CN1371897A - Process for synthesizing orthophenylphenol from cyclohexanone - Google Patents
Process for synthesizing orthophenylphenol from cyclohexanone Download PDFInfo
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- CN1371897A CN1371897A CN 01108229 CN01108229A CN1371897A CN 1371897 A CN1371897 A CN 1371897A CN 01108229 CN01108229 CN 01108229 CN 01108229 A CN01108229 A CN 01108229A CN 1371897 A CN1371897 A CN 1371897A
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- pimelinketone
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- orthoxenol
- cyclohexanone
- phenylphenol
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Abstract
The method for synthesizing o-phenylphenol by cyclohexanone includes the following main steps: under the condition of catalysis of sulfuric acid making cyclohexanone produce condensation reaction, then mkaing it undergo the processes of neutralization, separation, dehydration and rectification to obtain the mixture to dimer 2-(1-cyclohexenyl) cyclohexanone and 2-cyclohexylalkylene cyclohexanone; recovering non-reacted cyclohexanone and making dimerization reaction; using nitrogen gas or hydrogen gas as protective gas to make dimer undergo the dehydrogenation reaction, and making the dehydrogenated mixture undergo the process of petroleum ether recrystallization process so as to obtain the invented o-phenylphenol.
Description
The present invention relates to a kind of synthetic method of orthoxenol, particularly a kind of pimelinketone synthetic method of o-phenylphenol of using.
Domestic this field is Shanxi relevant report that coalification once had only, its method is under alchlor catalysis, by the direct one-step synthesis orthoxenol of pimelinketone, its as a result the initial transformation efficiency of pimelinketone be 55%, the selectivity of orthoxenol only is 36.5% in the product.
External relevant report relates generally to the catalytic dehydrogenation of the dimer 2-hexamethylene alkylidene group pimelinketone and 2-(1-cyclohexenyl) pimelinketone of pimelinketone, describe as Japanese Patent JP76131863, when the catalyzer of forming with Platinic chloride, vitriolate of tartar and alchlor carries out catalytic dehydrogenation to dimer, the initial yield of orthoxenol is 88.7%, but the decay of catalyst dehydrogenation activity is very fast, on the method that prolongs catalyst life, employing in dimer, add 0.1% 2,6-d-tert-butyl-p-cresol, but effect and not obvious.Other catalyzer such as palladium/gac or palladium/aluminum oxide, the initial yield of orthoxenol is 81%; Nickel-chromium-copper-aluminium-vitriolate of tartar, the initial yield of orthoxenol is 83%; Other has patent to adopt nickel content up to nickel-chromium-copper-aluminium catalyst of 54.3%, and the initial yield of orthoxenol is can also remain on 66.5% after 88%, 2000 hour.
Because pimelinketone is cheap raw material, thereby the production cost of orthoxenol will depend primarily on catalyzer, can adopt cheap catalyzer or prolong work-ing life of catalyzer, will help the suitability for industrialized production of orthoxenol.
The object of the present invention is to provide a kind of is the raw material production orthoxenol with the pimelinketone, with prolong catalyzer work-ing life, selectivity is good, production cost is low, yield is high uses the pimelinketone synthetic method of o-phenylphenol.
The technology solution method scheme that realizes the object of the invention is: a kind of pimelinketone synthetic method of o-phenylphenol of using, it is characterized in that: pimelinketone is under sulfuric acid catalysis, carry out condensation reaction, obtain the mixture of dimer 2-(1-cyclohexenyl) pimelinketone and 2-hexamethylene alkylidene group pimelinketone then after neutralization, separation, dehydration, rectifying, unreacted pimelinketone carries out dimerization reaction after reclaiming again; Dimer serves as that protection gas carries out dehydrogenation reaction with nitrogen or hydrogen, and dehydrogenated mixture obtains orthoxenol through the sherwood oil recrystallization.
