CN101205170B - Utilization method of solid catalyst for cyclohexanone self-condensation reaction - Google Patents
Utilization method of solid catalyst for cyclohexanone self-condensation reaction Download PDFInfo
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- CN101205170B CN101205170B CN2007101769853A CN200710176985A CN101205170B CN 101205170 B CN101205170 B CN 101205170B CN 2007101769853 A CN2007101769853 A CN 2007101769853A CN 200710176985 A CN200710176985 A CN 200710176985A CN 101205170 B CN101205170 B CN 101205170B
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- pimelinketone
- solid catalyst
- reaction
- cyclohexanone
- alumina base
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for using a solid catalyst for the self-condensing reaction of a cyclohexanone, which comprises the steps that an alumina-based solid catalyst is used in the first step of condensing and dehydrogenating the cyclohexanone to prepare the O-phenylphenol, namely the step of the self-condensing of the cyclohexanone, and a certain used amount of the appropriate water-carrying agents are used in the process of using the alumina-based solid catalyst for the condensation reaction of the cyclohexanone; wherein, the used amount of the solid catalysts corresponds to 2 per cent to 5 per cent of that of the cyclohexanone and the reaction time ranges from 4 to 8 hours; also that any water-carrying agents is unused is okay and the characteristic that the cyclohexanone carries water is utilized to accomplish the reaction; the cyclohexanone undergoes the self-condensing reaction so as to generate two resonance isomers, 2-(1-cyclohexenyl) (I) cyclohexanone and 2-cyclohexenyl alkylidene cyclohexanone (II), under the effect of the prepared solid catalysts, and two demeric products can be both used as the raw materials for carrying out the dehydrogenation to prepare the O-phenylphenol.
Description
Technical field
the present invention relates to the using method that a kind of solid catalyst is used for cyclohexanone self-condensation reaction, the method is to be that pimelinketone is in the step of condensation step in the standby orthoxenol the first step of pimelinketone condensation Oxidative Dehydrogenation, used the alumina base solid catalyst, the alumina base solid catalyst can used suitable band aqua for the pimelinketone condensation reaction, also can not use any band aqua and utilize pimelinketone self band water to complete reaction, pimelinketone is under the effect of made solid catalyst, self-condensation reaction occurs generate two kinds of resonance isomer 2-(1-cyclohexenyl) (I) pimelinketone and 2-hexamethylene alkylidene group pimelinketone (II), two kinds of dimerisation products all can be used as the raw material of the standby orthoxenol of Oxidative Dehydrogenation.
Background technology
Orthoxenol (OPP) is a kind of important Organic chemical products, and purposes is very extensive, has good development prospect, and production technique is a lot, but many superseded at present.Domesticly basically by sulfonation method, produce in the residue of phenol and separate and obtain OPP a few years ago, the method complex process, severe operational environment, environmental pollution is heavier, and along with progressively the closing down of China recent years sulfonation production line, the raw material sources of OPP are subject to great restriction.At present, the most promising is pimelinketone condensation dehydrogenation two step synthesis orthoxenol OPP, and this technique can simply represent with figure below.
