WO2013012203A2 - Procédé de préparation d'alcool cumylique et procédé de préparation de phénol, d'acétone et d'alpha méthylstyrène - Google Patents

Procédé de préparation d'alcool cumylique et procédé de préparation de phénol, d'acétone et d'alpha méthylstyrène Download PDF

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WO2013012203A2
WO2013012203A2 PCT/KR2012/005539 KR2012005539W WO2013012203A2 WO 2013012203 A2 WO2013012203 A2 WO 2013012203A2 KR 2012005539 W KR2012005539 W KR 2012005539W WO 2013012203 A2 WO2013012203 A2 WO 2013012203A2
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cumene hydroperoxide
reaction
catalyst
cumyl alcohol
methyl styrene
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PCT/KR2012/005539
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English (en)
Korean (ko)
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WO2013012203A3 (fr
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하승백
유석준
조동현
이태철
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주식회사 엘지화학
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Priority claimed from KR1020110070516A external-priority patent/KR101476376B1/ko
Priority claimed from KR1020110073166A external-priority patent/KR101447255B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2014502490A priority Critical patent/JP5642314B2/ja
Priority to CN201280023345.8A priority patent/CN103562168B/zh
Publication of WO2013012203A2 publication Critical patent/WO2013012203A2/fr
Publication of WO2013012203A3 publication Critical patent/WO2013012203A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Definitions

  • the present invention relates to a method for preparing cumyl alcohol and a method for preparing phenol, acetone, and alpha methyl styrene, and more particularly, to preparing cumyl alcohol capable of selectively increasing alpha methyl styrene without reducing the production of phenol. And to a process for the preparation of phenol, acetone, and alpha methyl styrene.
  • Alpha-methyl styrene is widely used as an additive in the manufacture of certain copolymers and novel polymers such as ABS.
  • Alpha methyl styrene also has use as an intermediate for the preparation of fine compounds such as unsaturated alpha methyl styrene dimers. These dimers have been used as molecular weight control agents in the preparation of copolymers such as acrylonitrile-butadiene-styrene resins and styrene-butadiene rubbers.
  • the hydrogenated form of alpha methyl styrene dimer has industrial value as a component in lubricating compositions.
  • Such alpha methyl styrene is generally produced as a by-product of the phenol production process for producing phenol through oxidation and dehydration processes using cumene as a raw material.
  • FIG. 1 is a process diagram briefly showing a conventional phenol production process.
  • a stream in which cumene is oxidized in the presence of oxygen in a cumene-supplied oxygen reactor (1) is converted into cumene hydroperoxide and a small amount of cumyl alcohol in an amount of about 24% by weight.
  • the stream is concentrated to 82 weight percent.
  • the concentrated cumene hydroperoxide and cumyl alcohol containing streams are then fed via a reservoir (4) to a cracking reaction vessel (5) to dehydrate under acid catalyst to produce phenol and acetone from cumene hydroperoxide and also from cumyl alcohol Produces alpha methyl styrene.
  • the conventional method discloses a method of converting the hydrogenation process of the alpha methyl styrene produced for recycling to the reaction reaction group back to cumene, not mainly for the purpose of increasing the alpha methyl styrene (US Pat. No. 5,905,178). Or, by treating alpha methyl styrene as a by-product of the phenol production process, attempts to minimize the production of alpha methyl styrene are mainly made (US Pat. No. 5,530,166). However, there is insufficient research to increase the production of alpha methyl styrene. to be.
  • the present invention provides a method for producing cumyl alcohol and phenol that can selectively increase the alpha methyl styrene was considered as a by-product in the phenol production process by hydrogenation from cumene hydroperoxide to cumyl alcohol To provide acetone, and a method for producing alpha methyl styrene.
  • the present invention provides a process for preparing cumyl alcohol in which hydrogenation of cumene hydroperoxide is carried out under a Pd-Co catalyst.
  • the steps (c) and (d) may be performed simultaneously in the same reaction period.
  • the steps (c) and (d) may be performed separately in a separate reaction period.
  • the weight ratio of Pd: Co in the Pd-Co catalyst may be 1: 0.05 to 1: 1.
  • the semi-ungmul containing cumyl alcohol may be dehydrated under an acidic catalyst.
  • the semi-ungmul containing cumyl alcohol may be dehydrated under a resin catalyst.
  • the cumene hydroperoxide stream may be produced at a concentration of 5 to 25% by weight.
  • cumene hydroperoxide switch by separating the stream of 5 to 50 parts by weight 0/0 can be used in the hydrogenation banung.
  • the selectivity of the hydrogenation reaction may be 95% or more, and the conversion of cumene hydroperoxide to cumyl alcohol may be 80% or more.
  • a method of preparing cumyl alcohol of the present invention and a method of preparing phenol, acetone, and alpha methyl styrene will be described in more detail.
