CN118978429B - Method for preparing o-phenylphenol by using cyclohexanone as raw material - Google Patents
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Abstract
The invention provides a method for preparing o-phenylphenol by using cyclohexanone as a raw material, belonging to the field of o-phenylphenol. The method for preparing o-phenylphenol by using cyclohexanone as a raw material comprises the following steps of aldol condensation, dehydration hydrogenation, dehydrogenation and post-treatment. The method for preparing o-phenylphenol by using cyclohexanone as the raw material can overcome the defects of the traditional cyclohexanone condensation dehydrogenation method, and simultaneously avoid the problems of low overall reaction efficiency, poor activity and long-term stability of a catalyst adopted in the dehydration hydrogenation and dehydrogenation processes caused by the stability difference of cis isomer and trans isomer of the o-cyclohexyl cyclohexanone in the preparation process, further improve the yield of dehydrogenation products, improve the production safety and reduce the operation difficulty.
Description
Technical Field
The invention relates to the field of o-phenylphenol, in particular to a method for preparing o-phenylphenol by taking cyclohexanone as a raw material.
Background
O-phenylphenol (OPP) is also called 2-hydroxy biphenyl and 2-phenylphenol, is an organic chemical product with very wide application, and is widely applied to the fields of sterilization and corrosion prevention, printing and dyeing auxiliary agents, printing and dyeing surfactants, stabilizers and flame retardants for synthesizing novel high polymer materials such as plastics, resins and the like. The o-phenylphenol and sodium salt thereof have broad-spectrum sterilization and mildew-removal capability, are low in toxicity and odorless, are good preservatives, can be used for mildew prevention and fresh-keeping of fruits and vegetables, are particularly suitable for mildew prevention of citrus, can be used for treating lemon, pineapple, pear, peach, tomato, cucumber and the like, and can minimize decay of the fruits and vegetables. Meanwhile, the o-phenylphenol and sodium salt thereof can be used as antiseptic and bactericide for products such as cosmetics, wood, leather, fiber, paper and the like. The o-phenylphenol and the water-soluble sodium salt thereof can be used as a dye carrier of polyester fibers, and can also be used as a dye carrier in carrier dyeing of chlorlon, terylene and the like. Furthermore, o-phenylphenol is used for replacing phenol, so that novel phenolic resin can be synthesized, has high thermal stability and low water absorbability, can be used for preparing paint products such as paint with excellent stability to water and alkali, and has wide market application.
The main production method of the o-phenylphenol from the end of the 70 th century of the 20 th century is a cyclohexanone condensation dehydrogenation method, wherein cyclohexanone is used as a starting material, unsaturated dimer is generated by condensation and dehydration, unreacted cyclohexanone is recovered by rectification, then the unsaturated dimer is subjected to dehydrogenation reaction to prepare a crude o-phenylphenol product, and the crude o-phenylphenol product is subjected to post-treatment and refining to prepare an o-phenylphenol finished product. However, the unsaturated dimer prepared by the process in the production process comprises two isomers of cyclohexenyl cyclohexanone and cyclohexenyl cyclohexanone, the two isomers have poor stability and are easy to oxidize, side reactions such as self-polymerization and cracking are easy to occur in the subsequent dehydrogenation reaction process, more byproduct impurities are produced in the product, and the post-treatment refining pressure is high, so that the large-scale production is not facilitated.
Aiming at the problems, the prior art discloses that cyclohexanone is used as a starting material, 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone is prepared through condensation reaction, unreacted cyclohexanone is recovered through rectification, then the 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone is dehydrated and hydrogenated to prepare a mixture containing cis-isomer and trans-isomer of the o-cyclohexylcyclohexanone, then the mixture is subjected to dehydrogenation reaction to prepare a crude product of the o-phenylphenol, and the crude product of the o-phenylphenol is subjected to post-treatment and refining to prepare a finished product of the o-phenylphenol. The method can solve the problems that unsaturated dimer in the traditional cyclohexanone condensation dehydrogenation method is poor in stability and unfavorable for dehydrogenation reaction, but in the prepared mixture containing cis-isomer and trans-isomer of the o-cyclohexyl cyclohexanone, the cis-isomer of the o-cyclohexyl cyclohexanone has larger steric hindrance, larger Van der Waals force and high molecular energy, and the stability of the mixture is obviously lower than that of the trans-isomer of the o-cyclohexyl cyclohexanone. In the large-scale production process of the o-phenylphenol, the overall reaction efficiency of the dehydrogenation reaction is low due to the existence of the cis isomer of the o-cyclohexyl cyclohexanone, and the yield of the dehydrogenation product cannot be further improved.
Meanwhile, in the preparation process, the existence of cis-isomer of the o-cyclohexyl cyclohexanone additionally occupies an active site of the catalyst, and due to the characteristic of low stability, the active site of the catalyst can be covered or blocked, so that the catalytic activity and long-term stability of the catalyst are reduced, the effective service life of the catalyst used in the dehydration hydrogenation and dehydrogenation processes is directly shortened, the catalyst needs to be replaced frequently, and the mass production is not facilitated. Furthermore, in the dehydrogenation reaction process, due to the coexistence of the cis isomer and the trans isomer of the o-cyclohexyl cyclohexanone under the conditions of high temperature and high pressure, the kinetic and thermodynamic properties of the cis isomer and the trans isomer of the o-cyclohexyl cyclohexanone are different in the dehydrogenation reaction, so that the reaction rate and the reaction equilibrium state are different, the safety risk exists in the large-scale production process, and the two configurations of the o-cyclohexyl cyclohexanone are required to be monitored and tracked simultaneously in the reaction process, so that the operation is complicated, and the large-scale production is not facilitated.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for preparing o-phenylphenol by using cyclohexanone as a raw material, which can overcome the defects of the traditional cyclohexanone condensation dehydrogenation method, and simultaneously avoid the problems of low overall reaction efficiency, poor activity of a catalyst and poor long-term stability adopted in dehydration hydrogenation and dehydrogenation processes caused by the stability difference of cis-isomer and trans-isomer of o-cyclohexyl cyclohexanone in the preparation process, further improve the yield of dehydrogenation products, improve the production safety and reduce the operation difficulty.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing o-phenylphenol from cyclohexanone includes such steps as aldol condensation, dewatering hydrogenation, dehydrogenation and post-treatment.
