CN104072343A - Method for preparing o-alkoxyphenol from epoxy cyclohexane - Google Patents
Method for preparing o-alkoxyphenol from epoxy cyclohexane Download PDFInfo
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- CN104072343A CN104072343A CN201310104549.0A CN201310104549A CN104072343A CN 104072343 A CN104072343 A CN 104072343A CN 201310104549 A CN201310104549 A CN 201310104549A CN 104072343 A CN104072343 A CN 104072343A
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- Prior art keywords
- hexalin
- alcohol
- dehydrogenation
- epoxy cyclohexane
- alcoholysis
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- 238000000034 method Methods 0.000 title claims abstract description 33
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XUKSWKGOQKREON-UHFFFAOYSA-N 1,4-diacetoxybutane Chemical class CC(=O)OCCCCOC(C)=O XUKSWKGOQKREON-UHFFFAOYSA-N 0.000 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims description 3
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 3
- XHEDLZYGAQSNTR-UHFFFAOYSA-N ethene;hexanedioic acid Chemical compound C=C.C=C.OC(=O)CCCCC(O)=O XHEDLZYGAQSNTR-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- -1 alkaline earth metal sulphate Chemical class 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- 235000011151 potassium sulphates Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical class OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 0 *OC1C=CC=CC1O Chemical compound *OC1C=CC=CC1O 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing o-alkoxyphenol from epoxy cyclohexane. The method comprises the following steps: (1) under an alcoholysis condition, contacting epoxy cyclohexane and alcohol with a catalyst, and separating so as to obtain o-alkoxyphenol; (2) under a catalytic dehydrogenation condition, contacting the o-alkoxyphenol with a dehydrogenation catalyst, whose active component comprises the VIII group metal elements. The method can synthesize o-alkoxyphenol directly from epoxy cyclohexane, and furthermore has the advantages of simple process and high efficiency.
Description
Technical field
The present invention relates to a kind of method of being prepared O--Alkoxy phenols by epoxy cyclohexane.
Background technology
The derivative of cyclohexanediol is numerous, wherein, is much important chemical intermediate.Derivative by cyclohexanediol is the important reaction of a class as the derivative of the synthetic diphenol of bridge dehydrogenation, the derivative of existing method synthesizing cyclohexane 1 glycol normally be take pyrocatechol and is synthesized as raw material, and the condition of such reaction is harsh, and side reaction is many, and poor selectivity, yield are not high.The method of dehydrogenating of derivative that particularly contains the cyclohexanediol of ehter bond, has no report.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of method of being prepared O--Alkoxy phenols by epoxy cyclohexane.
The present inventor finds in research process, adopts the Cyclohexanediole derivatives dehydrogenation that dehydrogenation catalyst that active ingredient contains group VIII metal element can catalysis contains ehter bond to obtain corresponding aromatics, and selectivity and transformation efficiency all higher.Based on above-mentioned discovery, completed the present invention.
For achieving the above object, the invention provides a kind of method of being prepared O--Alkoxy phenols by epoxy cyclohexane, the method comprises:
(1) under alcoholysis conditions, epoxy cyclohexane is contacted with alcoholysis catalysts with alcohol, separation obtains o-alkoxyl hexalin;
(2), under catalytic dehydrogenation condition, the dehydrogenation catalyst that o-alkoxyl hexalin and active ingredient are contained to group VIII metal element contacts.
Method of the present invention, can adopt epoxy cyclohexane to synthesize and obtain O--Alkoxy phenols, and method operation of the present invention is simple and efficient.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of method of being prepared O--Alkoxy phenols by epoxy cyclohexane, the method comprises: (1), under alcoholysis conditions, contacts with alcohol epoxy cyclohexane with alcoholysis catalysts, separation obtains o-alkoxyl hexalin; (2), under catalytic dehydrogenation condition, the dehydrogenation catalyst that o-alkoxyl hexalin and active ingredient are contained to group VIII metal element contacts.