  • Method for producing cumyl alcohol of the present invention is cumene hydroperoxide Pd-
  • Pd-Co catalysts in the hydrogenation of cumene hydroperoxide can convert cumene hydroperoxide to cumyl alcohol with high conversion and selectivity.
  • the hydrogenation reaction may be performed at a temperature of about 40 to about 80 ° C for about 0.2 to about 7 hours, but is not limited thereto.
  • the hydrogenation reaction can also be carried out under conditions of normal fluid space velocity.
  • the hydrogenation can be carried out by adding about 1 to about 10 moles of hydrogen with respect to 1 mole of cumene hydroperoxide in conventional reaction groups well known in the art. At this time, if the added mole number of hydrogen is less than 1 mole, there is a problem that the conversion and selectivity is lowered.
  • the Pd-Co catalyst may further include a carrier selected from the group consisting of alumina, silica, clay, carbon, zirconia, titania, mesoporous molecular sieves, and combinations thereof.
  • the Pd-Co catalyst is preferably used a Pd-Co / C catalyst containing carbon as a carrier.
  • the Pd-Co catalyst may be used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of cumene hydroperoxide stream at a concentration of 25% by weight.
  • the amount of the Pd-Co catalyst is 5 to 15 parts by weight, it may exhibit high conversion and selectivity. .
  • the weight ratio of Pd: Co in the Pd-Co catalyst of the present invention may be 1: 0.05 to 1: 1, preferably 1: 0.2 to 1: 0.5.
  • the weight ratio of Pd: Co is 1: 0.2, conversion to cumyl alcohol can be achieved with the highest conversion and selectivity within the same hydrogenation reaction time.
  • the production method of the present invention since the hydrogenation process of cumene hydroperoxide is carried out under mild conditions, it reduces the risk of explosion at runway reaction temperature of cumene hydroperoxide to increase the conversion to cumyl alcohol under the most stabilized conditions. Can be.
  • the selectivity of the hydrogenation reaction in the method for producing cumyl alcohol of the present invention is the selectivity of the hydrogenation reaction in the method for producing cumyl alcohol of the present invention.
  • a phenol manufacturing process is the cumene level of 25 weight 0/0 produced through an oxidation banung hydroperoxide (CHP) solution through the stripper concentrated to CHP solution of 80 increased 0/0, and phenol through an exploded banung, acetone , And a process for producing alpha methyl styrene.
  • CHP oxidation banung hydroperoxide
  • cumene hydroperoxide has a flash point of 57 to 79 ° C, it is explosive when mixed with air. Furthermore, there is a risk of explosion and fire upon contact with organic materials, acids, bases and metals. In addition, as the concentration of cumene hydroperoxide increases, the runway reaction temperature decreases, which may cause an explosion hazard. There is a report of increase (Thermochimica acta, 501, 2010, 65-71). Therefore, there is a need for a method for performing a phenol plant in a stable manner without using a high concentration of Cuman hydroperoxide as described above.
  • the production method of the present invention provides a process capable of producing cumyl alcohol in a stable state using a low concentration of cumene hydroperoxide.
  • cumyl alcohol has only about 0.035 moles of cumene hydroperoxide 1, thereby limiting the production of alpha methyl styrene.
  • the production method of the present invention after increasing the yield of cumyl alcohol through the hydrogenation process of cumene hydroperoxide to cumyl alcohol, it is possible to increase the production of alpha methyl styrene by dehydrating the cumyl alcohol. That is, in the prior art, while the cumene hydroperoxide stream obtained by the oxidation of cumene is concentrated in a stripper and then dehydrated as it is in a decomposition reactor, the method of the present invention provides the oxidation in a low concentration state before concentration in a stripper. By separating a part of cumene hydroperoxide obtained after the reaction and using it in the hydrogenation process, the selectivity of cumene hydroperoxide and conversion to cumyl alcohol can be improved.
  • the production method of the present invention shows a much better result than the conventional by converting cumene hydroperoxide to cumyl alcohol in the region of low concentration stability is secured in the production process.
  • the cumene hydroperoxide stream before passing through the stripper into the cleavage reactor is not used as a reaction counterpart of the hydrogenation reaction reaction, but the cumene hydroperoxide after cumene oxidation is used. Ensure stability of the process.
  • step (a) cumene is oxidized to produce a cumene hydroperoxide stream.
  • step (a) through the steps of: (a) the process of, the hydroperoxide stream of cumene in the range of about 5 to about 25 parts by weight 0/0 concentration can be produced eu also the oxidation of the cumene while the stream Via a small amount of cumyl alcohol.
  • the oxidation conditions in step (a) is not particularly limited, and may be performed under general conditions.