The aldol condensation method comprises the steps of metering cyclohexanone by a peristaltic pump, continuously introducing the cyclohexanone into a first fixed bed reactor filled with a condensation catalyst from the bottom, controlling the mass flow rate of the cyclohexanone relative to each kg of the condensation catalyst to be 200-210g/min, continuously carrying out aldol condensation reaction in the first fixed bed reactor at 25-30 ℃ in the presence of the condensation catalyst to generate 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone, continuously discharging the reacted material from the top of the first fixed bed reactor, feeding the material into a distillation kettle by a first buffer tank, controlling the distillation vacuum degree to be 0.09-0.098MPa, controlling the distillation temperature to be 95-100 ℃, and distilling and recovering unreacted cyclohexanone to obtain aldol condensation reaction liquid.
In the aldol condensation, the condensation catalyst is macroporous strong-alkaline anion exchange resin of quaternized styrene-divinylbenzene copolymer, and the average particle size of the macroporous strong-alkaline anion exchange resin is 0.6-0.7mm.
The dehydration and hydrogenation method comprises the steps of respectively metering aldol condensation reaction liquid and hydrogen, respectively preheating to 65-70 ℃, respectively continuously introducing the aldol condensation reaction liquid and the hydrogen into a second fixed bed reactor filled with a controlled catalyst from the top, controlling the mass flow of the aldol condensation reaction liquid relative to each kg of the controlled catalyst to be 240-260g/min, the feeding rate of the hydrogen to be 85-95mL/min, continuously performing dehydration and hydrogenation reaction in the second fixed bed reactor at the dehydration and hydrogenation temperature of 100-102 ℃ in the presence of the controlled catalyst to generate trans-isomerism o-cyclohexyl cyclohexanone and a small amount of cis-isomerism o-cyclohexyl cyclohexanone, continuously discharging the reacted materials from the bottom of the second fixed bed reactor, cooling to obtain the dehydration and hydrogenation reaction liquid, and temporarily storing the dehydration and hydrogenation reaction liquid in a second buffer tank, and recycling unreacted excessive hydrogen and dehydrogenation gas by a recycling device.
In the dehydration and hydrogenation, the controlled catalyst is prepared by adopting the following steps of carrier treatment and contact bonding.
The carrier treatment method comprises the steps of putting an MCM-41 molecular sieve into absolute ethyl alcohol with the weight being 8-10 times that of the molecular sieve, carrying out ultrasonic dispersion for 5-10min, stirring and heating to 40-45 ℃, carrying out heat preservation and stirring and dripping N, N-dimethylethylenediamine, controlling the dripping of the N, N-dimethylethylenediamine to be completed within 50-60min, then continuously heating to 68-72 ℃, carrying out heat preservation and reflux stirring for 32-36h, centrifuging to separate out solid matters, washing the solid matters by adopting absolute ethyl alcohol with the weight being 4-5 times that of the molecular sieve, transferring the solid matters into a vacuum drying oven, and drying to constant weight at the vacuum degree of 0.07-0.08MPa and 70-75 ℃ to obtain the modified carrier.
In the carrier treatment, the weight ratio of the MCM-41 molecular sieve to the N, N-dimethyl ethylenediamine is 1:0.4-0.5;
the MCM-41 molecular sieve has pore size of 4.5-5nm, average particle size of 8-10 μm and specific surface area of 1000-1100m 2/g.
The method for contact bonding comprises the steps of adding (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl into benzene, stirring for 20-30min, continuously adding a modified carrier, performing ultrasonic dispersion for 5-10min, adding triethylamine, stirring and heating to 68-70 ℃ in a nitrogen atmosphere environment, keeping warm and refluxing and stirring for 70-72h, naturally cooling to room temperature, continuously adding pentacarbonyl iron, stirring at room temperature for 22-24h, centrifuging to separate out solid matters, washing the solid matters with 4-5 times of absolute ethyl alcohol, and drying to obtain the controlled catalyst.
In the contact bonding, the weight ratio of the (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl, benzene, a modified carrier, triethylamine and pentacarbonyl iron is 4-4.2:100:12-12.5:0.2-0.3:2.6-2.8.
The dehydrogenation method comprises the steps of continuously introducing a dehydration and hydrogenation reaction liquid into a gasifier after metering, controlling the temperature of the gasifier to be 340-350 ℃, continuously introducing the dehydration and hydrogenation reaction liquid into a third fixed bed reactor filled with a dehydrogenation catalyst from the top after gasifying, controlling the mass flow rate of the dehydration and hydrogenation reaction liquid relative to each kg of the dehydrogenation catalyst to be 65-70g/min, controlling the dehydrogenation pressure in the third fixed bed reactor to be 0.65-0.75MPa, controlling the dehydrogenation temperature to be 370-380 ℃, continuously carrying out dehydrogenation reaction in the presence of the dehydrogenation catalyst, continuously discharging reacted materials from the bottom of the third fixed bed reactor, cooling to obtain crude o-phenylphenol, temporarily storing in a third buffer tank, and recycling hydrogen dehydrogenation gas generated in the dehydrogenation process by a hydrogen dehydrogenation gas recycling device.
In the dehydrogenation, the dehydrogenation catalyst is gamma-alumina loaded with copper oxide and zinc oxide, wherein the content of the copper oxide in the dehydrogenation catalyst is 6.5-7%, and the content of the copper oxide is 9-9.3wt%.
