WO2016091058A1 - Method for preparing 3-pentanone from 2-pentene - Google Patents

Method for preparing 3-pentanone from 2-pentene Download PDF

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WO2016091058A1
WO2016091058A1 PCT/CN2015/095258 CN2015095258W WO2016091058A1 WO 2016091058 A1 WO2016091058 A1 WO 2016091058A1 CN 2015095258 W CN2015095258 W CN 2015095258W WO 2016091058 A1 WO2016091058 A1 WO 2016091058A1
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reaction
pentene
pentanol
catalyst
pentanone
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Chinese (zh)
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石康明
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派尔科化工材料(启东)有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/128Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04Saturated compounds containing keto groups bound to acyclic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/04Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/52Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

Definitions

  • the present invention relates to a process for the preparation of 3-pentanone from 2-pentene, and in particular to a process for the preparation of 3-pentanone from 2-pentene by addition, transesterification and dehydrogenation.
  • 3-pentanone is an important intermediate in fine chemical products, mainly used in the preparation of pesticides, pharmaceuticals and other products.
  • 3-pentanone can be obtained by high temperature decarboxylation of propionic acid.
  • the reaction is a process of reducing the molecular weight and it is required to carry out the reaction at a very high temperature, the reaction conditions are severe and the production efficiency is not satisfactory.
  • 2-pentene obtained by processing petroleum to produce ethylene by-produced carbon five fractions as a raw material can also produce 3-pentanol by hydration reaction, including 2-pentene indirect hydration and direct hydration.
  • the present invention provides a process for producing 3-pentanone from 2-pentene, which solves the technical problem of attempting to prepare 3-pentanone from 2-pentene by addition, transesterification and dehydrogenation.
  • a method for preparing 3-pentanone from 2-pentene characterized in that the method comprises the steps of:
  • reaction liquid obtained in the step 1) is subjected to rectification in a rectification column having a theoretical plate of 30; first, unreacted 2-pentene and acetic acid are recovered under normal pressure; and the mass fraction is obtained at 99.50 under reduced pressure. % of amyl acetate; the obtained 2-pentene and acetic acid are recycled.
  • the methanol and the amyl acetate obtained in the step 2) are subjected to catalytic transesterification to obtain a mixture of 2-pentanol and 3-pentanol; the transesterification reaction temperature is 62-80 ° C, and the molar ratio of methanol to amyl acetate The ratio is 2.0 to 5.0:1; the catalyst is sodium methoxide, the catalyst is added in an amount of 0.3 to 2% by mass of the amyl acetate, and the methyl acetate as a by-product of the transesterification is separated from the top of the rectification column to control the reflux ratio of the rectification column. 1:1 to 4:1;
  • the 3-pentanol obtained in the step 4) is directly subjected to catalytic dehydrogenation distillation to obtain high-purity 3-pentanone; the catalytic dehydrogenation reaction temperature is 113-118 ° C, the reaction pressure is normal pressure, and the catalyst 3 -
  • the pentanol loading WWH is 2.5-5.5 hr -1 , and the dehydrogenation reaction uses a granular Raney nickel-type metal alloy as a catalyst, and its composition is:
  • A is one selected from the group consisting of Ce and Bi; the dehydrogenation reaction product is discharged in a gas phase, and the gas phase reaction product is directly purified into a rectification column having a theoretical plate of 50 to obtain a high-purity 3-pentanone product, and the rectification is controlled.
  • the reflux ratio is from 1:1 to 10:1.
  • the component A in the catalyst for the catalytic dehydrogenation reaction in the step 5) of the present invention is selected from Ce; and the catalyst in the step 5) has a particle size of 0.02 to 0.08 mm.
  • the molar ratio of acetic acid to 2-pentene in the step 1) of the present invention is 2.5 to 3.5:1, the mass space velocity of the addition reaction is 1.5 to 2.5 hr -1 ; and the reaction temperature is 85 to 90 ° C; The reaction pressure is 0.9 to 1.5 MPa.
  • the catalyst sulfonic acid cation exchange resin described in the step 1) of the present invention has a mass exchange capacity of 4 to 5 mmol/g.
  • the transesterification reaction temperature in the step 3) of the present invention is 65 to 75 ° C, and the molar ratio of methanol to amyl acetate is 3.0 to 4.0:1.
  • the catalyst sodium methoxide described in the step 3) of the present invention is added in an amount of 0.5 to 1% by mass of the amyl acetate.