The present invention compared with prior art, its remarkable advantage is: be that raw material carries out the synthetic of orthoxenol with the pimelinketone, pimelinketone obtains dimeric yield and reaches more than 95% through condensation, dehydration, and dimeric purity reaches more than 99%; Dimer is carrying out dehydrogenation reaction under catalyzer copper/magnesium oxide catalysis cheaply, and dimeric initial transformation efficiency is 100%, and the selectivity of orthoxenol is 100%, after 100 hours, dimeric transformation efficiency is 94%, and the selectivity of orthoxenol is 88%, and the catalyzer cost obviously descends; Dimer carries out dehydrogenation reaction in containing under the catalysis of palladium molecular sieve catalyst of preparing with ion exchange method, dimeric initial transformation efficiency is 98%, the selectivity of orthoxenol is 100%, after 200 hours, dimeric transformation efficiency is 94%, the selectivity of orthoxenol is 97%, and life of catalyst and selectivity significantly improve.
Accompanying drawing is the schema with the pimelinketone synthetic method of o-phenylphenol of the present invention.
Below in conjunction with accompanying drawing the present invention is further described.
Embodiment 1.
Pimelinketone condensation, dehydration.The 100mL pimelinketone is placed reactor, add the 1mL98% vitriol oil as catalyzer, in 120 ℃ of back flow reaction 2 hours, reaction stops the back and with 10% sodium hydroxide solution reaction system is adjusted to neutrality, behind the branch vibration layer, normal pressure reclaims unreacted pimelinketone, collects the cut of 272～274 ℃ of boiling ranges then, is the dimer 2-hexamethylene alkylidene group pimelinketone of pimelinketone and the mixture of 2-(1-cyclohexenyl) pimelinketone.
Catalytic dehydrogenation.Dimer carries out dehydrogenation reaction under catalyzer copper/magnesium oxide catalysis cheaply:
The temperature of control catalyst layer under hydrogen stream protection, joins dimer in the dehydrogenation reactor with 0.2 liquid air speed, with the selectivity of dimeric transformation efficiency of gas-chromatography on-line monitoring and orthoxenol between 280～300 ℃.Dimeric initial transformation efficiency is 100%, the selectivity of orthoxenol is 100%, after 100 hours, dimeric transformation efficiency is 94%, and the selectivity of orthoxenol is 88%, uses the sherwood oil recrystallization, obtain orthoxenol after the filtration, after filtrate was reclaimed sherwood oil, residuum carried out dehydrogenation reaction again after distillation, and the catalyzer cost obviously descends;
Embodiment 2.
Pimelinketone condensation, dehydration.The 100mL pimelinketone is placed reactor, add the 1mL98% vitriol oil as catalyzer, in 120 ℃ of back flow reaction 2 hours, reaction stops the back and with 10% sodium hydroxide solution reaction system is adjusted to neutrality, behind the branch vibration layer, normal pressure reclaims unreacted pimelinketone, collects the cut of 272～274 ℃ of boiling ranges then, is the dimer 2-hexamethylene alkylidene group pimelinketone of pimelinketone and the mixture of 2-(1-cyclohexenyl) pimelinketone.
Dimer carries out dehydrogenation reaction in containing of preparing with ion exchange method under the catalysis of palladium molecular sieve catalyst:
The temperature of control catalyst layer under nitrogen gas stream protection, joins dimer in the dehydrogenation reactor with 0.2 liquid air speed, with the selectivity of dimeric transformation efficiency of gas-chromatography on-line monitoring and orthoxenol between 290～310 ℃.Dimeric initial transformation efficiency is 98%, the selectivity of orthoxenol is 100%, after 200 hours, dimeric transformation efficiency is 92%, and the selectivity of orthoxenol is 97%, uses the sherwood oil recrystallization, obtain orthoxenol after the filtration, after filtrate was reclaimed sherwood oil, residuum carried out dehydrogenation reaction again after distillation, and life of catalyst and selectivity significantly improve.
