WO2015129740A1 - 脂環式多価カルボン酸の製造方法 - Google Patents

脂環式多価カルボン酸の製造方法 Download PDF

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Publication number
WO2015129740A1
WO2015129740A1 PCT/JP2015/055381 JP2015055381W WO2015129740A1 WO 2015129740 A1 WO2015129740 A1 WO 2015129740A1 JP 2015055381 W JP2015055381 W JP 2015055381W WO 2015129740 A1 WO2015129740 A1 WO 2015129740A1
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temperature
raw material
reaction
reactor
heat
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PCT/JP2015/055381
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English (en)
French (fr)
Japanese (ja)
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田中　善幸
浩哉 香川
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三菱化学株式会社
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Priority to CN201580010060.4A priority Critical patent/CN106029622B/zh
Publication of WO2015129740A1 publication Critical patent/WO2015129740A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a method for producing a corresponding alicyclic polyvalent carboxylic acid by continuously performing a hydrogenation reaction in the presence of a solid catalyst using an aromatic polyvalent carboxylic acid as a raw material, and more specifically, terephthalic acid (hereinafter referred to as “terephthalic acid”).
  • terephthalic acid The aromatic nucleus of an aromatic polyvalent carboxylic acid such as “TPA” may be hydrogenated (hereinafter also referred to as “nuclear hydrogenation”) to produce 1,4-cyclohexanedicarboxylic acid (hereinafter referred to as “1”).
  • 4-CHDA or simply" CHDA " and the like.
  • Alicyclic polycarboxylic acids such as 1,4-CHDA are raw materials for alicyclic polyhydric alcohols such as 1,4-cyclohexanedimethanol, and these alcohols include polyester-based paints and polyester-based synthetic fibers, It is useful as a raw material for synthetic resins and the like, and is particularly used as a raw material for resins and fibers having excellent heat resistance, weather resistance, physical strength and the like.
  • Japanese Patent Application Laid-Open No. 2002-255895 discloses a process for preparing a slurry liquid from an aromatic carboxylic acid and a solvent in a process for producing an aromatic carboxylic acid hydride by hydrogenating an aromatic carboxylic acid having a melting point of 250 ° C. or higher.
  • the slurry is continuously supplied to the reactor, the hydrogenation reaction is carried out in the presence of the solid catalyst, and at least a part of the reaction liquid continuously extracted from the reactor is circulated to the reactor, whereby the reaction is performed.
  • a method for producing an aromatic carboxylic acid hydride characterized in that the hydrogenation reaction is carried out in a state where substantially all of the aromatic carboxylic acid is dissolved in the vessel.
  • the reactor may be a fixed bed or a stirred tank type, but no mention is made of a method for controlling the temperature of the reactor.
  • a method for controlling the temperature of the reactor when trying to carry out a fixed bed reaction on an industrial scale, it is generally difficult to maintain a uniform reaction temperature in all of the reaction zones.
  • the reaction liquid when circulating the reaction liquid to the reactor, in both cases of the fixed bed type and the stirring tank type, the reaction liquid is cooled in the circulation line after being withdrawn from the reactor or is reacted for heat balance. In any case, a process of cooling the reaction liquid is required, such as whether to dilute thermally with the reaction raw material liquid in the step of mixing with the raw material liquid.
  • the first problem of the present invention is to stably maintain the heat removal performance of the reaction mixture in the reactor in the step of producing the corresponding alicyclic polycarboxylic acid by the hydrogenation reaction of the aromatic polycarboxylic acid. It is to obtain stable reaction results over a long period of time.
  • the second problem of the present invention is to perform heat removal from the reactor without relying only on heat exchange with the cooling medium. As a result, energy loss caused by remarkably increasing or decreasing the temperature of the heat medium or the like when heating or heat removal is performed rapidly, which is a problem in heat removal by heat exchange, can be reduced.
  • the third object of the present invention is to provide a method capable of hydrogenating an aromatic polyvalent carboxylic acid without requiring an additional structure for heat removal. This simplifies the structure of the reactor and maintains / improves the stirring efficiency in the reactor.
  • the present inventors have used a reaction apparatus including at least a raw material preparation tank and a reactor as the reaction apparatus, and the reaction heat of the exothermic reaction by the cold energy of the aqueous medium to be supplied. As a result, the present invention has been completed.
  • the gist of the present invention resides in the following [1] to [6].