  • the oxidation of cumene can usually be carried out by automatic oxidation with an oxygen-containing gas such as air or oxygen enriched air.
  • the oxidation reaction can also be carried out with or without additives such as alkalis.
  • the additives include alkali metal compounds such as sodium hydroxide (NaOH), potassium hydroxide (KOH), alkaline earth metal compounds, alkali metal carbonates such as sodium carbonate (Na 2 CO 3 ), sodium hydrogen carbonate (NaHC0 3 ), ammonia, ammonium carbonate Etc. may be used, but the present invention is not limited thereto.
  • the oxidation reaction can be carried out at a pressure of about 50 to about 200 ° C and a atmospheric pressure of about 5 MPa.
  • step (a) may be carried out through a plurality of oxidation reaction groups, preferably three oxidation reaction groups used in a conventional phenol process. Further, step (a) may oxidize a cumene containing stream having a cumene concentration of at least 80%, preferably at least 98% in the presence of an oxygen containing stream to form a cumene hydroperoxide containing stream.
  • conventional initiators may be used to promote oxidation of the cumene.
  • the initiator may be an organic hydroperoxide such as cumene hydroperoxide, t-butyl hydroperoxide, a peroxy free radical initiator, an azo free radical initiator, or the like, but is not limited thereto.
  • step (b) At least a part of the cumene hydroperoxide stream prepared in step (a) is separated and reacted with hydrogen under a Pd-Co catalyst to prepare cumyl alcohol (step (b)).
  • Part of the cumene hydroperoxide stream separated in step (b) is converted to cumyl alcohol and then produces alpha methyl styrene, thus hydrogenating
  • the amount of alpha methyl styrene can be controlled by appropriately adjusting the proportion of the cumene hydroperoxide stream used in the reaction.
  • a portion of the cumene hydroperoxide stream preferably about 5 to about 50% by weight, can be separated and used for the reaction.
  • the cumene hydroperoxide stream may be subjected to a hydrogenation reaction by separating at least a portion without concentration.
  • cumene hydroperoxide can be converted into cumyl alcohol with high conversion and selectivity by using a Pd-Co catalyst.
  • Pd-Co catalyst it is possible to shorten the time to convert cumene hydroperoxide to cumyl alcohol to enjoy the entire process time.
  • the Pd-Co catalyst may further include a carrier selected from the group consisting of alumina, silica, clay, carbon, zirconia, titania, mesoporous molecular sieves, and combinations thereof.
  • the Pd-Co catalyst may be a Pd-Co / C catalyst containing carbon as a carrier.
  • the Pd-Co catalyst may be used in an amount of about 0.5 to about 15 parts by weight based on 100 parts by weight of cumene hydroperoxide stream having a concentration of 25% by weight.
  • the amount of the Pd-Co catalyst is 0.5 to 15 parts by weight, it may exhibit high conversion and selectivity.
  • the weight ratio of Pd: Co in the Pd-Co catalyst of the present invention may be 1: 0.05 to 1: 1, preferably 1: 0.2 to 1 :(). 5.
  • the weight ratio of Pd: Co is 1: 0.2.
  • the hydrogenation reaction may be performed for about 0.2 to about 7 hours at a temperature condition of about 40 to about 80 ° C.
  • the hydrogenation reaction can also be carried out under conditions of ordinary fluid space velocity.
  • the hydrogenation reaction may be performed by adding about 1 to about 10 moles and hydrogen per 1 mole of cumene hydroperoxide. At this time, if the number of moles of hydrogen added is less than 1 mole, there is a problem of low conversion and selectivity. If exceeded, excessive amounts of hydrogen must be recycled, which may cause economic problems.
  • the process of hydrogenation of cumene hydroperoxide is carried out under mild conditions, so the runway reaction of cumene hydroperoxide may reduce the explosion risk of the city and increase the conversion to cumyl alcohol under the most stabilized conditions.
  • high concentrations of cumene hydroperoxide can be converted to cumyl alcohol, thereby increasing the alpha methyl styrene content in subsequent steps.
  • Selectivity of the hydrogenation reaction in the production method of the present invention may be 95% or more, more preferably 98% or more.
  • the conversion rate is 20 to 35%
  • the selectivity is 80%
  • the maximum yield is not 40%
  • the hydrogenation process of the present invention is about 3 hours.
  • Cumyl alcohol can be obtained with a conversion rate of 80%, a selectivity of 95%, and a yield of 80% or more within a hydrogenation reaction time, and a conversion rate of 99%, a selectivity of 98%, and a yield of 98% or more within a hydrogenation reaction time of about 4 hours. Cumyl alcohol can be obtained. Increasing the reaction time can also yield cumyl alcohol with substantially 100% conversion.
  • cumene which is mixed with cumene hydroperoxide in the hydrogenation process, may be converted to some cumyl alcohol, and thus, further yield improvement may be expected.
