CN1490293A - Preparation of o-phenyl phenol from cyclohexanone by condense dehydrogenation - Google Patents
Preparation of o-phenyl phenol from cyclohexanone by condense dehydrogenation Download PDFInfo
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- CN1490293A CN1490293A CNA021384339A CN02138433A CN1490293A CN 1490293 A CN1490293 A CN 1490293A CN A021384339 A CNA021384339 A CN A021384339A CN 02138433 A CN02138433 A CN 02138433A CN 1490293 A CN1490293 A CN 1490293A
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Abstract
A process for preparing O-phenylphenol from cyclohexanone includes such steps as condensation reaction between moleculae of cyclohexane under existance of inorganic acid or strong alkali as catalyst to generate 2-cyclohexalkylene cyclohexanone (A) and 2-(1-cyclohexenyl) cyclohexanone (B), dehydrogenation under existance of catalyst to generate O-phenylphenol, and vacuum rectification. Its advantages are high purity (99.5% or more) and high output rate up to 75-85%.
Description
The present invention relates to by pimelinketone under inorganic acid or highly basic effect, condensation generates two kinds of resonance isomery intermediate 2-hexamethylene alkylidene group pimelinketone and 2-(1-cyclohexenyl) pimelinketone, and under catalyst action, intermediate generates orthoxenol through dehydrogenation again.
Japanese Patent 58180448 is introduced, and by the support of diphenyl oxygen, at the Pt catalyzer with have in the presence of vitriol or the silicate, prepares orthoxenol through dehydrogenation.Be reflected under normal pressure and 330 ℃ of temperature and carry out, reaction preference can reach 80%.
United States Patent (USP) 4035428 is introduced, and is raw material with phenol and phenyl ether, and orthoxenol is made in reaction in two stages.Fs, be loaded with CeO
2Or ThO
2Catalyzer and temperature 495-562 ℃ condition under react; Subordinate phase is being loaded with Pd or Pt catalyzer and temperature 400-450 ℃ of reaction down.This method requires harsh processing condition, and the yield of product is not high.
Japanese Patent 76179248 is introduced, and is raw material with 2-cyclohexyl phenol, and catalyzer is Al
2O
3Be loaded with Pt1.0%, Ir0.2% and KOH5%, deoxidation prepares orthoxenol under 300-420 ℃ of temperature.
External some patents about synthesizing o-phenylphenol in addition, its emphasis all is placed in selection of catalysts and the preparation.And in domestic mainly the distillation residue, isolate orthoxenol by sulfonation method production phenol.This method operational path complexity, severe operational environment, environmental pollution is serious again.
The present invention is to be raw material with the pimelinketone, earlier under strong mineral acid or alkali catalyst effect, between pimelinketone and the cyclic ketones molecule condensation reaction taking place, generate two resonance isomery intermediate 2-hexamethylene alkylidene group pimelinketone (I) and 2-(1-cyclohexenyl) pimelinketone (II), also generates water simultaneously.Condensation reaction can be represented with following reaction equation:
Two kinds of resonate isomery intermediate compound I and II that condensation reaction generated can not detect respectively in vapor-phase chromatography detects, and just can detect and have only with gas chromatograph-mass spectrometer.But these two kinds of intermediates under catalyst action, all can dehydrogenation generate orthoxenol, and it reacts available following reaction equation and represents:
Dehydrogenation reaction except that generating purpose product orthoxenol, also generates the incomplete by product of some dehydrogenations, and is main
Deng, and the incomplete intermediate of these dehydrogenations, all can be by reclaiming, capable again dehydrogenation, and generate orthoxenol.
The first step condensation reaction, employed strong inorganic acid catalyst has the vitriol oil and concentrated hydrochloric acid, and comparatively suitable is the vitriol oil.Alkali catalyst has NaOH, KOH or C
2H
5ONa.Catalyst consumption is 0.3 of pimelinketone quality～5 0%, the optimum amount: strong inorganic acid is 1～3%; Highly basic is 10～30%.
Condensation reaction is carried out under 40～120 ℃ of normal pressure and temperature, and comparatively Shi Yi temperature is 80～100 ℃.In the situation of not using the band aqua, the pimelinketone transformation efficiency is lower, generally is no more than 70%.If use the band aqua, as benzene,, in time take the water that reaction is given birth to out of reaction system by forming azeotrope, can obtain very high pimelinketone transformation efficiency, can reach 〉=95%, the consumption of benzene is 30～120% of a pimelinketone quality, suitable consumption is 60～100%.
