102807481A
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- Prior art keywords
- methylethylketone
- butane
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 184
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000001590 oxidative effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000001273 butane Substances 0.000 claims abstract description 36
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 36
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011651 chromium Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 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 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 239000011135 tin Substances 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims description 43
- 238000007254 oxidation reaction Methods 0.000 claims description 43
- 235000013844 butane Nutrition 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000005838 radical anions Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000001282 iso-butane Substances 0.000 abstract 1
- 235000013847 iso-butane Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 230000009466 transformation Effects 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000000644 6-membered heterocyclic compounds Chemical class 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- WQRUARPAYKIKTP-UHFFFAOYSA-N hydrogen peroxide;2-methylpropylbenzene Chemical compound OO.CC(C)CC1=CC=CC=C1 WQRUARPAYKIKTP-UHFFFAOYSA-N 0.000 description 2
- -1 iso-butylene sulfuric acid Chemical compound 0.000 description 2
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- MNVUINJQZPTVFG-UHFFFAOYSA-N [Cr].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cr].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 MNVUINJQZPTVFG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 210000004124 hock Anatomy 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing methyl ethyl ketone by oxidizing normal butane. The method comprises the following steps of using normal butane or mixed butane prepared by normal butane and iso-butane and an oxygen source as reaction raw materials; and under the catalytic action of a catalyst, liquid phase is selectively catalyzed and oxidized to prepare the methyl ethyl ketone. The reaction temperature is 80-160 DEG C, the reaction pressure is 1.1-6.5MPa, the oxygen partial pressure is 0.05-1.0 MPa, and the response time is 1-10 hours. The catalyst is mononuclear metal phthalocyanine, polynuclear metal phthalocyanine or a mixture of the mononuclear metal phthalocyanine and the polynuclear metal phthalocyanine, and active center metal is one or several of aluminum, titanium, chromium, manganese, ferrum, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin and platinum. Compared with the prior art for preparing the methyl ethyl ketone, the method has the advantages of cheap raw materials, easiness in getting the raw materials, mild reaction condition, high selectivity of the methyl ethyl ketone, less pollution and low production cost.
Description
Technical field
The present invention relates to the method that a kind of n butane oxidation prepares methylethylketone.
Background technology
Normal butane or mixed butanes are mainly derived from the CCU of petrochemical enterprise or the by product of ethylene producing device, are the staples of " LPG liquefied petroleum gas ", are mainly used in industry or domestic gas at present.
Methylethylketone is claimed methyl ethyl ketone or butanone again; It is a kind of low boiling point organic solvent of excellent property; Be widely used in industries such as oil refining, fuel, coating, tackiness agent, pharmaceutical grade lubricating oil dewaxing, electronic component cleaning, also can be used for natural plant pharmaceutical extraction and azeotropic distillation etc.In addition, methylethylketone still is a kind of important fine chemical material, can be used for preparing inhibitor, catalyst intermediate, urethane, vinyl resin etc.
Methylethylketone is since realizing industriallization through indirect hydration method the sixties; Output every year is all with 5 ~ 10% speed increment; Be main with the U.S., West Europe, Japan at present; World's aggregated capacity reaches more than 1,000,000 t/a at present, and along with alkyls and side chain ketones solvent are limited to use gradually, the production of straight chain ketone attains full development.It is reported that what the methylethylketone production status was the most stable at present is Japan, China's methylethylketone throughput and output all lag behind other countries.