  • step (c) the reaction product containing the cumyl alcohol is dehydrated (step (c)), and the remaining portion of the Coman hydroperoxide stream which has not undergone the hydrogenation reaction is dehydrated (step (d)).
  • Step (c) is a step of obtaining alpha methyl styrene by dehydration reaction of cumyl alcohol.
  • step (d) is a step of obtaining phenol and acetone by dehydration reaction of cumene hydroperoxide. .
  • the steps (c) and (d) may be performed simultaneously in the same reaction period.
  • Concentration at a concentration of 80 to 82% by weight may proceed to dehydration reaction.
  • the semi-ungmul containing cumyl alcohol may be dehydrated under acidic catalyst.
  • step (d) the remainder of the cumene hydroperoxide stream that has not undergone the hydrogenation reaction can be dehydrated under acidic catalyst.
  • the acidic catalyst may be a liquid or solid acidic catalyst.
  • the liquid acidic catalyst is hydrochloric acid, sulfuric acid or nitric acid, preferably sulfuric acid can be used.
  • the solid acidic catalyst is also selected from the group consisting of Group 4 metal oxides modified by Group 6 metal oxides, sulfated transition metal oxides, mixed metal oxides of cerium oxides and Group 4 bimetallic oxides, and mixtures thereof. desirable.
  • the semi-ungmul containing cumyl alcohol may be dehydrated under a resin catalyst.
  • the remaining portion of the cumene hydroperoxide stream that has not undergone the hydrogenation reaction can be dewatered under a resin catalyst.
  • the resin catalyst may be, for example, a polystyrene-based cation exchange resin, it is preferable to use a sulfonated polystyrene-based cation exchange resin catalyst.
  • the 'it is a resin containing a sulfonic acid group at various concentrations in the polystyrene-based cation exchange resin can be appropriately selected.
  • a cation exchange resin having a concentration of sulfonic acid group of about 30 to 60% can be used.
  • the dehydration reaction using the resin catalyst may be performed for about 0.2 to about 7 hours at a temperature condition of about 50 to about 90 'C, but the present invention is not limited thereto.
  • step (b) By carrying out the dehydration of cumyl alcohol under the resin catalyst, there is an additional advantage that alpha methyl styrene can be produced with higher conversion and selectivity.
  • the product may further include trace amounts of acetophenone, cumene, and heavy compounds.
  • the obtained mixture of cumyl alcohol can also be diluted.
  • step (c) and step (d) may be performed separately in a separate reaction period.
  • the dehydration of cumyl alcohol converted by hydrogenation reaction and the dehydration of cumene hydroperoxide without hydrogenation may be performed in separate physically separated reactors.
  • the detailed process conditions of the dehydration process for producing phenol and acetone and the dehydration process for producing alpha methyl styrene can be optimized and set differently, so that there is an additional advantage of increasing both the yield of phenol and alpha methyl styrene. .
  • the dehydration reaction of cumyl alcohol may be performed under a resin catalyst, and the remainder of the cumene hydroperoxide stream which has not undergone the hydrogenation reaction may be dewatered under acidic catalyst.
  • the resin catalyst used for dehydration reaction of cumyl alcohol may be used in an amount of about 1 to about 10 parts by weight based on 100 parts by weight of cumyl alcohol.
  • a resin catalyst is used to undergo a neutralization reaction after the dehydration reaction. no need.
  • the remaining portion of the cumene hydroperoxide stream not subjected to the hydrogenation reaction may be concentrated to proceed with dehydration reaction.
  • the dehydration process is carried out in this way, there is an advantage that can increase the production of alpha methyl styrene without reducing the production of phenol and acetone as the main product.
  • the reaction has the additional advantage of preventing the production of by-products.
  • the amount of time to perform separating and dewatering step the impurity is less than 7% by weight based on the total amount of phenol, acetone and alpha methyl styrene, may be less than 5 parts by weight and preferably 0/0.
  • step (c) and step (d) it may further comprise the step of purifying the product containing the phenol, acetone and alpha methyl styrene and separating by distillation. Through this process, alpha methyl styrene, phenol, and acetone can each be separated.
  • the purification step can be used under ordinary conditions.
  • the distillation conditions are not particularly limited and may be made through a conventional method.
  • a method for preparing phenol, acetone and alpha methyl styrene according to one embodiment of the present invention will be described in more detail with reference to the accompanying drawings.
  • 2 is a simplified illustration of a process for producing phenol, acetone, and alpha methyl styrene in accordance with one embodiment of the present invention.