Resonance intermediate compound I and II that condensation reaction generated can separate purification by rectifying.Rectifying can be adopted atmospheric distillation, collects 272 ℃ fraction, also can adopt rectification under vacuum, collects pressure and the corresponding fraction of temperature, as 0.50mmHg, and 140 ℃.Higher because of the boiling point (272 ℃) of intermediate, adopt rectification under vacuum better.Rectifying can obtain to satisfy the intermediate of dehydrogenation specification of quality, content 97-99%.
Second the step dehydrogenation reaction, the catalyzer that uses as metal load on carrier.Such metal has Pt, Pd, Ni, Cu or Ir, Ru, and commonly used have Pt, Pd or a Cu, and available carrier has γ-Al
2O
3, MgO, gac, molecular sieve, effect is more satisfactory γ-Al
2O
3, ZSM-5.
The preparation method of dehydrogenation catalyst is: use metal soluble salt or the acid for the treatment of load, load on the carrier by dipping, through oven dry roasting and logical H
2The reduction and make.The temperature of roasting generally is controlled at 230～450 ℃, time 1.5～4h.H
2The reductive temperature is 150～400 ℃, air speed 75～150/h, time 2～6h.Different catalyzer is formed different dehydrogenation reaction temperature and air speed, and the metal of load can be single component, also can be two components or many components, and its content of metal is generally 0.1～1.5% of carrier quality, and optimum amount is 0.3～0.6%.
Dehydrogenation reaction adopts the trickle bed mode to carry out under normal pressure or decompression, and intermediate in the contact of catalyst surface dehydrogenation reaction takes place from the upper end drippage of fixed-bed reactor that catalyst is housed.The temperature of reaction is different different because of catalyst component, is generally 120～230 ℃, and air speed is controlled at 0.2～15/h.Lower air speed can make dehydrogenation reaction more become complete.
The dehydrogenation reaction mixture adopts normal pressure or rectification under vacuum method, or hot alkali solution technique is isolated product and reclaimed other intermediate.Usually use the rectification under vacuum method more feasible.Can reclaim unreacted intermediate compound I and II by rectifying, also can reclaim the incomplete newly-generated intermediate of dehydrogenation, go dehydrogenation again, obtain high-purity orthoxenol of content 〉=99.5% simultaneously.
Example 1
With 230g column (φ 2 * 50～80) γ-Al
2O
3, adding is dissolved with 2.8gH
2PtCl
6The 280ml deionized water in, low temperature dipping 20h, oven drying at low temperature places H
2In, be warming up to 330 ℃ by 3～5 ℃/minute, and lasting 4h.Keep H subsequently
2Feed, be cooled to room temperature.0.3gKOH be dissolved in the 300ml deionized water, above-mentioned catalyzer is immersed, at room temperature soak 15h.The Lian Shui oven dry, and under 100 ℃, dry 2h, stand-by.
With the catalyzer of above-mentioned preparation, in the stainless steel tubular type reactor of the φ 32 * 1200 that packs into, dress up 400～500mm high catalyst post, heat with the ribbon heater outside.Under 120～180 ℃, with the flow velocity feeding N of 10～25ml/min
2The time, drip condensation intermediate compound I and II mixture from the upper end, control air speed 0.5～1.2/h.The mixture that dehydrogenation obtains is analyzed the growing amount of conversion rate of dehydrogenation, orthoxenol selectivity and other various intermediates with gas chromatograph-mass spectrometer.Condensation intermediate transformation efficiency 70%～90%, orthoxenol selectivity 86～90%.
With 30%NaOH solution heating for dissolving dehydrogenation reaction mixture, use hcl acidifying again, obtain the orthoxenol crude product, use the sherwood oil recrystallization again, the product of content 〉=99.5%, outward appearance is a white crystal, mp56～56.5 ℃.Or employing rectification under vacuum method, directly rectifying separation each component.
Example 2
With 200g column (φ 2 * 50～100) ZSM-5, adding is dissolved with 1.8gH
2PtCl
6And 0.6gPdCl
2The 280ml deionized water in, low temperature dipping 20h, oven drying at low temperature places H
2In, be warming up to 300 ℃ by 3～5 ℃/minute, and lasting 3h.Keep H subsequently
2Feed, be cooled to room temperature.0.5gKOH be dissolved in the 300ml deionized water, above-mentioned catalyzer is immersed, at room temperature soak 18h.The Lian Shui oven dry, and under 110 ℃, dry 2h, stand-by.
With the catalyzer of above-mentioned preparation, in the stainless steel tubular type reactor of the φ 32 * 1200 that packs into, dress up 400～500mm high catalyst post, heat with the ribbon heater outside.Under 120～160 ℃, with the flow velocity feeding N of 10～25ml/min
2The time, drip condensation intermediate compound I and II mixture from the upper end, control air speed 0.2～1.1/h.The mixture that dehydrogenation obtains is analyzed the growing amount of conversion rate of dehydrogenation, orthoxenol selectivity and other various intermediates with gas chromatograph-mass spectrometer.Condensation intermediate transformation efficiency 80%～95%, orthoxenol selectivity 88～93%.
