WO2021135443A1 - Procédé et dispositif de synthèse de 2,3,5-triméthylhydroquinone - Google Patents

Procédé et dispositif de synthèse de 2,3,5-triméthylhydroquinone Download PDF

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WO2021135443A1
WO2021135443A1 PCT/CN2020/117529 CN2020117529W WO2021135443A1 WO 2021135443 A1 WO2021135443 A1 WO 2021135443A1 CN 2020117529 W CN2020117529 W CN 2020117529W WO 2021135443 A1 WO2021135443 A1 WO 2021135443A1
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hydrogen
trimethylhydroquinone
reaction
synthesizing
alcohol
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PCT/CN2020/117529
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English (en)
Chinese (zh)
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吕国锋
刘祥洪
王勇
田金金
毛晨东
刘丽丽
彭飞
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上虞新和成生物化工有限公司
浙江新和成药业有限公司
山东新和成维生素有限公司
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Publication of WO2021135443A1 publication Critical patent/WO2021135443A1/fr

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    • 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
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D2009/0086—Processes or apparatus therefor

Definitions

  • the invention relates to the field of fine organic chemistry synthesis, in particular to a synthesis method and device of 2,3,5-trimethylhydroquinone.
  • TMHQ 2,3,5-Trimethylhydroquinone
  • TMBQ 2,3,5-Trimethylbenzoquinone
  • TMBQ 2,3,5-Trimethylbenzoquinone
  • the reduction process of zinc powder/sulfuric acid process will produce a large amount of waste salt by-products.
  • the most popular application is the catalytic hydrogenation of precious metals, and the direct hydrogenation of palladium carbon, platinum carbon and Raney nickel is preferred.
  • Hydrogenation solvent adopts low-carbon alcohol (C 1 -C 3 ), the product TMHQ is easily dehydrated with alcohol to form etherate, and impurity 2 will be formed. Impurity 2 will be carried into the subsequent preparation of VE. The final product is an open-ring VE impurity. VE is difficult to separate and affects the quality of VE.
  • the specific reaction formula is as follows:
  • the hydrogenation solvent is a solvent with a strong polarity
  • the product and the raw material are likely to form hydrogen bonds, and the quinhydroquinone impurity 3 is obtained, especially when there is water, the impurity 3 is more likely to be generated.
  • Impurity 3 is reddish brown. If there is residue in the post-processing, the product is almost white or yellow. Impurity 3 is brought to the subsequent preparation of VE, which directly affects the purity and light transmittance of VE.
  • the color of impurity product is reddish brown and difficult It is removed by rectification and decolorization.
  • the reaction formula is as follows:
  • Patent CN201511021779.6 uses a method of passivating (poisoning) catalysts to control catalyst activity and increase reaction selectivity, thereby increasing the purity of the final product TMHQ. If the control is good, the maximum by-product content (impurities) can be controlled at about 0.5%.
  • the highest impurity content is 0.5%, which may be amplified in the subsequent VE preparation.
  • the results of the small-scale verification also have this trend, that is, the impurity of TMHQ
  • the content can be magnified 3-5 times in the preparation of VE.
  • the newly introduced catalyst deactivator is a new impurity, which has a certain impact on the subsequent VE preparation. The introduced deactivator cannot be effectively removed during TMHQ purification.
  • Patent US3839468 studied hydrogenation solvent systems such as ethanol, isopropyl ether, toluene, ethyl acetate, tert-butanol, dipropyl ether, acetone, methyl tert-butyl ether, etc., preferably acetone and methyl tert-butyl ether solvent systems. Both acetone and methyl tert-butyl ether have the disadvantages of high odor, low boiling point, high recovery loss, and low flash point, flammable and explosive.
  • raw materials are easily available and cheap, but the disadvantage is that the product purity is not high , The conversion rate is 98-99%, and there are 1-2% of the raw material residue; low-carbon esters, such as methyl acetate, ethyl acetate, isobutyl acetate, etc., have the advantages of higher conversion rate, high selectivity, and basic The above can reach 99%.
  • the disadvantage is that the solvent recovery rate is low, the esters are easily hydrolyzed, and the solvent treatment is troublesome; alkanes, such as pentane, heptane, hexane, cyclohexane, etc., have the advantage of easy to obtain, cheap and stable raw materials.
  • the disadvantages are volatile, large recovery loss, low flash point and unsafe; aromatic hydrocarbons, such as benzene, toluene, xylene, trimethylbenzene, etc., have the advantages of reaction selectivity and high product purity, but the disadvantage is that the reaction conversion rate is not high; others , Such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, N,N-dimethylformamide, etc., the advantages are small polarity, low boiling point, not easy to produce quinhydroquinone (ie impurity 3), the disadvantage is the safety risk of solvent recovery Large, etherate is easy to produce peroxide, tetrahydrofuran and N,N-dimethylformamide smell very big.
  • the current technical defects in the hydrogenation of TMBQ to prepare TMHQ are: the selectivity of the hydrogenation reaction needs to be further improved, the product has many impurities, and the impurity content is high. None of the currently adopted technical methods can effectively solve the problem.