In the present invention, optional a wider range of the kind of described alcohol, can all can be used for the present invention with the alcohol of epoxy cyclohexane generation alcoholysis, for the present invention, the alcohol that preferred described alcohol is C1-C12, the more preferably alcohol of C1-C6, more preferably methyl alcohol, ethanol, Virahol or hexalin.
In the present invention, o-alkoxyl hexalin has following structural formula:
the straight or branched alkyl that wherein R is C1-C12, is preferably the straight or branched alkyl of C1-C6;
In the present invention, O--Alkoxy phenols has following structural formula:
the straight or branched alkyl that wherein R is C1-C12, is preferably the straight or branched alkyl of C1-C6.
In the present invention, optional a wider range of the kind of described alcoholysis catalysts, the catalyzer that can be used in alcoholysis all can be used for the present invention, for the present invention, preferred described alcoholysis catalysts is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sulfuric acid, fluoroboric acid, Phenylsulfonic acid, sodium pyrosulfate, phosphoric acid, formic acid, acetic acid, Whitfield's ointment and resin cation (R.C.), and more preferably described alcoholysis catalysts is one or more in sodium pyrosulfate, phosphoric acid and fluoroboric acid.
In the present invention, described in step (1), alcoholysis conditions preferably includes: temperature is subzero 30 ℃ to 150 ℃ above freezing, and the mol ratio of epoxy cyclohexane and alcohol is 1:1-50, and the mass ratio of alcoholysis catalysts and epoxy cyclohexane is 0.002-0.1:1.
In the present invention, optional a wider range of the kind of the dehydrogenation catalyst that described in step (2), active ingredient contains group VIII metal element, the dehydrogenation catalyst that the active ingredient of prior art contains group VIII metal element all can be used for the present invention, for the present invention, preferred described group VIII metal element is nickel element, palladium element, platinum element, one or more in ruthenium element and rhodium element, therefore for the present invention, the dehydrogenation catalyst that contains group VIII metal element is preferably that nickel is dehydrogenation catalyst, palladium is dehydrogenation catalyst, platinum group dehydrogenation catalyst, ruthenium is that dehydrogenation catalyst and rhodium are one or more in dehydrogenation catalyst.
In the present invention, preferred described nickel is in dehydrogenation catalyst, and nickel content is 10-95 % by weight, and the content of auxiliary agent is 1-15 % by weight, and other is carrier.Wherein, described auxiliary agent is preferably one or more in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate, more preferably one or more in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard; Described carrier is preferably one or more in silicon-dioxide, aluminium sesquioxide, zirconium white and gac.
In the present invention, preferred described palladium is in dehydrogenation catalyst, and palladium content is 0.3-6 % by weight, and the content of auxiliary agent is 1-15 % by weight, and other is carrier.Wherein, described auxiliary agent is preferably one or more in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate, more preferably one or more in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard; Described carrier is preferably one or more in silicon-dioxide, aluminium sesquioxide, zirconium white and gac.
In the present invention, in preferred described platinum group dehydrogenation catalyst, platinum content is 0.3-6 % by weight, and the content of auxiliary agent is 1-15 % by weight, and other is carrier.Wherein, described auxiliary agent is preferably one or more in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate, more preferably one or more in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard; Described carrier is preferably one or more in silicon-dioxide, aluminium sesquioxide, zirconium white and gac.
In the present invention, preferred described ruthenium is in dehydrogenation catalyst, and ruthenium content is 0.3-10 % by weight, and the content of auxiliary agent is 1-15 % by weight, and other is carrier.Wherein, described auxiliary agent is preferably one or more in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate, more preferably one or more in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard; Described carrier is preferably one or more in silicon-dioxide, aluminium sesquioxide, zirconium white and gac.