Methylethylketone is with a wide range of applications, and main production methods has four kinds at present: sec-butyl alcohol dehydrogenizing method (hydration method), butane liquid phase non-catalytic oxidation method, butylene liquid phase oxidation, Isobuytel Benzene method.Sec-butyl alcohol dehydrogenizing has gas-phase dehydrogenation and two kinds of methods of dehydrogenation in liquid phase, and gas-phase dehydrogenation is made catalyzer with platina or zinc oxide, 400～500 ℃ of temperature; Normal pressure; Dehydrogenation in liquid phase is made catalyzer with Raney Ni (Raney nickel) or copper chromite, 150 ℃ of temperature, and dehydrogenation in liquid phase temperature of reaction and energy consumption are lower; Productive rate is higher, and catalyst life is long.But the raw material sources of sec-butyl alcohol dehydrogenizing method are in n-butene direct hydration or the indirect hydration of iso-butylene sulfuric acid, and not only raw material sources are well sold and in short supply, and hydration reaction answers per pass conversion low, and energy consumption is huge.The principal product of butane liquid phase non-catalytic oxidation is an acetate; Methylethylketone only accounts for 16% of yield of acetic acid as the output of by product, and temperature of reaction is up to 150～225 ℃, and pressure is up to 4.0～8.0MPa; Equipment corrosion is serious, and separation system is complicated, investment is high, energy consumption is big.The butylene liquid phase oxidation is in recent years by the method for broad research, development, is catalyzer with Palladous chloride/Cupric Chloride Solution, under 90～120 ℃, 1.0～2.0MPa condition, reacts; The transformation efficiency of n-butene is about 95%, and the methylethylketone yield is about 88%, and this method technological process is simple; But equipment corrosion is serious; Need to make catalyzer and catalyst life weak point with precious metal, raw material butylene source is limited, therefore is not applied to scale operation as yet.The Isobuytel Benzene method also is the method for studying, developing, and n-butene and benzene are that catalyzer gets isobutyl-benzene 50～70 ℃ of following hydrocarbonylations with the aluminum chloride, and isobutyl-benzene is under 110～130 ℃, 0.1～0.49MPa pressure; Generate the isobutyl-benzene hydrogen peroxide and decomposition in the presence of acid catalyst through liquid-phase oxidation; Generate methylethylketone and phenol, last separation and purification and finished product, these method characteristics are that the processing unit corrosion is lighter; Reaction conditions is gentle; But reaction scheme is longer, and relates to you and the decomposition proposed of isobutyl-benzene hydrogen peroxide, has certain potential safety hazard.
Chinese patent CN 1290681A, CN 1747922A etc. disclose the method for preparing phenol, acetone and methylethylketone through the mixture of oxidation isopropyl benzene and sec.-butylbenzene and hydroperoxide Hock scission reaction subsequently, and the composition that can control product through the ratio of adjusting two kinds of raw materials distributes.Chinese patent CN 101006033A, CN 101384526A, CN 101384533A etc. disclose benzene and the alkylation under zeolite or sieve catalyst effect of C4 alkene produces sec.-butylbenzene; Then sec-butylbenzene oxidation is produced hydroperoxidation and make it to decompose the method that produces phenol and methylethylketone, production process is similar with the Isobuytel Benzene method.Chinese patent CN 101293817A, CN 101580462A, CN 102351672A etc. disclose 2, and the 3-butyleneglycol dewaters under zeolite or molecular sieve or organic sulfonic acid catalysis and prepares the method for methylethylketone, and the selectivity of transformation efficiency and methylethylketone is higher.The described method for preparing methylethylketone of above patent has obtained certain effect, but in various degree have deficiencies such as technical process is long, temperature of reaction is high, raw material sources are limited.
U.S. Pat 3196182, US 3282994, US 3646128 etc. disclose the method that normal butane liquid phase non-catalytic oxidation prepares methylethylketone and acetate; Through changing form or the operating method and the condition of oxidation reactor, oxidation products is increased to the selectivity of methylethylketone.U.S. Pat 3904675 discloses normal butane in the presence of molecular oxygen, small amounts of aldehyde and solvent, and the liquid phase non-catalytic oxidation prepares the method for methylethylketone, acetate and ETHYLE ACETATE, and raw material availability and production efficiency increase.Above-mentionedly change the method that near normal butane non-catalytic oxidation prepares methylethylketone and obtained certain effect, but reaction needs carries out under HTHP, the selectivity of methylethylketone is lower.