  • the reflux ratio of the rectification described in the step 3) of the present invention is from 2:1 to 3:1.
  • the catalyst described in the step 5) of the present invention has a 3-pentanol loading WWH of from 3 to 4 hr -1 .
  • the reflux ratio of the rectification described in the step 5) of the present invention is from 2:1 to 6:1.
  • the molar ratio of acetic acid to 2-pentene in the above step 1) is preferably 2.5 to 3.5:1; the mass exchange capacity of the sulfonic acid cation exchange resin is preferably 4 to 5 mmol/g;
  • the reaction temperature is preferably from 1.5 to 2.5 hr -1 ; the reaction temperature is preferably from 85 to 90 ° C; and the reaction pressure is preferably from 0.9 to 1.5 MPa.
  • the molar ratio of methanol to amyl acetate in the above step 3) is preferably from 3.0 to 4.0:1; the reaction temperature is preferably from 65 to 75 ° C; and the amount of the catalyst is preferably from 0.5 to 1% by mass of the amyl acetate.
  • the reflux ratio of the rectification is preferably from 2:1 to 3:1.
  • the rectification described in the above step 4) can be carried out in a continuous operation or a batch operation, and the obtained 2-pentanol is also a fine chemical intermediate having a higher added value.
  • the component A in the dehydrogenation catalyst is preferably selected from Ce; the particle size of the catalyst is preferably 0.02 to 0.08 mm; the 3-pentanol load WWH of the catalyst is 3 to 4 hr -1 ; It is preferably from 2:1 to 6:1.
  • the surface of the sulfonic acid cation exchange resin in the above step 1) contains a sulfonic acid group.
  • acetic acid When catalyzing the addition reaction of 2-pentene with acetic acid, it preferentially adsorbs acetic acid and forms a liquid crystal film of acetic acid on the surface of the catalyst. After the pentenene molecule diffuses to the surface of the liquid film, it must pass through the liquid film and adsorb on the surface of the catalyst in a chemical adsorption state, and then an electrophilic addition reaction of the positive carbon ion with the acetic acid occurs.
  • acetic acid is more reactive than water, so that the conversion and selectivity of the reaction are significantly improved.
  • the addition reaction product of 2-pentene and acetic acid is a mixture of sec-amyl acetate and (3-pentyl) acetate, wherein sec-amyl acetate accounts for about 30% of the total mass.
  • the (3-pentyl) acetate was 70%.
  • catalytic distillation reaction can be carried out in a catalytic rectification plant comprising two upper and lower portions, the upper part being a rectification part and the lower part being a reaction part.
  • the reaction by-product methyl acetate is vaporized and then raised to the upper rectification column for rectification separation, methyl acetate is obtained at the top, and unreacted methanol is refluxed from the rectification portion to the transesterification reaction portion to continue the reaction.
  • the methyl acetate produced by transesterification can be treated as a by-product.
  • catalytic rectification reaction can also be carried out in a catalytic rectification plant comprising two upper and lower portions, the upper part being a rectification part and the lower part being a reaction part.
  • the reaction portion is a liquid phase slurry bed reactor, and the rectification portion may be a tray rectification column. After the reaction product is vaporized, it is raised to the upper rectification column for rectification, and a high-purity 3-pentanone product is obtained at the top of the column, and the unreacted 3-pentanol is directly refluxed from the rectification portion to the dehydrogenation reaction portion to continue the reaction.
  • a good performance Al-Ni-Ce or Bi catalyst is selected in the 3-pentanol dehydrogenation reaction, and the reaction can be carried out at a lower temperature due to the high catalyst activity, and the catalyst is
  • the treatment capacity is significantly improved while the product selectivity reaches 100%, which ensures that the reactants do not contain any by-products, and the conversion of 3-pentanol is the same as the purity of the product.
  • the key to the present invention is the development of a process for the preparation of 3-pentanone from 2-pentene. Compared with the existing process, it has the advantages of high conversion rate and good selectivity, which not only greatly reduces the production cost, but also is a green production process.
  • the transesterification reaction of the present invention is a catalytic transesterification distillation reaction
  • the dehydrogenation reaction is a catalytic dehydrogenation rectification reaction.
  • the conversion rate of the addition reaction, the transesterification reaction and the dehydrogenation reaction, the raw materials and products in the above-mentioned various formulas refer to the raw materials and direct products in which the corresponding reactions occur, and the addition reaction, transesterification reaction and dehydrogenation in the above various formulas
  • the raw materials, intermediate products, products, and catalysts involved in the conversion and selectivity of the reaction are all by mass.