In the present invention, preferred described rhodium is in dehydrogenation catalyst, and rhodium content is 0.3-10 % by weight, and the content of auxiliary agent is 1-15 % by weight, and other is carrier.Wherein, described auxiliary agent is preferably one or more in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate, more preferably one or more in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard; Described carrier is preferably one or more in silicon-dioxide, aluminium sesquioxide, zirconium white and gac.
In the present invention, the described catalytic dehydrogenation of step (2) can be carried out under solvent exists, optional a wider range of the consumption of described solvent, and for the present invention, the mass ratio of preferred solvent and o-alkoxyl hexalin is 0.1-100:1, is preferably 0.5-10:1.In the present invention, optional a wider range of the kind of described solvent, for example, can be one or more in alcohol, ester, nitrile, ketone and water; More preferably described solvent is one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, hexalin, butyleneglycol, octanol, ethyl acetate, glycol dicaproate, glycol diacetate, hexalin acetate, octyl phthalate, butyleneglycol diacetate esters, diethylene adipate, butyl phthalate, acetonitrile, adiponitrile, pimelinketone, acetone, isophorone and water.Further preferred described solvent is ester, is preferably one or more in ethyl acetate, glycol dicaproate, glycol diacetate, butyleneglycol diacetate esters, diethylene adipate and butyl phthalate.Adopt ester as solvent, can further improve according to the selectivity of the reaction-ure conversion-age of method of the present invention and target product.
In the present invention, optional a wider range of catalytic dehydrogenation condition described in step (2), specifically can determine according to actual reaction formation, for example, when the described catalytic dehydrogenation of step (2) is liquid-solid phase dehydrogenation reaction, the condition of preferred described catalytic dehydrogenation comprises: temperature is 170-380 ℃, is preferably 220-320 ℃; The mass concentration of catalyzer is 0.02-20%, be preferably 0.1-10%, the mass concentration of catalyzer can be selected according to the catalyzer of concrete use, for example, when using nickeliferous dehydrogenation catalyst, the large usage quantity of general catalyzer, the amount that refers to catalyzer for the mass concentration of catalyzer of the present invention accounts for the per-cent of the amount of liquid phase material, for example, when liquid phase material is only o-alkoxyl hexalin, the mass concentration of catalyzer refers to is the per-cent that the amount of catalyzer accounts for the amount of o-alkoxyl hexalin.And when liquid phase material contains solvent and o-alkoxyl hexalin simultaneously, the amount that the mass concentration of catalyzer refers to catalyzer accounts for the per-cent of the total amount of o-alkoxyl hexalin and solvent; The residence time is 0.5-100h, is preferably 2-20h.In the present invention, the residence time also refers to the catalytic time of dehydrogenation catalyst that o-alkoxyl hexalin and active ingredient contain group VIII metal element, the i.e. time of dehydrogenation.
And when described catalytic dehydrogenation is gas-solid phase dehydrogenation reaction, preferred described catalytic dehydrogenation condition comprises: temperature is 210-380 ℃, be preferably 240-320 ℃, mass space velocity is 0.02-4h
-1, be preferably 0.1-1h
-1.In the present invention, mass space velocity refers in the unit time amount of the reaction mass (for Cyclohexanediole derivatives and/or the solvent that contains ehter bond) by unit catalyzer.
In the present invention, optional a wider range of the pressure of the described catalytic dehydrogenation of step (2) generally can carry out under-0.095 to 10MPa pressure.
In the present invention, it is gaseous state that described gas-solid phase dehydrogenation reaction refers to reaction mass (comprising o-alkoxyl hexalin and/or solvent etc.), and catalyzer is solid-state catalytic dehydrogenating reaction.
In the present invention, it is gaseous state that described liquid-solid phase dehydrogenation reaction refers to reaction mass (comprising o-alkoxyl hexalin and/or solvent etc.), and catalyzer is solid-state catalytic dehydrogenating reaction.
Below will describe the present invention by embodiment, but the present invention is not limited to this.