U.S. Pat 4970348 discloses normal butane is prepared methylethylketone by molecular oxygen oxidation under the catalysis of halo chromium porphyrin method, and 100 ~ 170 ℃ of temperature of reaction, the selectivity of methylethylketone are more than 65%, but the transformation efficiency of normal butane generally is lower than 5%.
Know that at present there is the deficiency that the hydration reaction transformation efficiency is low, energy consumption is big in n-butylene hydration system sec-butyl alcohol through the process method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone again, not only raw material sources are limited, and production cost is high.Butane liquid phase non-catalytic oxidation method primary product is an acetate, and the selectivity of methylethylketone is low, and reaction needed is carried out complex process under HTHP.Butylene liquid phase oxidation and Isobuytel Benzene method also are in research, the development, and have catalyst life weak point, operational path length and certain potential safety hazard.It is higher that the normal butane liquid phase oxidation of catalysis of metalloporphyrin prepares the methylethylketone selectivity, but the normal butane per pass conversion is lower, and metalloporphyrin class Preparation of catalysts cost is high, is not suitable for industrial application.
Summary of the invention
The variety of issue that exists in the technology to existing preparation methylethylketone, the present invention provides a kind of n butane oxidation to prepare the method for methylethylketone.
Its technical solution is:
A kind of n butane oxidation prepares the method for methylethylketone; It is that mixed butanes and the oxygen source formed with normal butane or normal butane and Trimethylmethane are reaction raw materials, and under the katalysis of catalyzer, the liquid phase selective catalytic oxidation prepares methylethylketone; Temperature of reaction is 80 ~ 160 ℃; Reaction pressure is 1.1 ~ 6.5MPa, and oxygen partial pressure is 0.05 ~ 1.0MPa, and the reaction times is 1 ~ 10h; Said catalyzer is monokaryon metal phthalocyanine or multi-nuclear metal phthalocyanine shown in the logical formula II or their mixture shown in the logical formula I, and in logical formula I and the logical formula II, M is the metal as the active site; X is peripheral substituting group; Y is non-peripheral substituting group; L is an axial ligand; In the logical formula II, n is the integer more than or equal to 0, when n >=1, and i=2,3 ... (n+1);
N=0 or 1 situation, i.e. binuclear metallo phthalocyanine or three nuclear metal phthalocyanines in the above-mentioned catalyzer preferred formula (II).
In the above-mentioned logical formula I, M is a kind of in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, the platinum; In the above-mentioned logical formula II, M
1... M
i... M
N+2Be respectively a kind of in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, the platinum.
In above-mentioned logical formula I and the logical formula II; X, Y are respectively one or both in hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amino, sulfonic group or the carboxyl; Be that two substituent X on the phenyl ring can be the same or different; Two substituent X as on the phenyl ring can be H, this moment X=H, H; Can a substituent X be H also, another substituent X be alkoxyl group (X=H, OCH
3) etc., two substituting group Y on the same phenyl ring can be identical, also can be different.
In the above-mentioned logical formula I, the axial coordination group L
1, L
2Be respectively a kind of in oxygen, halogen, hydroxyl, methyl ethyl diketone, other acid radical anions and five yuan in imidazoles, pyridine, thiophene or furans etc. or the 6-membered heterocyclic compound, perhaps for not having; Axial coordinating group in the above-mentioned logical formula II, L
1, L
2... L
(2i-1), L
2i... L
(2n+3), L
(2n+4)Be respectively a kind of in oxygen, halogen, hydroxyl, methyl ethyl diketone, other acid radical anions and five yuan in imidazoles, pyridine, thiophene or furans etc. or the 6-membered heterocyclic compound, perhaps for not having.
Above-mentioned catalyst levels is 0.003～15% of a normal butane quality, and the preferred catalyst consumption is 0.005 ~ 2% of a normal butane quality.
Preferred 100～135 ℃ of above-mentioned temperature of reaction, the preferred 2.0 ~ 4.0MPa of reaction pressure, the preferred 0.1 ~ 0.5Mpa of oxygen partial pressure, preferred 5 ~ 7h of reaction times.