Wherein, the condensation reaction of the first step pimelinketone generally uses the liquid organic acids such as the liquid inorganic acids such as the vitriol oil, concentrated hydrochloric acid or methylsulfonic acid as catalyzer, wherein the vitriol oil is the most commonly used, as all having used the catalyzer of the vitriol oil as the pimelinketone condensation reaction in Chinese patent CN1371897A and CN1490293A, US Patent No. 4, also introduced the result of use of certain density sulfuric acid (as 50%) in 002,693; Also can use highly basic such as NaOH, KOH, CH
3COONa etc., as catalyzer, still contrast strong acid catalyst, and alkaline catalysts is large usage quantity not only, and catalytic effect is poor, industrial seldom use.Use consumption that the advantage of concentrated sulfuric acid catalyst is general catalyzer can be very not high (as use dilute sulphuric acid consumption increase to some extent), reaction time consumption shorter (2-3 hour get final product), the effect of catalysis still can (per pass conversion the highest can over 90%).But have many drawbacks with this type of strong acid catalyzed pimelinketone homogeneous phase condensation reaction,, due to high dehydrated energy and the strong oxidizing property that the vitriol oil itself has, must cause the side reaction of condensation reaction a lot, selectivity is poor, causes thick product color very heavy; Although being replaced by dilute sulphuric acid can the more problem of partial rcsponse by product, the introducing reaction system of too much water but can cause transformation efficiency that to a certain degree decline is arranged.Moreover, no matter adopt the sulfuric acid of which kind of concentration, crude product always needs the follow-up treatment steps such as alkali lye neutralization, standing and demixing and rectifying just can obtain pure dipolymer product, and find in actually operating that in the process of acid-base neutralisation, emulsion is serious, realize that layering preferably often needs long time, very unfavorable to industrial operation.In addition, large as the vitriol oil corrodibility of catalyzer, higher to the requirement of equipment, input ratio is larger in advance; Catalyzer is removed and can't be reclaimed use owing to being neutralized in addition, for the economic benefit of enterprise, has loss, and the aqueous phase after neutralization, owing to containing a large amount of salkali waste and other byproducts, has larger environmental issue.
, if solid catalyst is adopted in above-mentioned reaction, can effectively avoid problems.Itself does not have corrodibility solid catalyst, and select suitable catalyst type can also realize transformation efficiency and selectivity preferably, the thick product of dipolymer only need can be removed catalyzer through simple filtration like this, thereby need not loaded down with trivial details post-processing step and avoided environmental pollution, and improved production efficiency, and isolated catalyzer can be reused through simple regeneration, is undoubtedly a kind of environmentally friendly green catalyst, has very large economic interests and social benefit.Present research shows, the pimelinketone condensation reaction can be carried out under acid or alkaline catalysis, therefore has suitable acid or alkaline solid catalyst and all may have certain catalytic activity.Once had a small amount of bibliographical information to can be applicable to the solid catalyst of pimelinketone condensation reaction, as the Shanxi coalification once developed the modified alpha-Al that is used for the pimelinketone condensation reaction
2O
3Or the condensation reaction of magnesium-aluminium spinel catalysis of pimelinketone, adopt gas-phase reaction, temperature 350-400 ℃, but active poor (peak rate of conversion 44%) of catalyzer and rapid inactivation.Also have acidic cationic resin domestic and that Japanology is crossed also to have certain catalytic effect, but such catalyzer limitation is larger for industrial production.
Summary of the invention
Purpose of the present invention is exactly to avoid above-mentioned the deficiencies in the prior art part and provide a kind of solid catalyst to be used for the using method of cyclohexanone self-condensation reaction.Because the researchist, find, can use metal oxide as main body, alternatively carry out modification or with the composite solid catalyst that obtains of other materials, have desirable pimelinketone transformation efficiency and dipolymer selectivity under step operational condition.Available have alkali and alkaline earth metal ions oxide compound such as a K
2O, Na
2O, CaO, MgO etc., and transition metal oxide such as Fe
2O
3, TiO
2, ZrO
2, Al
2O
3, V
2O
5, CrO
3Deng.Especially, alkalimetal oxide and transition metal oxide, transition metal oxide and transition metal oxide, or nonmetal genus oxide compound such as SiO
2Higher with the catalyst compounded selectivity that certain proportion forms with transition metal oxide.Simultaneously, catalyzer preferably has suitable acid-basicity and certain pore passage structure (as specific surface and pore volume etc.).