In the present invention, adopt gas-chromatography to carry out each analysis forming in system, by proofreading and correct normalization method, undertaken quantitatively, all can carrying out with reference to prior art, calculate on this basis the evaluation indexes such as the transformation efficiency of reactant, the yield of product and selectivity.
In embodiments of the invention, catalyzer is according to the method for prior art synthetic.
In the present invention, the transformation efficiency calculation formula of o-alkoxyl hexalin is as follows:
The calculation formula of compositional selecting is as follows:
Wherein, X is transformation efficiency; S is selectivity; M is the quality of component; N is the amount of substance of component; M wherein
0and n
0represent respectively quality and molar weight before respective reaction.
Alcoholysis embodiment 1
Under alcoholysis conditions, epoxy cyclohexane is contacted with alcoholysis catalysts with methyl alcohol, separation obtains O-methoxy hexalin; Wherein, alcoholysis conditions comprises: temperature is 60 ℃, and the mass ratio of alcoholysis catalysts and epoxy cyclohexane is 0.05:1, and alcoholysis catalysts is sodium pyrosulfate, and the mol ratio of epoxy cyclohexane and methyl alcohol is 1:3; O-methoxy hexalin selectivity 96%, epoxy cyclohexane transformation efficiency 98.1%.
Alcoholysis embodiment 2
Under alcoholysis conditions, epoxy cyclohexane is contacted with alcoholysis catalysts with ethanol, separation obtains adjacent oxyethyl group hexalin; Wherein, alcoholysis conditions comprises: temperature is 80 ℃, and the mass ratio of alcoholysis catalysts and epoxy cyclohexane is 0.01:1, and alcoholysis catalysts is phosphoric acid, and the mol ratio of epoxy cyclohexane and ethanol is 1:20; Adjacent oxyethyl group hexalin selectivity 96%, epoxy cyclohexane transformation efficiency 99.3%.
Alcoholysis embodiment 3-6
According to the method for embodiment 1, prepare other o-alkoxyl hexalin, different is, the alcohol using is n-propyl alcohol, propyl carbinol, hexalin, n-Octanol, finally prepares adjacent positive propoxy hexalin, adjacent n-butoxy hexalin, adjacent cyclohexyloxy hexalin, adjacent n-octyloxy hexalin.
Embodiment 1-12
The o-alkoxyl hexalin that alcoholysis embodiment 1-6 is prepared carries out liquid-solid phase dehydrogenation reaction according to the method for step of the present invention (2), be specially dehydrogenation catalyst and raw material or solvent are joined in autoclave, be warming up to temperature of reaction, then open back pressure valve Controlling System pressure to stablize temperature of reaction, and the hydrogen of overflowing by back pressure valve release reaction.Experiment parameter and reaction result are as shown in table 1 below.
Table 1
Embodiment 13-19
The o-alkoxyl hexalin that alcoholysis embodiment 1-6 is prepared carries out gas-solid phase dehydrogenation reaction according to the method for step of the present invention (2), be specially the dehydrogenation catalyst of forming (trifolium-shaped) is encased in fixed-bed reactor, be warming up to after temperature of reaction, pass into reactant or reactant and solvent, experiment parameter and reaction result are as shown in table 2 below.
Table 2
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. by epoxy cyclohexane, prepared a method for O--Alkoxy phenols, the method comprises:
(1) under alcoholysis conditions, epoxy cyclohexane is contacted with alcoholysis catalysts with alcohol, separation obtains o-alkoxyl hexalin;
(2), under catalytic dehydrogenation condition, the dehydrogenation catalyst that o-alkoxyl hexalin and active ingredient are contained to group VIII metal element contacts.
2. method according to claim 1, wherein, the alcohol that described alcohol is C1-C12, is preferably the alcohol of C1-C6, more preferably methyl alcohol, ethanol, Virahol or hexalin.