  • the technical problem to be solved by the present invention is to overcome the above-mentioned defects in the prior art and provide a synthesis method and device of 2,3,5-trimethylhydroquinone (TMHQ), which can improve the hydrogenation of TMBQ
  • TMHQ 2,3,5-trimethylhydroquinone
  • a synthesis method of 2,3,5-trimethylhydroquinone including:
  • the mixed solvent is composed of alcohol and hydrocarbon solvent
  • the hydrogen-containing reaction liquid undergoes a hydrogenation reaction under the action of a catalyst, and after the reaction is completed, the 2,3,5-trimethylhydroquinone is obtained by post-processing.
  • the invention uses a solvent to absorb hydrogen, first mixes the hydrogen with the reaction liquid, and then performs the hydrogenation reaction under the action of the catalyst, which can effectively control the hydrogenation reaction speed, appropriately reduce the hydrogenation reaction activity, and improve the reaction selectivity.
  • a solvent to absorb hydrogen, first mixes the hydrogen with the reaction liquid, and then performs the hydrogenation reaction under the action of the catalyst, which can effectively control the hydrogenation reaction speed, appropriately reduce the hydrogenation reaction activity, and improve the reaction selectivity.
  • the hydrogen absorption capacity of the solvent determines that the hydrogenation reaction will proceed relatively mildly, and side reactions are not prone to occur. It can effectively control the impurities 1, impurities 2, and impurities in the catalytic hydrogenation of TMBQ precious metals. 3 content, experimental verification, the average content of total impurities is 0.11%.
  • the alcohol is a C 1 -C 6 alcohol
  • the hydrocarbon solvent is one or more of aromatic hydrocarbons and alkanes.
  • the invention adopts the alcohol-aromatic or alcohol-alkane mixed solvent system for hydrogenation to effectively change the hydrogen absorption capacity of the solvent and the polarity of the solvent system, so as to improve the quality of the hydrogenation reaction, that is, increase the selectivity of the hydrogenation reaction and reduce reaction impurities.
  • Aromatics and alkanes are used to replace water to adjust the polarity of the system solvent and the solubility of the product, to better separate the product from the solvent system, to achieve no waste water discharge in production, to reduce the cost of solvent recovery in the hydrogenation reaction, and to simplify the production process.
  • the alcohol is one or more of methanol, ethanol, propanol and butanol;
  • the aromatic hydrocarbon is one or more of benzene, toluene, xylene and trimethylbenzene, preferably toluene or xylene;
  • the alkanes are C 5 -C 8 alkanes, preferably n-hexane or cyclohexane.
  • the mass percentage of the alcohol in the mixed solvent is 10-90%, preferably 50-60%.
  • the mass percentage concentration of the 2,3,5-trimethylbenzoquinone solution is 5-50%, preferably 10-20%.
  • the TMBQ hydrogenation reaction system of the present invention has a slightly positive pressure, and the hydrogen pressure is below 0.1 MPa (gauge pressure).
  • the catalyst is a supported catalyst, the carrier is activated carbon, silica or resin, and the active ingredient is a precious metal, including palladium, platinum, nickel or gold; the catalyst is preferably palladium on carbon or Platinum-carbon catalyst, at this time, the catalytic hydrogenation conversion rate can reach more than 99%, and the selectivity is more than 99%.
  • the hydrogenation reaction temperature is 30-120°C, preferably 50-80°C.
  • the post-processing process is as follows:
  • reaction liquid undergoes gas-liquid separation to recover excess hydrogen, the liquid material is cooled and crystallized, and then the product TMHQ is separated by centrifugation for recrystallization, and the mother liquor is returned to step (1) for dissolving 2,3,5-trimethylbenzoquinone.
  • the present invention also provides a device for synthesizing 2,3,5-trimethylhydroquinone, including:
  • a mixing kettle for mixing 2,3,5-trimethylbenzoquinone and a reaction solvent, a hydrogen absorber for contacting the 2,3,5-trimethylbenzoquinone solution with hydrogen, and hydrogenation
  • the reaction device of the reaction is a mixing kettle for mixing 2,3,5-trimethylbenzoquinone and a reaction solvent, a hydrogen absorber for contacting the 2,3,5-trimethylbenzoquinone solution with hydrogen, and hydrogenation.
  • the reaction device is a fixed bed reactor, and the catalyst is packed in the fixed bed reactor, so that continuous production can be realized.
  • the hydrogen absorber is a self-made hydrogen absorber, specifically a venturi tube, the side port is provided with a hydrogen inlet, the reaction liquid is pumped into the venturi tube, the side port sucks in hydrogen, and the reaction liquid mist
  • the chemical ejection and hydrogen are mixed uniformly, and then enter the fixed bed reactor for hydrogenation reaction, which innovatively changes the reaction process of the noble metal catalytic hydrogenation reaction mechanism where hydrogen is first adsorbed on the catalyst and then hydrogenated with the target raw material. Firstly, the uniformly distributed solvent of hydrogen is put in the target raw material, and then it is contacted with the catalyst, which effectively balances the speed of each step of the reaction, suppresses side reactions, and reduces the generation of impurities.