The pimelinketone condensation reaction is normally carried out under normal pressure and temperature 80-200 ℃, we find the research by early stage, and comparatively suitable temperature range is 80-120 ℃ (concentrated sulfuric acid catalyst), 110-150 ℃ (self-control solid catalyst).Because the pimelinketone condensation reaction is reversible reaction, remove moisture that reaction generates and will be conducive to reaction and carry out to positive dirction, and in order fully to shift out moisture, using the band aqua is the most common, effective means.For the pimelinketone condensation reaction, common way is to use with the benzene of mentioning in aqua such as CN 1490293A, and we study discovery as the band such as hexanaphthene, normal heptane aqua, dependence with aqua and water form azeotrope will react in the water of generation in time take reaction system out of, can significantly improve the pimelinketone transformation efficiency, in general, be the 30-100% of pimelinketone consumption with the amount ranges of aqua, suitable scope is 40-80%.And likely because temperature of reaction is higher, cause that by product is more, the dipolymer selectivity descends while not using the band aqua to rely on pimelinketone self band water, be saved with purchase and the use cost of aqua and avoided the process of follow-up fractionation by distillation band aqua but do not use advantage with the operating procedure of aqua.Therefore, the contriver is summarized as follows the technological process of its use:
1. be that pimelinketone is in the step of condensation step in the standby orthoxenol the first step of pimelinketone condensation Oxidative Dehydrogenation, use the alumina base solid catalyst, its technical characterstic is: this alumina base solid catalyst is the alumina base solid catalyst that is obtained by the roasting of precursor pseudo-boehmite, and in reaction process under batch reaction conditions condensation generate two kinds of resonance isomer 2-(1-cyclohexenyl) pimelinketone and 2-hexamethylene alkylidene group pimelinketone; The alumina base solid catalyst is being used for the pimelinketone condensation reaction, use the band aqua and be not with aqua by the red-tape operati condition, namely when the band aqua that uses, wherein the consumption of solid catalyst is the 2-5% of pimelinketone consumption, and the reaction times is at 4-8 hour; When not using the band aqua, be to utilize pimelinketone self band water to complete reaction, wherein the consumption of solid catalyst is the 2-5% of pimelinketone consumption, the reaction times is at 2-4 hour.
2. the alumina base catalysis of solid catalyst pimelinketone condensation reaction of using can reduce reactions steps, and its typical product postprocessing step is:
1. at first through a step filtration procedure, the alumina base catalyst of solid phase can be separated with the product system of liquid phase after reaction finishes;
2. the product mixtures of liquid phase distills under normal pressure or decompression, can isolate respectively unreacted pimelinketone, band aqua and dimerisation products I and II according to boiling point difference, and the processing condition of still-process are 0.05-1.0atm, temperature range 100-280 ℃.
3. the preparation method for the alumina base solid catalyst is:
1. the preparation method of modified aluminas not
The typical preparation method of modified aluminas does not get a certain amount of pseudo-boehmite precursor, carries out roasting, and temperature is 300-600 ℃, and the time is 2-6 hour, decomposes and namely obtains Al
2O
3Catalyzer;
2. the preparation method of modified alumina catalyst
The typical preparation method of modified aluminas gets a certain amount of pseudo-boehmite precursor, first carries out roasting, and its temperature is 300-600 ℃, and the time is 2-6 hour, decomposes and namely obtains Al
2O
3Then with this Al
2O
3Adopt the equi-volume impregnating dipping to contain the aqueous solution of the modified metal ion precursor (being generally corresponding salt) of stoichiometry charge capacity, the room temperature dipping is after 6-8 hour, through the drying course at 100-120 ℃ of temperature, and then, at the roasting temperature 2-4 hour of 300-600 ℃, decompose and namely obtain Modification on Al
2O
3Catalyzer.
Description of drawings
Accompanying drawing 1 is solid catalyst of the present invention and is applied to the operational flowchart of catalysis of pimelinketone condensation reaction.
Accompanying drawing 2 is the technical process of adopting traditional concentrated sulfuric acid catalyst.
Embodiment
Carry out enumeration technical characterstic of the present invention below in conjunction with specific embodiment:
Embodiment 1
This example is the concentrated sulfuric acid catalyst Comparative Examples.With the 100mL pimelinketone as in the there-necked flask that thermometer, agitator and water trap are housed, add the vitriol oil of 2mL 98% as catalyzer, the 60mL cyclohexane give is the band aqua, in 110 ℃ of back flow reaction 2 hours, the NaOH solution with 10% after reaction stops transferred to neutrality with reaction system, after branch vibration layer, get oil phase and carry out stratographic analysis, pimelinketone transformation efficiency approximately 85.7%, selectivity approximately 83.5%, dipolymer yield 71.6%.