Other catalyzer copper-magnesium oxide-gac that the present invention relates to, palladium-magnesium oxide-gac, copper-zinc-aluminium, nickel-zinc-copper etc., under the catalysis of these catalyzer, dimeric initial transformation efficiency is 100%, the selectivity of orthoxenol is all more than 95%.
Claims (3)
1, a kind of pimelinketone synthetic method of o-phenylphenol of using, it is characterized in that: pimelinketone is under sulphuric acid catalysis, carry out condensation reaction, obtain the mixture of dimer 2-(1-cyclohexenyl) pimelinketone and 2-hexamethylene alkylidene group pimelinketone then after neutralization, separation, dehydration, rectifying, unreacted pimelinketone carries out dimerization reaction after reclaiming again; Dimer serves as that protection gas carries out dehydrogenation reaction with hydrogen or nitrogen, and dehydrogenated mixture obtains orthoxenol through the sherwood oil recrystallization after the filtration.
2, the pimelinketone synthetic method of o-phenylphenol of using according to claim 1, it is characterized in that: the temperature of control catalyst layer is between 290～310 ℃, dimer is joined in the reactor, the exit end of reactor is collected dehydrogenated mixture, use the sherwood oil recrystallization, obtain orthoxenol after the filtration, after filtrate was reclaimed sherwood oil, residuum carried out dehydrogenation reaction again after distillation.
3, the pimelinketone synthetic method of o-phenylphenol of using according to claim 1 and 2, it is characterized in that: setting-up point is 110-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011082291A CN1166604C (en) | 2001-02-23 | 2001-02-23 | Process for synthesizing orthophenylphenol from cyclohexanone |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011082291A CN1166604C (en) | 2001-02-23 | 2001-02-23 | Process for synthesizing orthophenylphenol from cyclohexanone |
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| CN1371897A true CN1371897A (en) | 2002-10-02 |
| CN1166604C CN1166604C (en) | 2004-09-15 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074187B (en) * | 2007-05-15 | 2011-06-22 | 盐城市华业医药化工有限公司 | Production of o-phenylphenol |
| CN102557908A (en) * | 2010-12-28 | 2012-07-11 | 中国石油化学工业开发股份有限公司 | Preparation method of 2- (cyclohex-1' -enyl) cyclohexanone |
| CN102898283A (en) * | 2011-07-29 | 2013-01-30 | 天津赛普泰克科技有限公司 | Industrial production technology of o-phenylphenol |
| CN105315442A (en) * | 2015-12-01 | 2016-02-10 | 仇颖超 | Preparation method of starch modified polycaprolactone plastic material |
| US9669395B2 (en) | 2015-05-07 | 2017-06-06 | China Petrochemical Development Corporation | Catalyst composition for preparing O-phenylphenol and method for preparing O-phenylphenol with the catalyst composition |
-
2001
- 2001-02-23 CN CNB011082291A patent/CN1166604C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074187B (en) * | 2007-05-15 | 2011-06-22 | 盐城市华业医药化工有限公司 | Production of o-phenylphenol |
| CN102557908A (en) * | 2010-12-28 | 2012-07-11 | 中国石油化学工业开发股份有限公司 | Preparation method of 2- (cyclohex-1' -enyl) cyclohexanone |
| CN102557908B (en) * | 2010-12-28 | 2015-09-23 | 中国石油化学工业开发股份有限公司 | Preparation method of 2- (cyclohex-1' -enyl) cyclohexanone |
| CN102898283A (en) * | 2011-07-29 | 2013-01-30 | 天津赛普泰克科技有限公司 | Industrial production technology of o-phenylphenol |
| US9669395B2 (en) | 2015-05-07 | 2017-06-06 | China Petrochemical Development Corporation | Catalyst composition for preparing O-phenylphenol and method for preparing O-phenylphenol with the catalyst composition |
| CN105315442A (en) * | 2015-12-01 | 2016-02-10 | 仇颖超 | Preparation method of starch modified polycaprolactone plastic material |
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| CN1166604C (en) | 2004-09-15 |
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