  • the method of the present invention comprises: an oxidation reaction reactor 10 for proceeding oxidation of cumene; A hydrogenation reactor 30 for using a portion of the cumene hydroperoxide stream obtained after the oxidation in a hydrogenation reaction; The hydrogenation stripper for concentrating the cumyl alkoeul and the remaining cumene hydroperoxide stream has not been used in the hydrogenation reaction resulting in banung (S tripper) (40); A cleavage reactor 60 for proceeding with dehydration reaction of the complex concentrated in the stripper; A refining apparatus (70) for purifying the product obtained by the dehydration reaction; And a separation device 80 for separating the product.
  • reservoirs 20 and 50 may be provided between the oxidation reaction reactor 10 and the stripper 40, and between the stripper 40 and the decomposition reaction reactor 60.
  • the present invention produces cumene hydroperoxide and cumyl alcohol having a low concentration by the oxidation of cumene, and at least a portion of the cumene hydroperoxide is directly reacted without hydrogenation to produce cumyl alcohol, the hydrogenation reaction when used Un Cumen
  • a product containing alpha methyl styrene having increased productivity is obtained.
  • the product also contains phenol and acetone, the product is purified and distilled after the step to obtain alpha methyl styrene with increased productivity with phenol and acetone.
  • the present invention feeds cumene to the reaction vessel 10 and proceeds the reaction reaction of cumene in the presence of oxygen.
  • the oxidative reaction reactor 10 may be provided with a plurality of oxidation reactions in stages. For example, the reaction may proceed in three stages in three oxidation reactors. In the oxidation reactor 10, a stream of cumene hydroperoxide of from 5 to 25 parts by weight 0/0 concentration is generated through the oxidation of the cumene, this may contain a small amount of cumyl alkoeul.
  • the present invention separates a part of the stream and transfers the reservoir 20 to the hydrogenation reactor 30 to proceed with the hydrogenation reaction.
  • the low concentration of cumene hydroperoxide stream conveyed to the reservoir 20 is fed to the top-down or bottom-up of the catalytic hydrogenation reaction reactor 30 to produce cumyl alcohol with hydrogenation reaction.
  • the reaction vessel used for the hydrogenation reaction is
  • the reaction may proceed through a CSTR continuous stirred-tank reactor, but the present invention is not limited thereto, and any reaction may be used as long as it is used under ordinary hydrogenation reaction conditions.
  • the catalyst is layered in the hydrogenation reactor 30, and reaction is performed by injecting hydrogen and maintaining the internal temperature.
  • the hydrogenation reaction reactor 30 has a Pd .
  • the reaction can be carried out by charging the Co / C catalyst.
  • the concentrated cumene hydroperoxide stream may be injected into the top of the reaction vessel using a pressure pump.
  • cumene hydroperoxide was converted to cumyl alcohol.
  • the produced cumyl alcohol is supplied back to the reservoir 20, and is transferred to the stripper 40 through it.
  • the remaining stream of cumene hydroperoxide that has not undergone the hydrogenation reaction is sent directly to stripper 40.
  • stripper 40 contains a small amount of cumyl alcohol by oxidation of cumene in the remaining stream of cumene hydroperoxide not used for hydrogenation reaction and cumene in the reaction vessel 10, in addition to cumyl alcohol obtained by the hydrogenation reaction. Includes the complex.
  • the stripper 40 concentrates the mixture and passes through the reservoir 50 to the decomposition reaction vessel 60.
  • the mixture may be concentrated to a concentration of 80 to 82% by weight.
  • the decomposing reaction device 60 may be filled with an acidic catalyst or a resin catalyst to perform dehydration reaction.
  • the mixture of phenol, acetone and alpha methyl styrene produced in the decomposition reaction reactor 60 is transferred to the purification apparatus 70 to proceed with the purification reaction.
  • the purified mixture is transferred to a separation device 80 and separated by distillation into phenol, acetone and alpha methyl styrene, respectively.
  • the phenol, acetone and alpha methyl styrene that are finally separated can be collected into a collection reservoir through separately connected outlets.
  • the reactor used for each reaction step is not particularly limited in its condition, it is possible to use a conventional reaction reaction well known in the art.
  • each semi-unggi can be connected through a separate transfer line.
  • Figure 3 is a simplified view of a process for producing phenol, acetone and alpha methyl styrene according to an embodiment of the present invention.
  • the oxidation reaction step for proceeding the oxidation of cumene (100);
  • a hydrogenation reactor 300 for using a portion of the cumene hydroperoxide stream obtained after the oxidation in a hydrogenation reaction;
  • a stripper 400 for concentrating the remaining cumene hydroperoxide stream not used in the hydrogenation reaction;
  • a first cleavage reactor 320 for proceeding with dehydration of cumyl alcohol obtained by the hydrogenation reaction;
  • a second cleavage reactor 600 for proceeding dehydration of the remaining cumene hydroperoxide stream not used for the hydrogenation reaction in the stripper;
  • a neutralization apparatus 700 for proceeding neutralization of the product obtained from the second decomposition reactor 600;
  • a separation apparatus 800 for separating the products.