  • the device of the present invention also includes auxiliary equipment, and the auxiliary equipment includes a gas-liquid separator, a crystallization kettle, a hydrogen booster pump and a hydrogen buffer tank.
  • auxiliary equipment includes a gas-liquid separator, a crystallization kettle, a hydrogen booster pump and a hydrogen buffer tank.
  • the gas-liquid separator is used for gas-liquid separation of the reaction liquid produced by the fixed bed reactor; the crystallization kettle is used for crystallization and separation of the liquid material produced by the gas-liquid separator; the hydrogen pressurization The pump pressurizes the hydrogen generated by the gas-liquid separator and delivers it to the hydrogen buffer tank; the hydrogen buffer tank is used to input hydrogen into the hydrogen absorber.
  • the hydrogen is first mixed with the target raw material TMBQ and solvent, and then enters the fixed bed reactor for reaction, which can effectively control the concentration of activated hydrogen in the reaction system, increase the reaction speed, and suppress the formation of by-products.
  • Figure 1 is a process flow diagram of the present invention.
  • Fig. 1 is a process flow diagram of the present invention.
  • the device includes a mixing kettle, a hydrogen absorber, a fixed bed reactor, a gas-liquid separator and a crystallization kettle which are connected in sequence.
  • the upper part of the mixing kettle is provided with a material inlet, and the lower part is provided with a solution outlet.
  • the solution from the solution outlet is input into the hydrogen absorber through a pump set on the pipeline.
  • a hydrogen inlet is provided on the side wall of the hydrogen absorber, and the hydrogen inlet is connected with a hydrogen buffer tank, and hydrogen is stored in the hydrogen buffer tank.
  • the gas-liquid separator is provided with a gas outlet and a liquid outlet.
  • the liquid outlet is connected to the crystallization kettle, and the recovered hydrogen can be obtained from the gas outlet.
  • the recovered hydrogen is passed into the hydrogen buffer tank through a booster pump. After the solution in the crystallization kettle is crystallized, the solid obtained is the product TMHQ, and the mother liquor can be returned to the mixing kettle for continuous application.
  • TMBQ is mixed with the solvent in a certain proportion in the mixing kettle to form a TMBQ solution.
  • the temperature is raised to the specified temperature.
  • the solution is mixed with hydrogen by the hydrogen absorber, it enters the fixed bed reactor filled with the catalyst.
  • the fixed bed reactor controls the temperature at the specified temperature. Temperature is required, and the hydrogenation reaction is completed in a fixed bed reactor.
  • the excess hydrogen is returned to the hydrogen buffer tank via a booster pump through the gas-liquid separator, and the liquid material enters the cooling crystallization kettle. After the cold treatment, the product is separated by centrifugation. TMHQ can be recrystallized again.
  • the mother liquor enters the TMBQ mixing kettle to prepare the TMBQ reaction liquid.
  • Example 2-20 The difference between Examples 2-20 and Example 1 lies in the selection of different solvents, different ratios and reaction temperatures. Other conditions are the same as those of Example 1. All experimental results are summarized in Table 1.
  • benzene 1:1 (W:W) mixed solvent 1000g, TMBQ200g, 20g 2% palladium-carbon catalyst into the 2000mL autoclave, stir, preheat to 50°C, and pass hydrogen (pressure ⁇ 0.4MPa) to carry out the reaction while maintaining the temperature at 50-60°C.
  • the reaction time is 2h.
  • the indicator for the completion of the reaction is that the hydrogen pressure rises.
  • the pressure is maintained for more than 10 minutes, the material is cooled and crystallized, and the product TMHQ is filtered by centrifugation: 202.67g, tracking detection, conversion rate: 99.24%, selectivity: 99.75%, yield: 98.99%, purity: 99.01%, total impurities: 0.99%.
  • the pressure is maintained for more than 10 minutes, the material is cooled and crystallized, and the product TMHQ is filtered by centrifugation: 201.69g, tracking detection, conversion rate: 99.17%, selectivity: 99.54%, yield: 98.71%, purity: 99.20%, total impurities: 0.80%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé et un dispositif de synthèse de 2,3,5-triméthylhydroquinone ; la 2,3,5-triméthylbenzoquinone (TMBQ) est mélangée avec un système de solvant mixte alcool-hydrocarbure aromatique ou alcool-alcane, ensuite le liquide de réaction est mélangé intimement avec de l'hydrogène par l'intermédiaire d'un absorbeur d'hydrogène, puis entre dans un lit fixe équipé d'un catalyseur à base de métal précieux pour effectuer une réaction d'hydrogénation afin d'obtenir de la 2,3,5-triméthylhydroquinone (TMHQ). La solution technique améliore la sélectivité de la réaction, supprime de manière efficace les réactions secondaires, réduit la teneur en impuretés du produit, améliore la pureté de la 2,3,5-triméthylhydroquinone (TMHQ), ce qui simplifie le processus de production, et réduit l'émission d'eaux usées, de gaz résiduaire et de déchets solides, et présente de bons avantages de protection de l'environnement.
PCT/CN2020/117529 2019-12-30 2020-09-24 Procédé et dispositif de synthèse de 2,3,5-triméthylhydroquinone WO2021135443A1 (fr)