Direct rectifying separation each component.
Example 3
With 200g column (φ 2 * 50～100) ZSM-5, adding is dissolved with 1.2gH
2PtCl
6, 0.3gNiCl
2And 0.6gPdCl
2The 250ml deionized water in, low temperature dipping 24h, oven drying at low temperature places H
2In, be warming up to 280 ℃ by 3～5 ℃/minute, and lasting 5h.Keep H subsequently
2Feed, be cooled to room temperature.0.9gKOH be dissolved in the 300ml deionized water, above-mentioned catalyzer is immersed, at room temperature soak 16h.The Lian Shui oven dry, and under 11 ℃, dry 2h, stand-by.
With the catalyzer of above-mentioned preparation, in the stainless steel tubular type reactor of the φ 32 * 1200 that packs into, dress up 400～500mm high catalyst post, heat with the ribbon heater outside.Under 130～150 ℃, with the flow velocity feeding N of 10～25ml/min
2The time, drip condensation intermediate compound I and II mixture from the upper end, control air speed 0.2～0.8/h.The mixture that dehydrogenation obtains is analyzed the growing amount of conversion rate of dehydrogenation, orthoxenol selectivity and other various intermediates with gas chromatograph-mass spectrometer.Condensation intermediate transformation efficiency 75%～85%, orthoxenol selectivity 76～87%.
With 30%NaOH solution heating for dissolving dehydrogenation reaction mixture, use hcl acidifying again, obtain the orthoxenol crude product, use the sherwood oil recrystallization, the product of content 〉=99.5%, outward appearance is a white crystal, mp56～56.5 ℃.
Example 4
With the 200g gac/magnesium oxide that suspends, add and be dissolved with 1.6gPdCl
2And 0.8gCuCl
2The 230ml deionized water in, add 150ml15% hydrochloric acid and 50ml37% formaldehyde solution simultaneously.Cool 5～10 ℃, stir and lasting 10 minutes.Transfer pH11 with NaOH solution.Filtration, washing and drying for standby.
With the catalyzer of above-mentioned preparation, in the stainless steel tubular type reactor of the φ 32 * 1200 that packs into, dress up 400～500mm high catalyst post, heat with the ribbon heater outside.Under 260～280 ℃, with the flow velocity feeding N of 15～20ml/min
2The time, drip condensation intermediate compound I and II mixture from the upper end, control air speed 0.3～1.2/h.The mixture that dehydrogenation obtains is analyzed the growing amount of conversion rate of dehydrogenation, orthoxenol selectivity and other various intermediates with gas chromatograph-mass spectrometer.Condensation intermediate transformation efficiency 80%～85%, orthoxenol selectivity 78～85%.
Directly rectification method separates each component.Orthoxenol, its content 〉=99.5%, outward appearance is a white crystal, mp56～56.5 ℃.
Claims (6)
1, a kind of method for preparing orthoxenol by pimelinketone condensation dehydrogenation, it is characterized in that pimelinketone is under the effect of mineral acid or alkali, condensation generates two kinds of resonance isomer 2-hexamethylene alkylidene group pimelinketone and 2-(1-cyclohexenyl) pimelinketone, in the effect of catalyzer, two kinds of resonance isomer all generate orthoxenol through dehydrogenation again.
2, according to the described orthoxenol preparation method of claim 1, it is characterized in that the employed catalyzer of condensation reaction is a strong inorganic acid, as the vitriol oil, concentrated hydrochloric acid, also can be highly basic, as NaOH, KOH and sodium acetate.The usage quantity of catalyzer is the 0.3%-50% of pimelinketone quality, and the optimum amount is 1%-15%.Condensation reaction is to carry out under normal pressure and temperature 40-120 ℃, also can use the band aqua, and as benzene, reflux is in time taken the water that reaction is generated out of reaction system.
3, according to the described orthoxenol preparation method of claim 1, it is characterized in that the condensation reaction mixture, unreacted pimelinketone apply mechanically and resonate isomer I and II are isolated in rectifying under decompression or normal pressure, its processing condition are pressure 0.01～0.10MPa, 80～270 ℃ of temperature.