The post-treatment method comprises the steps of introducing the crude product of the o-phenylphenol into a first rectifying tower, carrying out primary rectification to collect light components, introducing the light components into a second rectifying tower, carrying out secondary rectification, collecting fractions and cooling to obtain the o-phenylphenol.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for preparing o-phenylphenol by using cyclohexanone as a raw material comprises the steps of continuously carrying out aldol condensation reaction in a first fixed bed reactor to produce 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone to prepare aldol condensation reaction liquid, continuously carrying out dehydration hydrogenation on the aldol condensation reaction liquid and hydrogen in a second fixed bed reactor in the presence of a controlled catalyst in a dehydration hydrogenation step, and simultaneously carrying out asymmetric catalysis on 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone in a dehydration hydrogenation process after chiral catalytic ligand (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl and pentacarbonyl iron in the controlled catalyst to prepare the dehydration hydrogenation reaction liquid, wherein the generation of cis-isomerism o-cyclohexyl cyclohexanone is effectively catalyzed and highly selectively generated. In the carrier treatment step of preparing the controlled catalyst, a specific MCM-41 molecular sieve is selected as a basic carrier, N-dimethyl ethylenediamine is adopted to carry out surface amination treatment on the MCM-41 molecular sieve to prepare a modified carrier, and then in the contact bonding step, (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl is adopted to be in contact bonding with the modified carrier, and then iron pentacarbonyl is contacted for further contact bonding, so that the controlled catalyst is prepared. In the dehydrogenation step, the dehydration hydrogenation reaction liquid is gasified and then subjected to continuous dehydrogenation reaction in a third fixed bed reactor in the presence of a dehydrogenation catalyst to obtain an o-phenylphenol crude product, the o-phenylphenol crude product is subjected to post-treatment purification to finally obtain an o-phenylphenol product, the technical means are matched and synergistic, the defects of the traditional cyclohexanone condensation dehydrogenation method can be effectively overcome, trans-isomerised o-cyclohexylcyclohexanone is effectively catalyzed and generated in a high selectivity manner in the dehydration hydrogenation process, the generation of cis-isomerised o-cyclohexylcyclohexanone is inhibited, the problem that the overall dehydrogenation reaction efficiency is low due to the fact that a large amount of coexisting cis-isomer and trans-isomer of o-cyclohexylcyclohexanone are poor in the preparation process is avoided, the dehydrogenation reaction efficiency is effectively improved, the yield of a dehydrogenation product (o-phenylphenol) is further improved, meanwhile, the problem that the activity of the catalyst is effectively catalyzed and the activity of the cis-isomerised o-cyclohexylcyclohexanone is reduced in the dehydration hydrogenation process is effectively avoided, the problem that the activity of the catalyst is reduced in the dehydration hydrogenation process is prolonged, the dehydrogenation efficiency is effectively improved, the dehydrogenation efficiency is prolonged, and the service life of the catalyst is prolonged is effectively prevented. Furthermore, the generation of cis-isomerism ortho-cyclohexyl cyclohexanone is effectively inhibited in the dehydration and hydrogenation process, the safety risk caused by the property difference of cis-isomerism ortho-cyclohexyl cyclohexanone and trans-isomerism cyclohexyl cyclohexanone in the subsequent dehydrogenation process can be avoided, monitoring and tracking of two configurations of ortho-cyclohexyl cyclohexanone are not needed in the subsequent dehydrogenation reaction, the process control convenience is improved, the operation difficulty is reduced, and the large-scale production is facilitated.
(2) According to the method for preparing o-phenylphenol by using cyclohexanone as a raw material, under the condition that the mass flow rate of an aldol condensation reaction liquid per kg of a controlled catalyst in a dehydration hydrogenation step reaches 240-260g/min, the conversion rate of 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone in the aldol condensation reaction liquid is 99.5-99.6%, the selectivity of trans-isomerism o-cyclohexyl cyclohexanone is 99.3-99.4%, the selectivity of cis-isomerism o-cyclohexyl cyclohexanone is 0.18-0.21%, and the calculated yield of a target product trans-isomerism o-cyclohexyl cyclohexanone is 98.8-99.0%.
(3) According to the method for preparing the o-phenylphenol by using the cyclohexanone as the raw material, under the condition of high reaction efficiency that the mass flow rate of a dehydration hydrogenation reaction liquid per kg of dehydrogenation catalyst in the dehydrogenation step reaches 65-70g/min, the conversion rate of the o-cyclohexylcyclohexanone (cis-isomerism and trans-isomerism) in the dehydration hydrogenation reaction liquid is 99.7-99.8%, the selectivity of the o-phenylphenol is 99.6-99.7%, and the calculated yield of the target product o-phenylphenol is 99.4-99.5%.
(4) According to the method for preparing the o-phenylphenol by using the cyclohexanone as the raw material, the gas chromatographic purity of the finally prepared o-phenylphenol is 99.84-99.91%, and when the effective catalytic time of the control catalyst adopted in the dehydration and hydrogenation step is up to 1500 hours, the calculated yield of the target product trans-isomerism o-cyclohexylcyclohexanone can still reach 90.0-90.3%.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The embodiment provides a method for preparing o-phenylphenol by using cyclohexanone as a raw material, which specifically comprises the following steps:
1. Aldol condensation
The cyclohexanone is continuously introduced into a first fixed bed reactor filled with a condensation catalyst from the bottom after being metered by a peristaltic pump, the mass flow rate of the cyclohexanone relative to each kg of the condensation catalyst is controlled to be 200g/min, the aldol condensation temperature in the first fixed bed reactor is controlled to be 25 ℃, the aldol condensation reaction is continuously carried out in the presence of the condensation catalyst to generate 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone, the reacted material is continuously discharged from the top of the first fixed bed reactor, the material is fed into a distillation kettle through a first buffer tank, the distillation vacuum degree is controlled to be 0.09MPa, the distillation temperature is controlled to be 95 ℃, and the unreacted cyclohexanone is distilled and recovered to prepare aldol condensation reaction liquid.
Wherein the condensation catalyst is macroporous strong-alkaline anion exchange resin (the brand name is Langsheng MonoPlus MP500,500 macroporous strong-alkaline anion exchange resin) of quaternized styrene-divinylbenzene copolymer, and the average particle size of the strong-alkaline anion exchange resin is 0.6mm.
In this step, the conversion of cyclohexanone was 19.2%, and the selectivity of the objective 2- (1-hydroxycyclohexyl) cyclohex-1-one was 99.3%.
2. Dehydration hydrogenation
The aldol condensation reaction liquid and hydrogen are respectively preheated to 65 ℃ after being metered, are respectively continuously introduced into a second fixed bed reactor filled with a controlled catalyst from the top, the mass flow rate of the aldol condensation reaction liquid is controlled to be 240g/min per kg of the controlled catalyst, the feeding rate of the hydrogen is 85mL/min, the dehydration hydrogenation temperature in the second fixed bed reactor is 100 ℃, the dehydration hydrogenation reaction is continuously carried out in the presence of the controlled catalyst to generate trans-isomerism o-cyclohexyl cyclohexanone and a small amount of cis-isomerism o-cyclohexyl cyclohexanone, the reacted materials are continuously discharged from the bottom of the second fixed bed reactor, the dehydration hydrogenation reaction liquid is obtained after cooling and is temporarily stored in a second buffer tank, and unreacted excessive hydrogen and dehydrogenation gas are recycled by a recycling device.