  • receivers 200 and 500 may be further provided between the oxidation reaction reactor 100 and the stripper 400, and between the stripper 400 and the second decomposition reaction reactor 600.
  • a reservoir 310 may be further provided between the hydrogenation reaction vessel 300 and the first decomposition reaction reactor 320.
  • the present invention produces cumene hydroperoxide and cumyl alcohol having a low concentration by the oxidation of cumene, and at least a portion of the cumene hydroperoxide is directly reacted without hydrogenation to produce cumyl alcohol, which is then dehydrated under a resin catalyst.
  • a product containing phenol, acetone and alpha methyl styrene with increased productivity can all be obtained.
  • cumene is supplied to the oxidative reaction reactor 100 to perform an oxidation reaction of cumene in the presence of oxygen.
  • a plurality of dogs may be provided in step by step oxidation reaction.
  • the oxidation reaction may be performed in three stages in three oxidation reactions. Oxidation of the cumene produces a cumene hydroperoxide ' stream at a concentration of 5 to 25% by weight.
  • the present invention separates a part of the cumene hydroperoxide stream and supplies it to the hydrogenation reactor 300 via the reservoir 200 to proceed with the hydrogenation reaction.
  • the low concentration cumene hydroperoxide stream sent to reservoir 200 can feed catalyst to the top-down or bottom-up of hydrogenation reactor 300 to produce cumyl alcohol as a hydrogenation reaction.
  • the reaction vessel used for the hydrogenation reaction may be subjected to reaction through a CSTR reaction reactor, but is not limited thereto, and any reaction may be used as long as it is used under ordinary conditions of hydrogenation reaction.
  • the catalyst is layered in the hydrogenation reaction reactor 300, and reaction is performed by injecting hydrogen and maintaining the internal temperature.
  • the reaction may be performed by layering a Pd-Co / C catalyst on the hydrogenation reaction reactor 300.
  • the concentrated cumene hydroperoxide stream may be injected into the top of the reaction counter using a pressurized pump.
  • the hydrogenation reaction converts the cumene hydroperoxide to cumyl alcohol.
  • the prepared cumyl alcohol is supplied back to the low-term (310), and is transferred to the first decomposition reaction vessel (320).
  • Dehydration reaction to alpha methyl styrene is performed in the first decomposition reactor 320.
  • the dehydration and reaction can be carried out using an acid catalyst.
  • the dehydration reaction may be performed using a resin catalyst.
  • cumyl is passed through the cumyl alcohol in the first cracking reactor 320 immobilized via a beads or the like. The alcohol undergoes a decomposition reaction to produce a product comprising alpha methyl ethylene.
  • the product comprising alpha methyl ethylene produced in the first cracking reactor 320 is then combined with the product comprising phenol and acetone via the second cracking reactor 600 and the neutralizer 700 described below.
  • the remaining stream of cumene hydroperoxide that has not undergone the hydrogenation reaction is sent directly to stripper 400.
  • the stripper 400 includes cumene hydroperoxide not used in the hydrogenation reaction.
  • the stripper 400 may also include small amounts of cumyl alcohol obtained by the oxidation of cumene.
  • dehydration reaction is performed on the cumene hydroperoxide in the second decomposition reactor 600 to decompose the cumene hydroperoxide into phenol and acetone.
  • the dehydration reaction in the second decomposition reaction reactor 600 may be performed under an acidic catalyst. Reaction conditions such as temperature, pressure, reaction time, catalyst type, and catalyst amount in the first decomposition reaction reactor 320 and the second decomposition reaction reactor 600 may be independently set.
  • the product containing phenol and acetone produced in the second decomposition reaction step 600 is transferred to the neutralization device 700 to perform a neutralization process.
  • the product comprising the phenol and acetone, which have undergone the neutralization process, and the product containing alpha methyl styrene produced in the first cracking reaction step 320, are combined and transferred to the separation device 800.
  • Separation device 800 separates into phenol, acetone and alpha methyl styrene, respectively, through purification and distillation.
  • the final separated phenols, acetone and alpha methyl styrene can also be collected into collection reservoirs through separate connected outlets.
  • alpha methyl increases productivity simultaneously without reducing the production of the main products phenol and acetone. You can get styrene.
  • cumyl alcohol and cumene hydroperoxide are separated from each other in the process, there is no fear of byproducts caused by their reaction, so that the total impurities are lowered and subsequent purification processes can be simplified to reduce production costs. Can be.
  • the present invention proceeds to the hydrogenation reaction of cumene hydroperoxide obtained by the oxidation of cumene at the most stabilized conditions of low concentration and low temperature, it is possible to produce cumyl alcohol in a more stable state without the explosion risk of cumene hydroperoxide.