The massfraction of Trimethylmethane is preferably 2%～60% in the above-mentioned mixed butanes.
The volume(tric)fraction of oxygen is 10%～100% in the above-mentioned oxygen source, can be a kind of in oxygen-denuded air, air, oxygen-rich air or the pure oxygen like oxygen source, and the volume(tric)fraction of oxygen is 80%～100% in the preferred oxygen source.
The contriver finds that in research process metal phthalocyanine class material can quicken the n butane oxidation speed of reaction, reduce the temperature required and pressure of reaction, and significantly improves the selectivity of methylethylketone.On the one hand; The center reactive metal of metal phthalocyanine catalyst can activate molecular oxygen; Thereby the reaction of acceleration molecular oxygen and substrate normal butane; On the other hand, metal phthalocyanine catalyst can significantly promote the decomposition of intermediate product hydroperoxide, decomposes the selectivity that the radical that produces has increased speed of response and improved methylethylketone.The contriver also finds in research process, in normal butane, adds a spot of Trimethylmethane, can significantly improve the oxidizing reaction rate of normal butane.
In sum, than the technology of existing preparation methylethylketone, present method is when guaranteeing that n-butane conversion is high, and the selectivity of methylethylketone can reach more than 90% in the resulting oxidation products; And the low in raw material cost that the present invention adopts is easy to get, and catalyst activity is high, consumption is few, be easy to the oxidation products solid-liquid separation, be convenient to reclaim, and preparation easily, and cost is low; Reaction conditions of the present invention in addition is gentle, need not use other solvents in the reaction process, pollutes less, production cost is low.
Embodiment
Through specific embodiment the present invention is further described below, but does not therefore limit protection scope of the present invention.
Embodiment 1
In the 250ml autoclave, add the metal phthalocyanine that 8.6mg has logical formula I structure, X=Y=H wherein, H, M=Cr, L
1=Cl, L
2=not having, the 50.2g normal butane is at 120 ℃ of oxygen that continue to feed 3.0MPa down; Stirring reaction 6h postcooling; Slowly emit unreacted normal butane and remaining oxygen, obtain product liquid 4.3g, the transformation efficiency that normal butane is measured in gas chromatographic analysis is 6.4%; The selectivity of methylethylketone is 95.9%, and main by product is an acetate.
Embodiment 2
In the 250ml autoclave, add the metal phthalocyanine that 8.6mg has logical formula I structure, X=Y=H wherein, H, M=Cr, L
1=Cl, L
2=there are not 45.1g normal butane, 5.1g Trimethylmethane; At 120 ℃ of oxygen that continue to feed 3.0MPa down, stirring reaction 6h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 7.1g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 8.3%, and the selectivity of methylethylketone is 92.1% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol, methyl alcohol, acetone etc.
Embodiment 3
In the 250ml autoclave, add the metal phthalocyanine that 5.9mg has logical formula II structure, X=Y=H wherein, H, n=0, M
1=Co, M
2=Cu, L
1~ L
4=not having, the 49.9g normal butane is at 130 ℃ of oxygen that continue to feed 3.5MPa down; Stirring reaction 5h postcooling; Slowly emit unreacted normal butane and remaining oxygen, obtain product liquid 6.1g, the transformation efficiency that normal butane is measured in gas chromatographic analysis is 9.1%; The selectivity of methylethylketone is 93.7%, and main by product is acetate, ETHYLE ACETATE etc.
Embodiment 4
In the 250ml autoclave, add the metal phthalocyanine that 5.9mg has logical formula II structure, X=Y=H wherein, H, n=0, M
1=Fe, M
2=Cr, L
1=L
3=Cl, L
2=L
4=there are not 47.8g normal butane, 2.5g Trimethylmethane; At 100 ℃ of oxygen that continue to feed 2.6MPa down, stirring reaction 10h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 1.7g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 2.2%, and the selectivity of methylethylketone is 92.7% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol etc.