Embodiment 2
With the 100mL pimelinketone as in the there-necked flask that thermometer, agitator and water trap are housed, normal heptane band water (consumption 60mL), the γ-Al that adds 4g to obtain in 4 hours prior to 500 ℃ of roastings in advance
2O
3Catalyzer (pore volume 0.52mL/g, specific surface 207m
2/ g), be heated to system boiling reflux reaction 6 hours, pimelinketone transformation efficiency 75.7%, dipolymer selectivity 99.0%, dipolymer yield 74.9%; The band aqua is constant, and more catalyst changeout is 5%K
2O-Al
2O
3Catalyst compounded, pimelinketone transformation efficiency 82.1%, dipolymer selectivity 96.6%, dipolymer yield 79.3%; The band aqua is constant, and more catalyst changeout is 10%TiO
2-Al
2O
3Catalyst compounded catalyzer, pimelinketone transformation efficiency 78.3%, dipolymer selectivity 98.6%, dipolymer yield 77.2%; Catalyzer is γ-Al
2O
3, more the tape swapping aqua is toluene (consumption is constant), pimelinketone transformation efficiency 88.8%, dipolymer selectivity 96.8%, dipolymer yield 85.9%.
Embodiment 3
With the 100mL pimelinketone as in the there-necked flask that thermometer, agitator and water trap are housed, normal heptane band water (consumption 60mL), the industrial macropore Al that adds 4g to obtain in 4 hours prior to 500 ℃ of roastings in advance
2O
3Catalyzer (pore volume 0.79mL/g, specific surface 281m
2/ g), be heated to system boiling reflux reaction 6 hours, pimelinketone transformation efficiency 81.8%, dipolymer selectivity 96.5%, dipolymer yield 78.9%.Other conditions are constant, and more catalyst changeout is 33.5%MgO-macropore Al
2O
3Catalyst compounded, pimelinketone transformation efficiency 76.5%, dipolymer selectivity 95.2%, dipolymer yield 72.8%.
Embodiment 4
This example is that the alumina base solid catalyst does not use with the example of the investigation in the aqua situation for the pimelinketone condensation reaction.With the 100mL pimelinketone as in the there-necked flask that thermometer, agitator and water trap are housed, the γ-Al that adds 3g to obtain in 4 hours prior to 500 ℃ of roastings in advance
2O
3Catalyzer (pore volume 0.52mL/g, specific surface 207m
2/ g), be heated to system boiling reflux reaction 2 hours, pimelinketone transformation efficiency 73.9%, dipolymer selectivity 97.5%, dipolymer yield 72.1%; If this γ-Al
2O
3Catalyst levels is 4g, reacts after 2 hours pimelinketone transformation efficiency 82.8%, dipolymer selectivity 95.8%, dipolymer yield 79.3% under similarity condition.This example is saved with purchase and the use cost of aqua and avoided the process of follow-up fractionation by distillation band aqua with respect to using advantage with the operating procedure of aqua in example 2 and example 3.
Embodiment 5
This example alumina base solid catalyst regeneration Performance example.With the 100mL pimelinketone as in the there-necked flask that thermometer, agitator and water trap are housed, normal heptane band water (consumption 60mL), the γ-Al that adds 4g to obtain in 4 hours prior to 500 ℃ of roastings in advance
2O
3Catalyzer (pore volume 0.52mL/g, specific surface 207m
2/ g), be heated to system boiling reflux reaction 6 hours, pimelinketone transformation efficiency 80.9%, dipolymer selectivity 95.8%, yield 77.5%.γ-the Al that will leach after reaction
2O
3Catalyzer can have its catalytic activity of efficient recovery through 500 ℃ of lower roasting regenerations of 2 hours in retort furnace.γ-Al through primary recycling
2O
3The result of use of catalyzer is pimelinketone transformation efficiency 86.1%, dipolymer selectivity 95.7%, dipolymer yield 82.3%; γ-Al through 10 regeneration
2O
3The result of use of catalyzer is pimelinketone transformation efficiency 85.3%, dipolymer selectivity 96.3%, dipolymer yield 82.1%.