  • the present invention can produce alpha methyl styrene with high selectivity and conversion through a dehydration process using a hydrogenation process using a Pd-Co catalyst.
  • alpha methyl styrene can be produced with higher conversion and selectivity by performing dehydration of cumyl alcohol under a resin.
  • FIG. 1 is a process diagram briefly illustrating a conventional phenol production process.
  • FIG. 2 is a process diagram briefly illustrating a process for producing phenol, acetone and alpha methyl styrene according to an embodiment of the present invention.
  • FIG. 3 is a process diagram briefly illustrating a process for producing phenol, acetone and alpha methyl styrene according to an embodiment of the present invention.
  • the reaction was carried out by filling the hydrogenation reactor with Pd-Co / C as a catalyst, injecting hydrogen and maintaining the internal temperature.
  • the reaction product was injected with a cumene hydroperoxide stream at a concentration of 25% by weight using a pressure pump.
  • the hydrogenation reaction was carried out by injecting 150 g of cumene hydroperoxide (CHP) at a concentration of 25% by weight and Pd-Co / C catalyst lg having a weight ratio of 1: 1 to Pd: Co.
  • CHP cumene hydroperoxide
  • Pd-Co / C catalyst lg having a weight ratio of 1: 1 to Pd: Co.
  • the molar ratio of cumene hydroperoxide stream and injected hydrogen was maintained at 1: 8.
  • the reaction time was 3 hours. Examples 2-5
  • Example 1 It carried out similarly to Example 1 except having used the Pd-Co / C catalyst which changed the weight ratio of Pd: Co.
  • the weight ratio of Pd: Co is shown in Table 1 below.
  • Phenol, acetone and alpha methyl styrene were prepared according to the process diagram shown in FIG.
  • the concentration of the CHP stream was changed to 8.4 to 24% by weight through three oxidation reactions.
  • the hydrogenation reaction was filled with Pd-Co / C as a catalyst, injected with hydrogen, and maintained at an internal temperature.
  • cumene hydroperoxide stream is water banung 25 weight 0/0 concentration is by using a pressure pump and injected into the reactor top (top-down).
  • the hydrogenation banung is cumene hydroperoxide (CHP) 150g, Pd 25 wt. 0/0 concentration was carried out under the conditions of one of Pd-Co / C catalyst lg, hydrogen flow rate of 150 cc / min: the weight ratio of Co is 1 .
  • the molar ratio of cumene hydroperoxide stream and injected hydrogen was maintained at 1: 8.
  • the hydrogenation reaction time was carried out for 3 hours.
  • the prepared cumyl alcohol was to be supplied to the reservoir 20, which was transferred to the stripper 40. Therefore . Accordingly, the stripper 40 is filled with a mixture of cumyl alcohol obtained from the hydrogenation reaction and cumyl alcohol and cumene hydroperoxide not used in the hydrogenation reaction.
  • the mixture was concentrated in the stripper 40, and transferred to the decomposition reaction vessel 60 through the reservoir 50, and the rest was transferred directly to the decomposition reaction vessel 60.
  • dehydration reaction is performed on the mixture using a polystyrene-based cation exchange resin (hereinafter, Resin A) having a sulfonic acid group concentration of 40% as a resin in the decomposition reaction reactor 60, cumene hydride.
  • Resin A polystyrene-based cation exchange resin having a sulfonic acid group concentration of 40% as a resin in the decomposition reaction reactor 60, cumene hydride.
  • Loperoxide Digestion with phenol and acetone was allowed to dehydrate cumyl alcohol with alpha methyl styrene.
  • the decomposition reaction was carried out by using a resin A 5% by weight based on 150g of the mixture.
  • the reaction temperature was maintained at 65 ° C. was converted until the concentration of cumene hydroperoxide is less than
  • the mixture of phenol, acetone and alpha methyl styrene produced in the decomposition reactor 60 was transferred to the purification apparatus 70 and the purification reaction was carried out. It after purification, the product was separated into each phenol, alpha-methylstyrene and acetone by distillation and transferred to a separation device 70.
  • Polystyrene cation exchange resin (hereinafter, Resin B) having a concentration of 48% of sulfonic acid as a resin catalyst (Example 11), polystyrene cation exchange resin (hereinafter, Resin C) having a concentration of 5 % of sulfonic acid (hereinafter, Resin C) (Example 12 Was carried out in the same manner as in Example 8, except that) was used.
  • Example 13 Resin catalyst instead was carried out in the same manner as in Example 8, except the sulfuric acid decomposition for the 150g common compound unggi half (60) (H 2 S0 4 ) by putting the lg that the "proceed to dehydration banung.
  • Phenol, acetone and alpha methyl styrene were prepared according to the flowchart shown in FIG. 3.