Embodiment 5
In the 250ml autoclave, add the metal phthalocyanine that 16.4mg has logical formula II structure, wherein X=OCH
3, H, Y=H, H, n=0, M
1=M
2=Cr, L
1~ L
4=there are not 42.9g normal butane, 7.6g Trimethylmethane; At 130 ℃ of air that continue to feed 4.0MPa down, stirring reaction 8h postcooling is slowly emitted unreacted butane and remaining air; Obtain product liquid 10.9g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 10.7%, and the selectivity of methylethylketone is 90.6% in the n butane oxidation product, and main by product is the trimethyl carbinol, acetate, methyl alcohol etc.
Embodiment 6
In the 250ml autoclave, add the metal phthalocyanine that 9.3mg has logical formula I structure, X=Y=H wherein, H, M=Co, L
1=L
2=there are not 47.7g normal butane, 2.5g Trimethylmethane; At 145 ℃ of oxygen that continue to feed 4.0MPa down, stirring reaction 2h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 7.6g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 9.7%, and the selectivity of methylethylketone is 91.4% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol, ETHYLE ACETATE, acetone, CO
2Deng.
Embodiment 7
In the 250ml autoclave, add the metal phthalocyanine that 14.6mg has logical formula I structure, X=Y=H wherein, H, M=Mo, L
1=O, L
2=there are not 48.1g normal butane, 2.6g Trimethylmethane; At 130 ℃ of oxygen that continue to feed 3.6MPa down, stirring reaction 6h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 3.1g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 3.9%, and the selectivity of methylethylketone is 93.2% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol etc.
Embodiment 8
In the 250ml autoclave, add the metal phthalocyanine that 11.3mg has logical formula II structure, X=Y=H wherein, H, n=3, M
1=M
2=M
3=M
4=M
5=Co, L
1~ L
10=there are not 50.9g normal butane, 4.3g Trimethylmethane; At 130 ℃ of oxygen that continue to feed 4.0MPa down, stirring reaction 5h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 15.3g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 18.4%, and the selectivity of methylethylketone is 91.2% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol etc.
Embodiment 9
In the 250ml autoclave, add the 0.05g imidazoles, 14.6mg has the metal phthalocyanine of logical formula I structure, wherein X=Y=H, M=Cr, L
1=imidazoles, L
2=there are not 48.3g normal butane, 2.6g Trimethylmethane; At 130 ℃ of oxygen that continue to feed 3.6MPa down, stirring reaction 6h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 8.9g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 11.1%, and the selectivity of methylethylketone is 93.7% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol etc.
Embodiment 10
In the 250ml autoclave, add the 0.05g imidazoles, 14.6mg has the metal phthalocyanine of logical formula I structure, X=Y=H wherein, H, M=Cr, L
1=imidazoles, L
2=there are not 48.3g normal butane, 2.6g Trimethylmethane; At 130 ℃ of oxygen that continue to feed 3.6MPa down, stirring reaction 6h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 8.9g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 11.1%, and the selectivity of methylethylketone is 93.7% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol etc.
Embodiment 11
In the 250ml autoclave, add the metal phthalocyanine that 12.7mg has logical formula II structure, X=Y=H wherein, H, n=1, M
1=M
2=M
3=Fe, L
1~ L
6=there are not 50.1g normal butane, 2.8g Trimethylmethane; At 135 ℃ of oxygen that continue to feed 4.1MPa down, stirring reaction 7h postcooling is slowly emitted unreacted butane and remaining oxygen; Obtain product liquid 17.8g; The transformation efficiency that normal butane is measured in gas chromatographic analysis is 21.4%, and the selectivity of methylethylketone is 92.9% in the n butane oxidation product, and main by product is acetate, the trimethyl carbinol etc.