  • [1] Adjusting the temperature of the raw material mixture supplied to the reactor in the method of continuously producing the corresponding alicyclic polycarboxylic acid by hydrogenating the aromatic nucleus of the aromatic polycarboxylic acid in an aqueous medium A process for producing an alicyclic polyvalent carboxylic acid by controlling the reaction temperature.
  • the mixing ratio of the aromatic polyvalent carboxylic acid and the aqueous medium in the raw material mixture is in the range of 5/95 to 50/50 as the weight ratio of the aromatic polyvalent carboxylic acid / the aqueous medium.
  • the reaction temperature is 100 ° C. or more and 200 ° C. or less, and the temperature of the raw material mixture supplied to the reactor is 40 ° C. to 120 ° C. lower than the reaction temperature, according to any one of [1] to [3] A method for producing an alicyclic polycarboxylic acid.
  • the heat removal performance of the reaction heat is less affected by deposits and the like, the reaction can be kept stable, and additional heat removal equipment is also provided inside the reactor. Therefore, the temperature of the reactor can be easily controlled.
  • FIG. 1 is a schematic view of a reaction apparatus showing an example in which a temperature of a raw material mixture can be adjusted by installing a heat exchanger between a raw material preparation tank and a reactor in the present invention.
  • FIG. 2 is a schematic diagram showing the heat balance of the embodiment of the present application.
  • the aromatic polyvalent carboxylic acid used in the present invention is not particularly limited as long as it is a compound having two or more carboxyl groups bonded to an aromatic ring.
  • the aromatic polyvalent carboxylic acid preferably has 2 to 4 carboxyl groups in one molecule, particularly preferably 2. This is because an alicyclic diol is obtained from an alicyclic dicarboxylic acid that is a hydrogenated product of an aromatic dicarboxylic acid, and this can be used as a raw material for producing a polymer.
  • the aromatic polyvalent carboxylic acid may be used alone or as a mixture of two or more.
  • aromatic polycarboxylic acid examples include aromatic polycarboxylic acids having an aromatic ring having 4 to 14 carbon atoms. Specific examples include phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalene. Examples thereof include dicarboxylic acid, 1,1′-biphenyl-4,4′-dicarboxylic acid, trimellitic acid, and pyromellitic acid. Among these compounds, aromatic dicarboxylic acids having an aromatic ring having 4 to 10 carbon atoms are preferable, and phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid are more preferable. Most preferred is terephthalic acid.
  • the hydrogenation reaction in the method of the present invention is a liquid phase reaction, and is usually performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not react with the raw materials or products in the reaction step, does not inhibit the reaction, does not poison the catalyst, and does not adversely affect the progress of the reaction.
  • examples of such a solvent include water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; hydrocarbons such as hexane and decalin and the like. These solvents can be used alone or in combination.
  • a solvent that has a small temperature rise due to reaction heat that is, a solvent that has a large specific heat is desirable.
  • a solvent having a high boiling point is desirable.
  • the vapor pressure of the solvent increases due to an increase in the liquid temperature due to the heat of reaction, and as a result, the hydrogen partial pressure in the gas phase decreases, and hydrogen enters the solvent.
  • the solubility decreases and the reaction rate decreases. That is, it is preferable to use an aqueous medium containing water, particularly water as the solvent.
  • the alicyclic polyvalent carboxylic acid which is a product may be contained in the solvent.
  • the mixing ratio (weight ratio) of the aromatic polycarboxylic acid and the aqueous medium supplied to the reactor is preferably 5/95 to 50/50.
  • a more preferable ratio is 10/90 to 30/70.
  • the mixing ratio (weight ratio) of the aromatic polyvalent carboxylic acid and the aqueous medium in the slurry is low, such as less than 5/95, the amount of heat generated during the reaction is small, so that the reaction temperature can be easily controlled. However, it becomes difficult to separate the reactant and the solvent from the reaction product solution.
  • the reaction temperature of the hydrogenation reaction of the aromatic polyvalent carboxylic acid to which the method of the present invention is applied is preferably 100 ° C. to 200 ° C., more preferably 150 to 190 ° C.
  • the reaction temperature is lower than 100 ° C., the reaction rate is remarkably slow, and the production efficiency tends to decrease.
  • the reaction temperature exceeds 200 ° C., many side reactions occur and the yield of the target product decreases, and the vapor pressure of the solvent increases. Therefore, excessive pressure is required to maintain the same hydrogen partial pressure. Since a pressure reaction is required, and equipment with high pressure strength is required, equipment costs increase and economy tends to be inferior.
  • the temperature when the slurry (mainly containing a mixture of aromatic polycarboxylic acid and aqueous medium), which is a raw material mixture used in the method of the present invention, is preferably 25 to 100 ° C.