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CN201911396053.9A CN111253218A (zh) 2019-12-30 2019-12-30 一种2,3,5-三甲基氢醌的合成方法和装置

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CN111253218A (zh) * 2019-12-30 2020-06-09 上虞新和成生物化工有限公司 一种2,3,5-三甲基氢醌的合成方法和装置
CN114621060B (zh) * 2020-12-12 2023-07-07 中国科学院大连化学物理研究所 对苯醌加氢制备对苯二酚的方法
CN113680287A (zh) * 2021-09-01 2021-11-23 南京延长反应技术研究院有限公司 一种制备三甲基苯醌的强化氧化系统及方法
CN115784860B (zh) * 2023-01-17 2023-05-12 山东新和成维生素有限公司 一种2，3，5-三甲基氢醌的制备方法和应用

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US3842130A (en) * 1971-11-05 1974-10-15 Kuraray Co Process for preparing 2,3,5-trimethyl hydroquinone
CN105461518A (zh) * 2015-12-30 2016-04-06 浙江新和成股份有限公司 一种2,3,5-三甲基对苯二酚的合成方法
CN106565423A (zh) * 2016-11-15 2017-04-19 浙江新和成药业有限公司 一种三甲苯合成三甲基氢醌的方法
CN108084006A (zh) * 2017-10-30 2018-05-29 浙江新和成药业有限公司 一种三甲基苯醌及三甲基氢醌的制备方法
CN111253218A (zh) * 2019-12-30 2020-06-09 上虞新和成生物化工有限公司 一种2,3,5-三甲基氢醌的合成方法和装置

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JPH07103055B2 (ja) * 1985-04-16 1995-11-08 三菱瓦斯化学株式会社 ２，３，５−トリメチルハイドロキノンの製造方法
FR2784104B1 (fr) * 1998-09-18 2002-12-27 Rhone Poulenc Nutrition Animal Procede de preparation de la vitamine e
CN110201663B (zh) * 2019-05-28 2020-06-30 浙江大学 一种选择性加氢催化剂在加氢反应中作为催化剂的应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3842130A (en) * 1971-11-05 1974-10-15 Kuraray Co Process for preparing 2,3,5-trimethyl hydroquinone
CN105461518A (zh) * 2015-12-30 2016-04-06 浙江新和成股份有限公司 一种2,3,5-三甲基对苯二酚的合成方法
CN106565423A (zh) * 2016-11-15 2017-04-19 浙江新和成药业有限公司 一种三甲苯合成三甲基氢醌的方法
CN108084006A (zh) * 2017-10-30 2018-05-29 浙江新和成药业有限公司 一种三甲基苯醌及三甲基氢醌的制备方法
CN111253218A (zh) * 2019-12-30 2020-06-09 上虞新和成生物化工有限公司 一种2,3,5-三甲基氢醌的合成方法和装置

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