In the step, the conversion rate of 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone in the aldol condensation reaction liquid is 99.5%, the selectivity of trans-isomerism ortho-cyclohexyl cyclohexanone is 99.3%, the selectivity of cis-isomerism ortho-cyclohexyl cyclohexanone is 0.21%, and the calculated yield of the target product trans-isomerism ortho-cyclohexyl cyclohexanone is 98.8%.
The calculation method of the calculated yield of the target product trans-isomerism ortho-cyclohexyl cyclohexanone is (the conversion rate of 2- (1-hydroxy cyclohexyl) cyclohexyl-1-ketone in aldol condensation reaction liquid is multiplied by 100 percent of the selectivity of the trans-isomerism ortho-cyclohexyl cyclohexanone).
Wherein, the control catalyst is prepared by the following method:
1) Carrier treatment
Adding MCM-41 molecular sieve into absolute ethyl alcohol with the weight being 8 times that of the molecular sieve, dispersing the molecular sieve in ultrasonic for 5min, stirring and heating to 40 ℃, keeping the temperature and stirring, dripping N, N-dimethylethylenediamine, controlling the dripping of N, N-dimethylethylenediamine to be completed in 50min, then continuously heating to 68 ℃, keeping the temperature and refluxing and stirring for 32h, centrifugally separating out solid matters, washing the solid matters by adopting absolute ethyl alcohol with the weight being 4 times that of the molecular sieve, transferring the solid matters into a vacuum drying oven, and drying the solid matters to constant weight at the vacuum degree of 0.07MPa and 70 ℃ to obtain the modified carrier.
Wherein the weight ratio of the MCM-41 molecular sieve to the N, N-dimethyl ethylenediamine is 1:0.4.
The MCM-41 molecular sieve has a pore diameter of 4.5nm, an average particle diameter of 9 mu m and a specific surface area of 1050m 2/g.
2) Contact bonding
Adding (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl into benzene, stirring for 20min, continuously adding a modified carrier, performing ultrasonic dispersion for 5min, adding triethylamine, stirring and heating to 68 ℃ in a nitrogen atmosphere, performing heat preservation and reflux stirring for 70h, naturally cooling to room temperature, continuously adding pentacarbonyl iron, stirring at room temperature for 22h, centrifuging to separate a solid, washing the solid with 4 times of absolute ethyl alcohol, and drying to obtain the controlled catalyst.
Wherein the weight ratio of the (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl, benzene, the modified carrier, triethylamine and pentacarbonyl iron is 4:100:12:0.2:2.6.
3. Dehydrogenation
Continuously introducing the dehydration-hydrogenation reaction liquid into a gasifier after metering, controlling the temperature of the gasifier to 340 ℃, continuously introducing the gasified dehydration-hydrogenation reaction liquid into a third fixed bed reactor filled with a dehydrogenation catalyst from the top, controlling the mass flow rate of the dehydration-hydrogenation reaction liquid per kg of the dehydrogenation catalyst to be 65g/min, controlling the dehydrogenation pressure in the third fixed bed reactor to be 0.65MPa, continuously performing dehydrogenation reaction at the dehydrogenation temperature to 370 ℃, continuously discharging the reacted material from the bottom of the third fixed bed reactor, cooling to obtain crude o-phenylphenol, temporarily storing the crude o-phenylphenol in a third buffer tank, and recycling hydrogen produced in the dehydrogenation process by a hydrogen dehydrogenation gas recovery device.
Wherein the dehydrogenation catalyst is gamma-alumina loaded with copper oxide and zinc oxide, the content of the copper oxide in the dehydrogenation catalyst is 6.5 percent, and the content of the copper oxide is 9 percent by weight.
In the step, the conversion rate of the o-cyclohexyl cyclohexanone (cis-isomerism and trans-isomerism) in the dehydration hydrogenation reaction liquid is 99.7%, the selectivity of the o-phenylphenol is 99.7%, and the calculated yield of the target product o-phenylphenol is 99.4%.
The calculation method of the calculated yield of the target product o-phenylphenol is (the conversion rate of the o-cyclohexyl cyclohexanone in the dehydration hydrogenation reaction liquid is multiplied by the selectivity of the o-phenylphenol is multiplied by 100 percent).
4. Post-treatment
And (3) introducing the crude product of the o-phenylphenol into a first rectifying tower, carrying out primary rectification to collect light components, introducing the crude product of the o-phenylphenol into a second rectifying tower, carrying out secondary rectification, collecting fractions, and cooling to obtain the o-phenylphenol.
In the embodiment, the gas chromatographic purity of the o-phenylphenol obtained by post-treatment is 99.84%, and when the effective catalytic time of the control catalyst adopted in the dehydration and hydrogenation step reaches 1500 hours, the calculated yield of the target product trans-isomerism o-cyclohexyl cyclohexanone can still reach 90.1%.
Example 2
The embodiment provides a method for preparing o-phenylphenol by using cyclohexanone as a raw material, which specifically comprises the following steps:
1. Aldol condensation
The cyclohexanone is continuously introduced into a first fixed bed reactor filled with a condensation catalyst from the bottom after being metered by a peristaltic pump, the mass flow rate of the cyclohexanone relative to each kg of the condensation catalyst is controlled to be 210g/min, the aldol condensation temperature in the first fixed bed reactor is controlled to be 27 ℃, the aldol condensation reaction is continuously carried out in the presence of the condensation catalyst to generate 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone, the reacted material is continuously discharged from the top of the first fixed bed reactor, the material is fed into a distillation kettle through a first buffer tank, the distillation vacuum degree is controlled to be 0.095MPa, the distillation temperature is controlled to be 99 ℃, and unreacted cyclohexanone is distilled and recovered to prepare aldol condensation reaction liquid.
Wherein the condensation catalyst is macroporous strong-alkaline anion exchange resin (the brand name is Langsheng MonoPlus MP500,500 macroporous strong-alkaline anion exchange resin) of quaternized styrene-divinylbenzene copolymer, and the average particle size of the strong-alkaline anion exchange resin is 0.6mm.