  • the supply temperature of the slurry is less than 25 ° C., the temperature difference between the internal temperature of the reactor and the periphery of the slurry supply port becomes large, the components dissolved in the reaction liquid are deposited around the supply port, and the slurry supply port is narrowed. Or blockage.
  • the reaction rate becomes very fast.
  • the reaction temperature may be further increased due to the reaction heat, resulting in a runaway reaction. is there.
  • measures such as limiting the volume of the reaction solution or providing a large cooling facility are required. It is preferable to set the slurry supply temperature to the reactor within the above range because the reaction can be stably and efficiently advanced.
  • the present invention is characterized in that the reaction temperature is controlled by adjusting the temperature of the raw material mixture slurry supplied to the reactor.
  • the method of adjusting the temperature of the raw material mixture slurry supplied to the reactor is not particularly limited, but a reactor including a raw material preparation tank and a reactor is used, and the raw material preparation tank or the raw material preparation tank and the reactor are interposed between them. It is preferable to control the reaction temperature by adjusting the temperature of the raw material mixture using the provided raw material temperature controller.
  • FIG. 1 An example in which a heat exchanger is installed between the raw material preparation tank and the reactor so that the raw material temperature can be adjusted is shown in FIG.
  • a raw material temperature controller 4 is installed on a transfer pipe connecting the raw material preparation tank 1 and the reactor 2, and a hydrogen booster compressor 3 is connected to the reactor 2.
  • the raw material mixture stored in the raw material preparation tank 1 is transferred to the reactor 2 by a pump 5.
  • the reaction heat generated per unit time is calculated based on the supply amount of the raw material and the reaction conditions, 2) By dividing this by the specific heat of the mixture of the product and solvent, the temperature at which the reaction system rises due to the reaction is estimated, 3) Adjust the temperature of the slurry from the heat capacity of the slurry of the raw material component supplied into the system so as to meet the above temperature rise. Or the like.
  • Such adjustment of the reaction temperature can be achieved by adjusting the temperature of the feedstock using a raw material preparation tank or a heat exchanger (raw material temperature controller) provided between the raw material preparation tank and the reactor.
  • a raw material preparation tank is supplied using a material having a raw material temperature controller (temperature adjusting means) such as a jacket (which may be an external type or an internal type), an internal coil, and an external circulation heat exchanger.
  • a method of preparing a raw material (slurry) and controlling the temperature a method of adjusting a temperature by installing a heat exchanger as a raw material temperature controller in a transfer pipe connecting the raw material preparation tank and the reactor, or a combination thereof.
  • a method of providing a multi-tube heat exchanger (shell-and-tube heat exchanger) in the raw material preparation tank and / or transfer pipe is preferable.
  • the reaction temperature of the present invention is adjusted or controlled by the temperature of the raw material mixture (slurry) supplied to the reactor. Furthermore, in order to improve the controllability of the reaction, a temperature adjusting jacket may be provided in the reactor as an auxiliary. According to the present invention, regardless of the type of solvent and the charged concentration of the raw material aromatic polycarboxylic acid, it is usually possible to achieve a heat balance only by heating the raw material mixture. According to the present invention, the reaction temperature can be maintained by adjusting the temperature of the raw material mixture supplied to the reactor and the heat of reaction. That is, the temperature of the raw material mixture supplied to the reactor is preferably set to a temperature that can be compensated by the reaction heat with respect to the reaction temperature.
  • a suitable temperature of the raw material mixture supplied to the reactor depends on the slurry concentration, but when the reaction temperature is 100 ° C. to 200 ° C., it is preferably 40 ° C. to 120 ° C. lower than the reaction temperature, and 50 ° C. below the reaction temperature. It is preferable that the temperature is lower by 115 ° C to 115 ° C.
  • the reaction temperature is adjusted by providing a solid component (such as a Pd / C catalyst or a raw material component that cannot be completely dissolved in the liquid) using a filtration device from a slurry taken out of the reactor by providing an external circulation line.
  • a solid component such as a Pd / C catalyst or a raw material component that cannot be completely dissolved in the liquid