Claims (9)
1. a n butane oxidation prepares the method for methylethylketone; It is characterized in that: mixed butanes and oxygen source with normal butane or normal butane and Trimethylmethane composition are reaction raw materials, and under the katalysis of catalyzer, the liquid phase selective catalytic oxidation prepares methylethylketone; Temperature of reaction is 80 ~ 160 ℃; Reaction pressure is 1.1 ~ 6.5MPa, and oxygen partial pressure is 0.05 ~ 1.0MPa, and the reaction times is 1 ~ 10h; Said catalyzer is monokaryon metal phthalocyanine or multi-nuclear metal phthalocyanine shown in the logical formula II or their mixture shown in the logical formula I, and in logical formula I and the logical formula II, M is the metal as the active site; X is peripheral substituting group; Y is non-peripheral substituting group; L is an axial ligand; In the logical formula II, n is the integer more than or equal to 0, when n >=1, and i=2,3 ... (n+1);
2. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone, it is characterized in that: in the logical formula I, M is a kind of in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, the platinum; In the logical formula II, M
1... M
i... M
N+2Be respectively a kind of in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, the platinum.
3. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone; It is characterized in that: in logical formula I and the logical formula II, X, Y are respectively one or both in hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amino, sulfonic group or the carboxyl.
4. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone, it is characterized in that: in the logical formula I, and L
1, L
2Be respectively a kind of in oxygen, halogen, hydroxyl, methyl ethyl diketone, acid radical anion, imidazoles, pyridine, thiophene or the furans, perhaps for not having; In the logical formula II, L
1, L
2... L
(2i-1), L
2i... L
(2n+3), L
(2n+4)Be respectively a kind of in oxygen, halogen, hydroxyl, methyl ethyl diketone, acid radical anion, imidazoles, pyridine, thiophene or the furans, perhaps for not having.
5. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone, it is characterized in that: said catalyst levels is 0.003 ~ 15% of a normal butane quality.
6. a kind of n butane oxidation according to claim 5 prepares the method for methylethylketone, it is characterized in that: said catalyst levels is 0.005 ~ 2% of a normal butane quality.
7. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone, it is characterized in that: said temperature of reaction is 100 ~ 135 ℃, and reaction pressure is 2.0 ~ 4.0MPa, and oxygen partial pressure is 0.1 ~ 0.5Mpa, and the reaction times is 5 ~ 7h.
8. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone, it is characterized in that: the massfraction of Trimethylmethane is 2%～60% in the said mixed butanes.
9. a kind of n butane oxidation according to claim 1 prepares the method for methylethylketone, it is characterized in that: the volume(tric)fraction of oxygen is 80%～100% in the said oxygen source.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709725A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst for production of ethyl methyl ketone, and preparation method and application thereof |
| CN115106115A (en) * | 2021-03-19 | 2022-09-27 | 中国石油大学(华东) | Method for preparing acetone from alkane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970348A (en) * | 1989-11-06 | 1990-11-13 | Sun Refining And Marketing Company | Chromium halogenated coordination complexes for the oxidation of butane to methylethylketone |
-
2012
- 2012-08-22 CN CN201210301836.6A patent/CN102807481B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970348A (en) * | 1989-11-06 | 1990-11-13 | Sun Refining And Marketing Company | Chromium halogenated coordination complexes for the oxidation of butane to methylethylketone |
Non-Patent Citations (2)
| Title |
|---|
| 李雪萍等: "金属酞菁催化苯乙烯液相氧化反应", 《石油化工高等学校学报》 * |
| 盖洪涛: "酞菁与分子氧对烷烃氧化反应的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709725A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst for production of ethyl methyl ketone, and preparation method and application thereof |
| CN105709725B (en) * | 2014-12-04 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of catalyst for producing methyl ethyl ketone and its preparation method and application |
| CN115106115A (en) * | 2021-03-19 | 2022-09-27 | 中国石油大学(华东) | Method for preparing acetone from alkane |
| CN115106115B (en) * | 2021-03-19 | 2023-11-03 | 中国石油大学(华东) | Method for preparing acetone from alkane |
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