In this step, the conversion of cyclohexanone was 19.5%, and the selectivity of the objective 2- (1-hydroxycyclohexyl) cyclohex-1-one was 99.3%.
2. Dehydration hydrogenation
The aldol condensation reaction liquid and hydrogen are respectively preheated to 68 ℃ after being metered, are respectively continuously introduced into a second fixed bed reactor filled with a controlled catalyst from the top, the mass flow rate of the aldol condensation reaction liquid per kg of the controlled catalyst is controlled to be 260g/min, the feeding rate of the hydrogen is 95mL/min, the dehydration hydrogenation temperature in the second fixed bed reactor is 101 ℃, the dehydration hydrogenation reaction is continuously carried out in the presence of the controlled catalyst to generate trans-isomerism o-cyclohexyl cyclohexanone and a small amount of cis-isomerism o-cyclohexyl cyclohexanone, the reacted materials are continuously discharged from the bottom of the second fixed bed reactor, the dehydration hydrogenation reaction liquid is obtained after cooling and is temporarily stored in a second buffer tank, and unreacted excessive hydrogen and dehydrogenation gas are recycled by a recycling device.
In the step, the conversion rate of 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone in the aldol condensation reaction liquid is 99.6%, the selectivity of trans-isomerism ortho-cyclohexyl cyclohexanone is 99.4%, the selectivity of cis-isomerism ortho-cyclohexyl cyclohexanone is 0.18%, and the calculated yield of the target product trans-isomerism ortho-cyclohexyl cyclohexanone is 99.0%.
Wherein, the control catalyst is prepared by the following method:
1) Carrier treatment
Adding MCM-41 molecular sieve into absolute ethyl alcohol with the weight being 9 times that of the molecular sieve, dispersing the molecular sieve in ultrasonic for 8min, stirring and heating to 42 ℃, keeping the temperature and stirring, dripping N, N-dimethylethylenediamine, controlling the dripping of N, N-dimethylethylenediamine to be completed in 55min, then continuously heating to 70 ℃, keeping the temperature and refluxing and stirring for 34h, centrifugally separating out solid matters, washing the solid matters by adopting absolute ethyl alcohol with the weight being 4.5 times that of the molecular sieve, transferring the solid matters into a vacuum drying oven, and drying the solid matters to constant weight at the vacuum degree of 0.075MPa and 72 ℃ to obtain the modified carrier.
Wherein the weight ratio of the MCM-41 molecular sieve to the N, N-dimethyl ethylenediamine is 1:0.45.
The MCM-41 molecular sieve has a pore diameter of 4.5nm, an average particle diameter of 9 mu m and a specific surface area of 1050m 2/g.
2) Contact bonding
Adding (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl into benzene, stirring for 25min, continuously adding a modified carrier, performing ultrasonic dispersion for 8min, adding triethylamine, stirring and heating to 69 ℃ in a nitrogen atmosphere, performing heat preservation and reflux stirring for 71h, naturally cooling to room temperature, continuously adding iron pentacarbonyl, stirring for 23h at room temperature, centrifuging to separate a solid, washing the solid with 4.5 times of absolute ethyl alcohol, and drying to obtain the controlled catalyst.
Wherein the weight ratio of the (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl, benzene, the modified carrier, triethylamine and pentacarbonyl iron is 4.1:100:12.3:0.25:2.7.
3. Dehydrogenation
Continuously introducing the dehydration-hydrogenation reaction liquid into a gasifier after metering, controlling the temperature of the gasifier to be 345 ℃, continuously introducing the gasified dehydration-hydrogenation reaction liquid into a third fixed bed reactor filled with a dehydrogenation catalyst from the top, controlling the mass flow rate of the dehydration-hydrogenation reaction liquid per kg of the dehydrogenation catalyst to be 70g/min, continuously carrying out dehydrogenation reaction at the dehydrogenation temperature of 375 ℃ under the existence of the dehydrogenation catalyst, continuously discharging the reacted material from the bottom of the third fixed bed reactor, cooling to obtain crude o-phenylphenol, temporarily storing the crude o-phenylphenol in a third buffer tank, and recycling hydrogen produced in the dehydrogenation process by a hydrogen dehydrogenation gas recycling device.
Wherein the dehydrogenation catalyst is gamma-alumina loaded with copper oxide and zinc oxide, the content of the copper oxide in the dehydrogenation catalyst is 6.8 percent, and the content of the copper oxide is 9.2 percent by weight.
In the step, the conversion rate of the o-cyclohexyl cyclohexanone (cis-isomerism and trans-isomerism) in the dehydration hydrogenation reaction liquid is 99.8%, the selectivity of the o-phenylphenol is 99.7%, and the calculated yield of the target product o-phenylphenol is 99.5%.
4. Post-treatment
And (3) introducing the crude product of the o-phenylphenol into a first rectifying tower, carrying out primary rectification to collect light components, introducing the crude product of the o-phenylphenol into a second rectifying tower, carrying out secondary rectification, collecting fractions, and cooling to obtain the o-phenylphenol.
In the embodiment, the gas chromatographic purity of the o-phenylphenol prepared by post-treatment is 99.91%, and when the effective catalytic time of the control catalyst adopted in the dehydration and hydrogenation step reaches 1500 hours, the calculated yield of the target product trans-isomerism o-cyclohexyl cyclohexanone can still reach 90.3%.
Example 3
The embodiment provides a method for preparing o-phenylphenol by using cyclohexanone as a raw material, which specifically comprises the following steps:
1. Aldol condensation
The cyclohexanone is continuously introduced into a first fixed bed reactor filled with a condensation catalyst from the bottom after being metered by a peristaltic pump, the mass flow rate of the cyclohexanone relative to each kg of the condensation catalyst is controlled to be 205g/min, the aldol condensation temperature in the first fixed bed reactor is controlled to be 30 ℃, the aldol condensation reaction is continuously carried out in the presence of the condensation catalyst to generate 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone, the reacted material is continuously discharged from the top of the first fixed bed reactor, the material is fed into a distillation kettle through a first buffer tank, the distillation vacuum degree is controlled to be 0.098MPa, the distillation temperature is controlled to be 100 ℃, and the unreacted cyclohexanone is distilled and recovered to prepare aldol condensation reaction liquid.