  • the process is performed by a method of providing a heat exchanger for fluid heating in the line while separating the component.
  • a cross-flow type filtration system it is usually necessary to flow a significantly larger amount of fluid (for example, about 10 times) on the primary side than the permeation amount.
  • the heating is performed on the upstream side of the reactor, that is, in the raw material supply line, there is no restriction on the heat transfer area, and it is not necessary to provide a coil or the like inside the reactor, so the structure of the reactor Even simple things are enough.
  • a pump or the like does not require a new device other than a fluid drive device such as a pump necessary for supplying raw materials, and the liquid flow rate passing through the heat exchanger is about 1 compared to the above external circulation method. Since only about / 10 is sufficient, the pressure loss is small and the additional driving force required for the pump or the like is small and sufficient.
  • Example 1 1,4-cyclohexanedicarboxylic acid (CHDA) is produced by hydrogenating terephthalic acid (TPA) using a reactor configured as shown in FIG.
  • TPA terephthalic acid
  • TPA 15 ° C.
  • 20 ° C. water 6397 kg / h
  • TPA / water (weight Ratio) 20/80
  • This slurry was pressurized to 6.1 MPa ⁇ G (gauge pressure, the same applies hereinafter) with hydrogen, and supplied at 7996 kg / h, 91 ° C. using a multi-tube heat exchanger provided in the middle of the slurry transfer pipe. And the temperature is adjusted to 170.degree. C. and fed to a reactor equipped with a stirrer.
  • the raw material slurry supply temperature (91 ° C.) at this time is estimated and determined as follows.
  • FIG. 2 shows the reactor 2 taken out from the reactor shown in FIG. 1, and cannot be completely dissolved in the two heat exchangers 4 for the heat balance control and the solid catalyst or liquid. It has a filtration module 6 for separating solid components such as raw material components and reaction products.
  • Raw material slurry supply temperature X ° C Reaction temperature: 170 ° C. (However, set temperature is 172 ° C. in consideration of heat dissipation loss)
  • Raw material hydrogen gas supply temperature 113 ° C
  • Product extraction temperature 170 ° C
  • Unreacted gas extraction temperature 172 ° C
  • Unreacted gas condensed water return temperature 40 ° C
  • Reaction solution circulation heating temperature input temperature 170 ° C ⁇ output temperature 172 ° C
  • Heat balance calculation Based on the above assumptions, heat balance calculation was performed using “ASPEN Plus Ver. 7.2” from ASPEN Tech. Thermodynamic property values such as specific heat used for the calculation were quoted or calculated using the property database built in the software.
  • the raw material slurry supply temperature (112 ° C.) at this time is estimated and determined as follows. A rough calculation procedure is described below. (1) From the TPA supply amount (800 kg / h) and the reaction conditions (reaction temperature 170 ° C., 6.1 MPa ⁇ G) in the operation of the above example, the calorific value due to hydrogen addition is 257 Mcal / h. (2) When the temperature of the supplied hydrogen gas is set to 113 ° C. (6.1 MPa ⁇ G, 1342 Nm 3 / h), heating of 42 Mcal / h is required to raise the temperature to 172 ° C. of the reaction liquid temperature. It becomes.
  • the raw material slurry supply temperature (58 ° C.) at this time is estimated and determined as follows. A rough calculation procedure is described below. (1) From the TPA supply amount (2399 kg / h) and the reaction conditions (reaction temperature 170 ° C., 6.1 MPa ⁇ G) in the operation of the above example, the calorific value due to hydrogenation is 257 Mcal / h. (2) When the temperature of the supplied hydrogen gas is set to 128 ° C. (6.1 MPa ⁇ G, 3990 Nm 3 / h), heating of 56 Mcal / h is necessary to raise the temperature to 172 ° C. of the reaction liquid temperature. It becomes.
  • the heat removal performance of the reaction heat is affected by the deposits, etc. Accordingly, there is provided a method capable of controlling the temperature of the reactor, which makes it possible to keep the reaction stable because it is less susceptible to heat and does not require additional heat removal equipment inside the reactor.
  • Raw material preparation tank 2 Reactor 3: Hydrogen booster compressor 4: Raw material temperature controller (heat exchanger) 5: Pump 6: Filtration module

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/JP2015/055381 2014-02-26 2015-02-25 脂環式多価カルボン酸の製造方法 WO2015129740A1 (ja)

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CN114105767A (zh) * 2020-08-28 2022-03-01 中国石油化工股份有限公司 一种连续化生产1,4-环己烷二甲酸的固定床生产装置及使用方法

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WO2015093849A1 (ko) * 2013-12-19 2015-06-25 한화케미칼 주식회사 프탈레이트 화합물의 수소화 방법

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JP2002255895A (ja) * 2000-12-26 2002-09-11 Mitsubishi Gas Chem Co Inc 芳香族カルボン酸水素化物の製造方法

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN114105767A (zh) * 2020-08-28 2022-03-01 中国石油化工股份有限公司 一种连续化生产1,4-环己烷二甲酸的固定床生产装置及使用方法
CN114105767B (zh) * 2020-08-28 2024-06-11 中国石油化工股份有限公司 一种连续化生产1,4-环己烷二甲酸的固定床生产装置及使用方法

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