3. method according to claim 1 and 2, wherein, described alcoholysis catalysts is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, sulfuric acid, fluoroboric acid, Phenylsulfonic acid, sodium pyrosulfate, phosphoric acid, formic acid, acetic acid, Whitfield's ointment and resin cation (R.C.).
4. according to the method described in any one in claim 1-3, wherein, described in step (1), alcoholysis conditions comprises: temperature is subzero 10 ℃ to 150 ℃ above freezing, and the mol ratio of epoxy cyclohexane and alcohol is 1:1-50, and the mass ratio of alcoholysis catalysts and epoxy cyclohexane is 0.002-0.1:1.
5. according to the method described in any one in claim 1-4, wherein, the dehydrogenation catalyst that described in step (2), active ingredient contains group VIII metal element is that nickel is that dehydrogenation catalyst, palladium are that dehydrogenation catalyst, platinum group dehydrogenation catalyst, ruthenium are that dehydrogenation catalyst and rhodium are one or more in dehydrogenation catalyst.
6. according to the method described in any one in claim 1-5, wherein, described in step (2), the condition of catalytic dehydrogenation comprises: temperature is 210-380 ℃, and mass space velocity is 0.02-4h
-1.
7. method according to claim 6, wherein, the condition of described catalytic dehydrogenation comprises: temperature is 240-320 ℃, mass space velocity is 0.1-1h
-1.
8. according to the method described in any one in claim 1-5, wherein, the condition of the described catalytic dehydrogenation of step (2) comprises: temperature is 170-380 ℃, and catalyst quality concentration is 0.01-20%, and the residence time is 0.5-100h.
9. method according to claim 8, wherein, the condition of described catalytic dehydrogenation comprises: temperature is 220-300 ℃, and catalyst quality concentration is 0.1-10%, and the residence time is 2-20h.
10. according to the method for dehydrogenating described in any one in claim 1-9, the described catalytic dehydrogenation of step (2) is carried out under solvent exists, and the mass ratio of solvent and o-alkoxyl hexalin is 0.1-100:1, more preferably 0.2-20:1; Preferred described solvent is one or more in alcohol, ester, nitrile, ketone and water, more preferably one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, hexalin, butyleneglycol, octanol, ethyl acetate, glycol dicaproate, glycol diacetate, hexalin acetate, octyl phthalate, butyleneglycol diacetate esters, diethylene adipate, butyl phthalate, acetonitrile, adiponitrile, pimelinketone, acetone, isophorone and water.
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| CN104744222A (en) * | 2013-12-31 | 2015-07-01 | 岳阳昌德化工实业有限公司 | Method for preparing 2-alkoxy cyclohexanol |
| CN104926625A (en) * | 2015-05-26 | 2015-09-23 | 岳阳昌德化工实业有限公司 | 2-alkoxycyclohexanol dehydrogenation method |
| CN104974112A (en) * | 2015-05-26 | 2015-10-14 | 岳阳昌德化工实业有限公司 | o-alkoxy cyclohexanol glycidyl ether and synthetic method thereof |
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| CN105016986A (en) * | 2015-05-26 | 2015-11-04 | 岳阳昌德化工实业有限公司 | (3-alkoxy-4-hydroxy)-cyclohexyl methylal diol, isomer thereof and synthesis methods and use for (3-alkoxy-4-hydroxy)- cyclohexyl methylal diol and isomer thereof |
| CN105037110A (en) * | 2015-05-26 | 2015-11-11 | 岳阳昌德化工实业有限公司 | Dehydrogenizing method for o-alkoxylcyclohexanol |
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| CN105037299A (en) * | 2015-05-26 | 2015-11-11 | 岳阳昌德化工实业有限公司 | 3,4-epoxy cyclohexyl methylal diol, and synthesis method and application thereof |
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| CN104974112A (en) * | 2015-05-26 | 2015-10-14 | 岳阳昌德化工实业有限公司 | o-alkoxy cyclohexanol glycidyl ether and synthetic method thereof |
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