4, according to the described orthoxenol preparation method of claim 1, it is characterized in that the employed catalyzer of dehydrogenation reaction is metal Pt, Pd, Ni or Cu, load on active C, MgO, Al
2O
3On molecular sieve ZSM-5.Metal can singlely use, and also can mix use, and its usage quantity is 0.1～1.5% of a carrier quality, and optimum consumption is 0.3～0.6%.Adopt dipping, hot coating method loaded metal, will and use H through roasting before catalyzer uses
2Reduction, roasting can be carried out in air, and uses N
2Protection is better.Maturing temperature is 230 ℃～450 ℃, time 1.5～4h; H
2The reductive temperature is 150 ℃～400 ℃, air speed 75-150/h, time 2-6h.
5,, it is characterized in that dehydrogenation reaction takes the trickle bed mode according to the described orthoxenol preparation method of claim 1.The condensation intermediate is from the upper end drippage of fixed-bed reactor that catalyst is housed, in the contact dehydrogenation of catalyst surface.Dehydrogenation reaction is to carry out under normal pressure or decompression, and temperature of reaction changes with the composition of catalyzer is different, and general temperature range is 100～300 ℃, and optimal temperature is 120～230 ℃, air speed 0.2～15/h, and lower air speed has dehydrogenation effect preferably.Conversion rate of dehydrogenation can reach 60-90%, and the selectivity of orthoxenol can reach 80～95%.
6, according to the described orthoxenol preparation method of claim 1, it is characterized in that the dehydrogenation reaction mixture can be under normal pressure or decompression rectifying separation, the incomplete resultant of the intermediate of dehydrogenation and dehydrogenation not wherein can reclaim and go dehydrogenation again.Control pressure is corresponding with temperature, the product fraction of institute's extraction, the content of orthoxenol 〉=99.5%.After also can adopting hot NaOH solution dissolving, the method for separating out with hcl acidifying is obtained product again, and the available sherwood oil of the purification of substandard product, petroleum naphtha are made the solvent recrystallization method.
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| CNA021384339A CN1490293A (en) | 2002-10-15 | 2002-10-15 | Preparation of o-phenyl phenol from cyclohexanone by condense dehydrogenation |
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Cited By (9)
| 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 |
| CN102399135A (en) * | 2010-09-09 | 2012-04-04 | 东营远大化工有限公司 | O-phenylphenol preparation and separating and refining method |
| CN102740965A (en) * | 2010-02-05 | 2012-10-17 | 埃克森美孚化学专利公司 | Dehydrogenation process |
| 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 |
| CN103319370A (en) * | 2012-03-21 | 2013-09-25 | 黑龙江福和华星制药集团股份有限公司 | Preparation method of (7-methoxy-1-naphthyl)acetonitrile |
| US9169181B2 (en) | 2009-09-17 | 2015-10-27 | Exxonmobil Chemical Patents Inc. | Production of cyclohexylbenzene hydroperoxide |
| CN105195147A (en) * | 2015-10-21 | 2015-12-30 | 扬州大学 | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst |
| CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
| CN106179338A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化学工业开发股份有限公司 | Catalyst composition for preparing o-phenylphenol and method for preparing o-phenylphenol by using catalyst composition |
-
2002
- 2002-10-15 CN CNA021384339A patent/CN1490293A/en active Pending
Cited By (12)
| 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 |
| US9169181B2 (en) | 2009-09-17 | 2015-10-27 | Exxonmobil Chemical Patents Inc. | Production of cyclohexylbenzene hydroperoxide |
| CN102740965A (en) * | 2010-02-05 | 2012-10-17 | 埃克森美孚化学专利公司 | Dehydrogenation process |
| US9035107B2 (en) | 2010-02-05 | 2015-05-19 | Exxonmobil Chemical Patents Inc. | Dehydrogenation process |
| CN102399135A (en) * | 2010-09-09 | 2012-04-04 | 东营远大化工有限公司 | O-phenylphenol preparation and separating and refining method |
| 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 |
| CN103319370A (en) * | 2012-03-21 | 2013-09-25 | 黑龙江福和华星制药集团股份有限公司 | Preparation method of (7-methoxy-1-naphthyl)acetonitrile |
| CN103319370B (en) * | 2012-03-21 | 2016-08-03 | 黑龙江福和华星制药集团股份有限公司 | A kind of preparation method of (7-methoxy-1-naphthyl) acetonitrile |
| CN106179338A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化学工业开发股份有限公司 | Catalyst composition for preparing o-phenylphenol and method for preparing o-phenylphenol by using catalyst composition |
| CN106179338B (en) * | 2015-05-07 | 2019-11-15 | 中国石油化学工业开发股份有限公司 | Catalyst composition for preparing o-phenylphenol and method for preparing o-phenylphenol by using catalyst composition |
| CN105195147A (en) * | 2015-10-21 | 2015-12-30 | 扬州大学 | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst |
| CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
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