Wherein the condensation catalyst is macroporous strong-alkaline anion exchange resin (the brand name is Langsheng MonoPlus MP500,500 macroporous strong-alkaline anion exchange resin) of quaternized styrene-divinylbenzene copolymer, and the average particle size of the strong-alkaline anion exchange resin is 0.6mm.
In this step, the conversion of cyclohexanone was 19.4%, and the selectivity of the objective 2- (1-hydroxycyclohexyl) cyclohex-1-one was 99.2%.
2. Dehydration hydrogenation
The aldol condensation reaction liquid and hydrogen are respectively preheated to 70 ℃ after being metered, are respectively continuously introduced into a second fixed bed reactor filled with a controlled catalyst from the top, the mass flow rate of the aldol condensation reaction liquid is controlled to be 250g/min, the feeding rate of the hydrogen is 90mL/min, the dehydration hydrogenation temperature in the second fixed bed reactor is 102 ℃, the dehydration hydrogenation reaction is continuously carried out in the presence of the controlled catalyst to generate trans-isomerism o-cyclohexyl cyclohexanone and a small amount of cis-isomerism o-cyclohexyl cyclohexanone, the reacted materials are continuously discharged from the bottom of the second fixed bed reactor, the dehydration hydrogenation reaction liquid is obtained after cooling and is temporarily stored in a second buffer tank, and unreacted excessive hydrogen and dehydrogenation gas is recycled by a recovery device.
In the step, the conversion rate of 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone in the aldol condensation reaction liquid is 99.6%, the selectivity of trans-isomerism ortho-cyclohexyl cyclohexanone is 99.4%, the selectivity of cis-isomerism ortho-cyclohexyl cyclohexanone is 0.20%, and the calculated yield of the target product trans-isomerism ortho-cyclohexyl cyclohexanone is 99.0%.
Wherein, the control catalyst is prepared by the following method:
1) Carrier treatment
Adding MCM-41 molecular sieve into 10 times of absolute ethyl alcohol, dispersing by ultrasonic for 10min, stirring and heating to 45 ℃, keeping the temperature and stirring, dripping N, N-dimethyl ethylenediamine, controlling the dripping of N, N-dimethyl ethylenediamine to be completed in 60min, then continuously heating to 72 ℃, keeping the temperature and refluxing and stirring for 36h, centrifugally separating out solid, washing the solid by adopting 5 times of absolute ethyl alcohol, transferring into a vacuum drying oven, and drying to constant weight at the vacuum degree of 0.08MPa and 75 ℃ to obtain the modified carrier.
Wherein the weight ratio of the MCM-41 molecular sieve to the N, N-dimethyl ethylenediamine is 1:0.5.
The MCM-41 molecular sieve has a pore diameter of 4.5nm, an average particle diameter of 9 mu m and a specific surface area of 1050m 2/g.
2) Contact bonding
Adding (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl into benzene, stirring for 30min, continuously adding a modified carrier, performing ultrasonic dispersion for 10min, adding triethylamine, stirring and heating to 70 ℃ in a nitrogen atmosphere environment, performing heat preservation and reflux stirring for 72h, naturally cooling to room temperature, continuously adding pentacarbonyl iron, stirring at room temperature for 24h, centrifuging to separate out a solid, washing the solid with 5 times of absolute ethyl alcohol, and drying to obtain the controlled catalyst.
Wherein the weight ratio of the (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl, benzene, the modified carrier, triethylamine and pentacarbonyl iron is 4.2:100:12.5:0.3:2.8.
3. Dehydrogenation
Continuously introducing the dehydration-hydrogenation reaction liquid into a gasifier after metering, controlling the temperature of the gasifier to be 350 ℃, continuously introducing the gasified dehydration-hydrogenation reaction liquid into a third fixed bed reactor filled with a dehydrogenation catalyst from the top, controlling the mass flow rate of the dehydration-hydrogenation reaction liquid per kg of the dehydrogenation catalyst to be 68g/min, controlling the dehydrogenation pressure in the third fixed bed reactor to be 0.75MPa, continuously performing dehydrogenation reaction at the dehydrogenation temperature to be 380 ℃, continuously discharging the reacted material from the bottom of the third fixed bed reactor, cooling to obtain crude o-phenylphenol, temporarily storing in a third buffer tank, and recycling hydrogen and dehydrogenation gas generated in the dehydrogenation process by a hydrogen dehydrogenation gas recycling device.
Wherein the dehydrogenation catalyst is gamma-alumina loaded with copper oxide and zinc oxide, the content of the copper oxide in the dehydrogenation catalyst is 7 percent, and the content of the copper oxide is 9.3 weight percent.
In the step, the conversion rate of the o-cyclohexyl cyclohexanone (cis-isomerism and trans-isomerism) in the dehydration hydrogenation reaction liquid is 99.8%, the selectivity of the o-phenylphenol is 99.6%, and the calculated yield of the target product o-phenylphenol is 99.4%.
4. Post-treatment
And (3) introducing the crude product of the o-phenylphenol into a first rectifying tower, carrying out primary rectification to collect light components, introducing the crude product of the o-phenylphenol into a second rectifying tower, carrying out secondary rectification, collecting fractions, and cooling to obtain the o-phenylphenol.
In the embodiment, the gas chromatographic purity of the o-phenylphenol prepared by post-treatment is 99.90%, and when the effective catalytic time of the control catalyst adopted in the dehydration and hydrogenation step reaches 1500 hours, the calculated yield of the target product trans-isomerism o-cyclohexyl cyclohexanone can still reach 90.0%.