The invention effect
Compare with the technical process of traditional concentrated sulfuric acid catalyst, because the present invention has used solid catalyst at pimelinketone condensation Oxidative Dehydrogenation for the first step in the orthoxenol process, namely cyclohexanone self-condensation reaction generates the alumina base solid catalyst that uses in the reaction of dimerisation products 2-(1-cyclohexenyl) pimelinketone (I) and 2-hexamethylene alkylidene group pimelinketone (II).Under the katalysis of alumina base solid catalyst, under the temperature of reaction condition of normal pressure and 100-150 ℃, use suitable band aqua, the per pass conversion of pimelinketone can reach 70-95%, selectivity 90-99%, the dipolymer yield can reach 70-88%.And while using pimelinketone self band water, control reaction conditions and also can reach pimelinketone transformation efficiency 82.8%, dipolymer selectivity 95.8%, the ideal effect of dipolymer yield 79.3%.The advantage of catalyzer is to react thick product and does not need complicated subsequent processing steps, only need remove by filter catalyzer, the I that liquid distillation can be obtained making with extra care and the mixture of II can be used for the step of the standby orthoxenol of follow-up Oxidative Dehydrogenation, unreacted pimelinketone can reclaim by distillation, and described solid catalyst can roasting repeat the regeneration use more than 10 times.
Claims (2)
1. a solid catalyst is used for the using method of cyclohexanone self-condensation reaction, the method is to be that pimelinketone is in the step of condensation step in the standby orthoxenol the first step of pimelinketone condensation Oxidative Dehydrogenation, used the alumina base solid catalyst, it is characterized in that this alumina base solid catalyst is the alumina base solid catalyst that is obtained by the roasting of precursor pseudo-boehmite, and in reaction process under batch reaction conditions condensation generate two kinds of resonance isomer 2-(1-cyclohexenyls) pimelinketone and 2-hexamethylene alkylidene group pimelinketone; The alumina base solid catalyst is being used for the pimelinketone condensation reaction, use the band aqua and be not with aqua by the red-tape operati condition, namely when the band aqua that uses, wherein the consumption of solid catalyst is the 2-5% of pimelinketone consumption, and the reaction times is at 4-8 hour; When not using the band aqua, be to utilize pimelinketone self band water to complete reaction, wherein the consumption of solid catalyst is the 2-5% of pimelinketone consumption, the reaction times is at 2-4 hour; Wherein, the preparation method of alumina base solid catalyst, for being to get a certain amount of pseudo-boehmite precursor, carries out roasting, and temperature is 300-600 ℃, and the time is 2-6 hour, decomposes and namely obtains Al
2O
3Catalyzer.
2. a kind of solid catalyst according to claim 1 is used for the using method of cyclohexanone self-condensation reaction, it is characterized in that using the condensation reaction of alumina base catalysis of solid catalyst pimelinketone can reduce reactions steps, and its product postprocessing step is:
(1) at first through a step filtration procedure, the alumina base catalyst of solid phase can be separated with the product system of liquid phase after reaction finishes;
(2) product mixtures of liquid phase distills under normal pressure or decompression, can isolate respectively unreacted pimelinketone, band aqua and dimerisation products I and II according to boiling point difference, and the processing condition of still-process are 0.05-1.0atm, temperature range 100-280 ℃.
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| TW201226379A (en) | 2010-12-28 | 2012-07-01 | China Petrochemical Dev Corp | Method of producing 2-(cyclohex-1'-enyl) cyclohexanone |
| TWI759615B (en) | 2019-07-22 | 2022-04-01 | 中國石油化學工業開發股份有限公司 | A method for preparing 2-cyclohexyl cyclohexanol |
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| CN101003471A (en) * | 2006-11-02 | 2007-07-25 | 盐城市华业医药化工有限公司 | Method for producing cyclohexenyl anone from continuous condensating anone |
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| CN101003471A (en) * | 2006-11-02 | 2007-07-25 | 盐城市华业医药化工有限公司 | Method for producing cyclohexenyl anone from continuous condensating anone |
Non-Patent Citations (2)
| Title |
|---|
| 《从环己酮一步合成邻苯基苯酚》;冯月兰等;《精细化工》;19941231;第11卷(第5期);42-45 * |
| 冯月兰等.《从环己酮一步合成邻苯基苯酚》.《精细化工》.1994,第11卷(第5期),42-45. |
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