  • the oxidation of cumene proceeds with an oxidant using the oxidizing half unggi 100 to prepare a stream comprising cumene hydroperoxide in 24 parts by weight 0/0 concentration was carried out in the same manner as in Example 1.
  • the hydrogenation reaction reactor 300 was filled with Pd-Co / C with a catalyst, hydrogen was injected, and the reaction was performed by maintaining the internal temperature at 65 ° C.
  • cumene hydroperoxide stream of the reaction is 25 wt. 0/0 concentration is by using a pressure pump was injected in half unggi the bottom (bottom-up).
  • the hydrogenation reaction was subjected to hydrogenation reaction under conditions of 150 g of cumene hydroperoxide at a concentration of 25% by weight, Pd-Co / C catalyst lg having a weight ratio of 1: 0.2 of Pd: Co, and a hydrogen flow rate of 150 cc / min.
  • the molar ratio of cumene hydroperoxide stream and injected hydrogen was maintained at 1: 8.
  • the hydrogenation reaction time was carried out for 3 hours.
  • Resin A was fixed to the first decomposition reaction reactor 320 by a bead by means of beads to allow dehydration to alpha methyl styrene by passing through cumyl alcohol.
  • the first decomposition half unggi 320 there was used a resin A with respect to the supplied cumyl alcohol with 5 parts by weight 0 /. Banung the degree was converted until held at 80 ° C and the concentration of cumyl alkoeul less than 2% .
  • An acidic catalyst was added to the second decomposition reactor 600 to decompose cumene hydroperoxide into phenol and acetone. At this time, a sulfuric acid catalyst was added to the second cracking reactor to react the reaction. In addition, the reaction temperature was maintained at 65 ° C and switched until the concentration of cumene hydroperoxide was less than 1%.
  • Phenol and acetone produced in the second decomposition reaction reactor 600 is combined with alpha methyl styrene produced in the first decomposition reaction reactor 320 through the neutralization device 700, and transferred to the separation device 800, The process of separating into phenol, acetone and alpha methyl styrene, respectively. Examples 15-16
  • Example 14 The same process as in Example 14 was carried out except that resin B (Example 15) and resin C (Example 16) were used as the resin catalyst. Comparative Example 1
  • Sulfuric acid (3 ⁇ 4S0 4 ) was added as an acidic catalyst to the decomposition reaction reactor, and the acidic catalyst was cumene by continuously dehydrating the mixture. Hydroperoxide was decomposed to phenol and acetone and cumyl alcohol was dehydrated with alpha methyl styrene. In the decomposition reaction, 4.5 wt% of sulfuric acid was added to 150 g of the mixture to carry out the reaction. In addition, the reaction temperature was maintained at 65 ° C.
  • the reaction was carried out by transferring the reaction product to a decomposition reactor.
  • CHP conversion rate (%) (CHP feed (wt%) - CHP product (weight 0/0)) / (CHP feed (weight 0/0))
  • CA selectivity (%) (CA product (mol%) / (CHP feed (mol 0/0) - CHP product (mol 0/0))
  • AMS selectivity (%) (AMS product (mol 0/0) / (CA feed (mol 0/0) - CA product (mol 0/0))
  • AMS yield (%) CA conversion (%) * AMS selectivity (%)
  • Examples 14 to 16 of the present invention is carried out by separating the dehydration reaction from cumyl alcohol to alpha methyl styrene and using a resin catalyst, the conversion rate of cumyl alcohol (CA) compared to Comparative Example 1 And excellent selectivity, and finally it can be seen that the production of alpha methyl styrene was significantly increased compared with the case of using an acid catalyst.
  • CA cumyl alcohol

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Abstract

La présente invention a pour objet un procédé de préparation d'alcool cumylique et un procédé de préparation de phénol, d'acétone et d'alpha méthylstyrène. Selon la présente invention, par un procédé d'hydrogénation pour l'hydroperoxyde de cumène obtenu par l'oxydation de cumène dans un procédé de préparation de phénol, la sélectivité peut être améliorée et la quantité d'alcool cumylique peut être accrue. En outre, la quantité de l'alpha méthylstyrène peut être sélectivement accrue. En outre, la quantité produite de l'alpha méthylstyrène peut être contrôlée en fonction de la demande du marché par le contrôle de la quantité de l'hydroperoxyde de cumène.
PCT/KR2012/005539 2011-07-15 2012-07-12 Procédé de préparation d'alcool cumylique et procédé de préparation de phénol, d'acétone et d'alpha méthylstyrène WO2013012203A2 (fr)

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CN201280023345.8A CN103562168B (zh) 2011-07-15 2012-07-12 异丙苯醇的制备方法和苯酚、丙酮及α-甲基苯乙烯的制备方法

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