According to the method for preparing o-phenylphenol by using cyclohexanone as a raw material, disclosed by the embodiment 1-3, the cyclohexanone is used as the raw material, aldol condensation reaction is continuously carried out in a first fixed bed reactor to produce 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone, aldol condensation reaction liquid is prepared, then dehydration hydrogenation is continuously carried out in a second fixed bed reactor in the presence of a controlled catalyst by aldol condensation reaction liquid and hydrogen in a dehydration hydrogenation step, and meanwhile, chiral catalytic ligand (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl and pentacarbonyl iron are matched to perform asymmetric catalytic action on 2- (1-hydroxycyclohexyl) cyclohexyl-1-ketone in the dehydration hydrogenation process, so that trans-isomerism o-cyclohexyl cyclohexanone can be effectively catalyzed and highly selectively generated, and generation of cis-isomerism o-cyclohexyl cyclohexanone is inhibited, and the dehydration hydrogenation reaction liquid is prepared. In the carrier treatment step of preparing the controlled catalyst, a specific MCM-41 molecular sieve is selected as a basic carrier, N-dimethyl ethylenediamine is adopted to carry out surface amination treatment on the MCM-41 molecular sieve to prepare a modified carrier, and then in the contact bonding step, (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl is adopted to be in contact bonding with the modified carrier, and then iron pentacarbonyl is contacted for further contact bonding, so that the controlled catalyst is prepared. In the dehydrogenation step, the dehydration hydrogenation reaction liquid is gasified and then subjected to continuous dehydrogenation reaction in a third fixed bed reactor in the presence of a dehydrogenation catalyst to obtain an o-phenylphenol crude product, the o-phenylphenol crude product is subjected to post-treatment purification to finally obtain an o-phenylphenol product, the technical means are matched and synergistic, the defects of the traditional cyclohexanone condensation dehydrogenation method can be effectively overcome, trans-isomerised o-cyclohexylcyclohexanone is effectively catalyzed and generated in a high selectivity manner in the dehydration hydrogenation process, the generation of cis-isomerised o-cyclohexylcyclohexanone is inhibited, the problem that the overall dehydrogenation reaction efficiency is low due to the fact that a large amount of coexisting cis-isomer and trans-isomer of o-cyclohexylcyclohexanone are poor in the preparation process is avoided, the dehydrogenation reaction efficiency is effectively improved, the yield of a dehydrogenation product (o-phenylphenol) is further improved, meanwhile, the problem that the activity of the catalyst is effectively catalyzed and the activity of the cis-isomerised o-cyclohexylcyclohexanone is reduced in the dehydration hydrogenation process is effectively avoided, the problem that the activity of the catalyst is reduced in the dehydration hydrogenation process is prolonged, the dehydrogenation efficiency is effectively improved, the dehydrogenation efficiency is prolonged, and the service life of the catalyst is prolonged is effectively prevented. Furthermore, the generation of cis-isomerism ortho-cyclohexyl cyclohexanone is effectively inhibited in the dehydration and hydrogenation process, the safety risk caused by the property difference of cis-isomerism ortho-cyclohexyl cyclohexanone and trans-isomerism cyclohexyl cyclohexanone in the subsequent dehydrogenation process can be avoided, monitoring and tracking of two configurations of ortho-cyclohexyl cyclohexanone are not needed in the subsequent dehydrogenation reaction, the process control convenience is improved, the operation difficulty is reduced, and the large-scale production is facilitated.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the method is characterized in that 1) a conventional catalyst (1 percent Rh-5 percent phosphotungstic acid/active carbon) is adopted to replace a control catalyst in the dehydration and hydrogenation step, the mass flow rate of an aldol condensation reaction liquid relative to each kg of catalyst in the dehydration and hydrogenation step is controlled to be 70g/min, and 2) the mass flow rate of the dehydration and hydrogenation reaction liquid relative to each kg of dehydrogenation catalyst in the dehydrogenation step is controlled to be 20g/min.
In the dehydration hydrogenation step of comparative example 1, the conversion of 2- (1-hydroxycyclohexyl) cyclohex-1-one in the aldol condensation reaction liquid was 97.7%, the selectivity for trans-isomer o-cyclohexylcyclohexanone was 57.2%, and the selectivity for cis-isomer o-cyclohexylcyclohexanone was 40.1%.
Meanwhile, due to the limitation of the catalyst in the dehydration and hydrogenation step, the optimal mass flow rate of the aldol condensation reaction liquid relative to each kg of catalyst is 70g/min, and due to the existence of cis-isomerism ortho-cyclohexyl cyclohexanone, the surface active sites of the dehydrogenation catalyst can be covered or blocked in the dehydrogenation step, the optimal mass flow rate of the dehydration and hydrogenation reaction liquid relative to each kg of dehydrogenation catalyst is 20g/min, and the effective catalytic duration of the dehydrogenation catalyst is shortened by 41.9% compared with that of the embodiment 2.
As can be seen from comparative example 1, the conventional catalyst is adopted in the dehydration-hydrogenation step, in the dehydration-hydrogenation reaction process, the asymmetric catalytic effect on 2- (1-hydroxycyclohexyl) cyclohexane-1-one cannot be realized by the cooperation of chiral catalytic ligand (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl and pentacarbonyl iron in the controlled catalyst, so that trans-isomerised o-cyclohexyl cyclohexanone cannot be effectively catalyzed and generated in a high selectivity manner, and the generation of cis-isomerised o-cyclohexyl cyclohexanone cannot be effectively inhibited at the same time. In particular, the reaction efficiency in the dehydration hydrogenation and dehydrogenation steps is reduced, the selectivity of trans-isomerised ortho-cyclohexyl cyclohexanone is significantly reduced, and the effective catalytic duration of the dehydrogenation catalyst employed in comparative example 1 is significantly shortened compared to that of example 2.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that 1) the carrier treatment step is omitted in the preparation of the controlled catalyst, and 2) the addition of (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl is omitted in the contact bonding step in the preparation of the controlled catalyst.
In the dehydration hydrogenation step of comparative example 2, the conversion of 2- (1-hydroxycyclohexyl) cyclohex-1-one in the aldol condensation reaction liquid was 98.9%, the selectivity for trans-isomeric orthocyclohexyl cyclohexanone was 51.0%, the selectivity for cis-isomeric orthocyclohexyl cyclohexanone was 43.7%, and the effective catalytic duration of the control catalyst used in the dehydration hydrogenation step was about 800 hours.
Meanwhile, due to the existence of cis-isomerism ortho-cyclohexyl cyclohexanone in the dehydrogenation step, the covering or blocking of the surface active sites of the dehydrogenation catalyst can be caused, and the effective catalytic duration of the dehydrogenation catalyst is shortened by 39.8 percent compared with that of the embodiment 2.
As can be seen from comparative example 2, in the preparation of the controlled catalyst, the carrier treatment step and the addition of (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl are omitted, and in the dehydration hydrogenation reaction process, the asymmetric catalysis of 2- (1-hydroxycyclohexyl) cyclohexane-1-one cannot be realized by the cooperation of chiral catalytic ligand (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl and pentacarbonyl iron in the controlled catalyst, so that trans-isomerism o-cyclohexyl cyclohexanone cannot be generated effectively and selectively, and the generation of cis-isomerism o-cyclohexyl cyclohexanone cannot be restrained effectively at the same time, and the method is characterized in that the reaction efficiency is reduced in the dehydration hydrogenation and dehydrogenation steps, and the selectivity of the trans-isomerism o-cyclohexyl cyclohexanone is remarkably reduced. Meanwhile, the surface amination treatment of the MCM-41 molecular sieve by N, N-dimethyl ethylenediamine is omitted, the combination property of a molecular sieve carrier and iron pentacarbonyl is reduced, and the effective catalytic duration of a control catalyst adopted in the dehydration and hydrogenation step is obviously reduced. Furthermore, cis-isomerism ortho-cyclohexyl cyclohexanone can additionally occupy active sites of the catalyst, so that the active sites on the surface of the catalyst are covered or blocked, the catalytic activity and long-term stability of the catalyst adopted in the dehydrogenation step are further reduced, and the effective service life of the catalyst is reduced. In particular, the effective catalytic duration of the dehydrogenation catalyst employed in comparative example 2 was significantly shortened compared to that of example 2.
The percentages used in the present invention are mass percentages unless otherwise indicated.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, but may be modified or substituted for some of the technical features thereof by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for preparing o-phenylphenol by using cyclohexanone as a raw material is characterized by comprising the following steps of aldol condensation, dehydration hydrogenation, dehydrogenation and post-treatment;
The aldol condensation method comprises the steps of continuously introducing cyclohexanone into a first fixed bed reactor filled with a condensation catalyst, continuously performing aldol condensation reaction, continuously discharging reacted materials from the first fixed bed reactor, and distilling to recover unreacted cyclohexanone to obtain aldol condensation reaction liquid;
The dehydration and hydrogenation method comprises the steps of respectively preheating aldol condensation reaction liquid and hydrogen, continuously introducing the aldol condensation reaction liquid and the hydrogen into a second fixed bed reactor filled with a controlled catalyst, continuously carrying out dehydration and hydrogenation reaction, and continuously discharging reacted materials from the second fixed bed reactor to obtain dehydration and hydrogenation reaction liquid;
In the dehydration and hydrogenation, the mass flow rate of an aldol condensation reaction liquid relative to each kg of a control catalyst is controlled to be 240-260g/min, the feeding rate of hydrogen is 85-95mL/min, and the dehydration and hydrogenation temperature in a second fixed bed reactor is 100-102 ℃;
The control catalyst is prepared by the following steps of carrier treatment and contact bonding;
The carrier treatment method comprises the steps of putting an MCM-41 molecular sieve into absolute ethyl alcohol, dispersing uniformly, heating to 40-45 ℃, keeping the temperature, stirring, dripping N, N-dimethylethylenediamine, continuously heating to 68-72 ℃ after dripping, keeping the temperature, refluxing, stirring for 32-36h, separating out solid matters, washing and drying the solid matters to obtain a modified carrier;
In the carrier treatment, the dripping time of N, N-dimethyl ethylenediamine is controlled to be 50-60min;
In the carrier treatment, the weight ratio of the MCM-41 molecular sieve to the N, N-dimethyl ethylenediamine is 1:0.4-0.5;
The contact bonding method comprises the steps of adding (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl into benzene, continuously adding a modified carrier after uniform dispersion, uniformly dispersing, adding triethylamine, stirring and heating to 68-70 ℃ in a nitrogen atmosphere, keeping warm and refluxing and stirring for 70-72h, cooling to room temperature, continuously adding pentacarbonyl iron, stirring at room temperature for 22-24h, separating out solid matters, washing and drying the solid matters, and preparing the control catalyst;
In the contact bonding, the weight ratio of the (R) - (+) -2,2 '-bis (diphenylphosphine) -1,1' -binaphthyl, benzene, a modified carrier, triethylamine and pentacarbonyl iron is 4-4.2:100:12-12.5:0.2-0.3:2.6-2.8;
The dehydrogenation method comprises the steps of continuously introducing a dehydration hydrogenation reaction liquid into a third fixed bed reactor filled with a dehydrogenation catalyst after gasification, continuously carrying out dehydrogenation reaction, and continuously discharging reacted materials from the third fixed bed reactor to obtain crude o-phenylphenol;
The post-treatment method is that the crude product of the o-phenylphenol is purified by rectification to obtain the o-phenylphenol.
2. The method for preparing o-phenylphenol from cyclohexanone according to claim 1, wherein in the aldol condensation, the mass flow rate of cyclohexanone relative to each kg of condensation catalyst is controlled to be 200-210g/min, and the aldol condensation temperature in the first fixed bed reactor is controlled to be 25-30 ℃;
The condensation catalyst is a macroporous strong base anion exchange resin of a quaternized styrene-divinylbenzene copolymer.
3. The method for preparing o-phenylphenol from cyclohexanone according to claim 1, wherein in the carrier treatment, the MCM-41 molecular sieve has a pore diameter of 4.5-5nm, an average particle diameter of 8-10 μm and a specific surface area of 1000-1100m 2/g.
4. The method for preparing o-phenylphenol from cyclohexanone according to claim 1, wherein in the dehydrogenation, a mass flow rate of a dehydration hydrogenation reaction liquid relative to a dehydrogenation catalyst per kg is controlled to be 65-70g/min, a dehydrogenation pressure in a third fixed bed reactor is controlled to be 0.65-0.75MPa, and a dehydrogenation temperature is controlled to be 370-380 ℃.
5. The method for preparing o-phenylphenol by using cyclohexanone as raw material according to claim 1, wherein in the dehydrogenation, the dehydrogenation catalyst is gamma-alumina loaded with copper oxide and zinc oxide, the content of copper oxide in the dehydrogenation catalyst is 6.5-7%, and the content of copper oxide is 9-9.3wt%.
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| CN115745750B (en) * | 2022-09-28 | 2023-12-15 | 山东天隅新材料科技有限公司 | O-phenylphenol, preparation method and application thereof |
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