  • Addition reaction 2-pentene is mixed with acetic acid and then subjected to an addition reaction in a liquid phase through a catalyst bed to convert 2-pentene and acetic acid into amyl acetate to obtain a reaction liquid; wherein the acetic acid and 2
  • the molar ratio of pentene is 2 to 5:1, the mass space velocity of the addition reaction is 1 to 3 hr -1 , the reaction temperature is 80 to 100 ° C, and the reaction pressure is 0.8 to 2.0 MPa.
  • the catalyst in the sulfonic acid-based cation exchange resin has a mass exchange capacity of 3 to 5.5 mmol/g.
  • reaction liquid obtained above is subjected to rectification in a rectification column having a theoretical plate of 30, and unreacted 2-pentene and acetic acid are first recovered under normal pressure, and then the mass percentage is 99.50% or more under reduced pressure.
  • Amyl acetate is a theoretical plate of 30, and unreacted 2-pentene and acetic acid are first recovered under normal pressure, and then the mass percentage is 99.50% or more under reduced pressure.
  • the above addition reaction was carried out in a tubular fixed bed reactor having a size of ⁇ 25 mm ⁇ 1500 mm.
  • the reactor was charged with 100 g of a spherical sulfonic acid cation exchange resin catalyst having a particle diameter of 0.40 to 1.25 mm to constitute a fixed bed catalyst bed, and the mass exchange capacity of the resin was 3 to 5.5 mmol/g.
  • the reactor is equipped with a circulating hot water temperature control jacket, and a temperature measuring platinum resistor is installed on the upper, middle and lower sides of the catalyst bed.
  • the reaction feed is controlled by the feed pump and the system pressure is regulated by the back pressure valve.
  • the reaction raw material is reacted through a fixed bed at a set feed amount, and an addition reaction is carried out under the reaction conditions set as described above.
  • the addition reaction products obtained in each of Examples 1-10 were subjected to component analysis by a chromatographic method, and the conversion ratio and product selectivity of the addition reactions of the respective examples were respectively calculated.
  • the reaction conditions and results of the respective examples are shown in Table 1.
  • Transesterification reaction a mixture of methanol and pentyl acetate obtained in Examples 1 to 10, respectively, is subjected to catalytic transesterification to obtain a mixture of 2-pentanol and 3-pentanol; wherein the molar ratio of methanol to amyl acetate a ratio of 2.0 to 5.0:1, a reaction temperature of the catalytic transesterification reaction is 62 to 80 ° C, a catalyst is sodium methoxide, and a catalyst is added in an amount of 0.3 to 2% by mass of the amyl acetate;
  • the methyl acetate, a by-product of the catalytic transesterification distillation reaction is discharged in a vapor phase, and the gas phase reaction product directly enters the distillation column of the theoretical plate of 30 and is separated from the top of the rectification column, and the reflux ratio of the controlled rectification is 1:1. ⁇ 4:1.
  • the obtained mixture of 2-pentanol and 3-pentanol was separately subjected to rectification in a rectification column having a theoretical plate of 70.
  • the temperature of the column is 118 to 125 ° C and the reflux ratio is 10 to 20:1
  • the fraction of 115 to 116 ° C is collected from the top of the column to obtain a content of 99.5% 3-pentanol
  • the temperature of the column is 126-130 ° C and the reflux ratio is 10-20:1
  • the fraction of 118-119 ° C is collected from the top of the column, and the fraction product is 99.5 by mass. More than % of pentaerythritol.
  • the above transesterification reaction is carried out in a reactive rectification unit consisting of a transesterification reactor and a rectification column.
  • the reactor was a 1000 ml glass reactor.
  • the top of the reactor is connected to the rectification column.
  • the number of theoretical plates of the rectification column is 30, and a condensing reflux device with a discharge port is arranged at the top of the rectification column.
  • the transesterification reaction products obtained in Examples 11 to 20 were subjected to component analysis by chromatography, and the conversion of the reaction and the selectivity of the product were calculated.
  • the reaction conditions and results of the respective Examples 11 to 20 are shown in Table 2.
  • the 3-pentanol obtained in Examples 11 to 20 was directly subjected to a catalytic dehydrogenation distillation reaction to obtain a high purity of the 3-pentanone.
  • the reaction temperature of the catalytic dehydrogenation distillation reaction is 113-118 ° C
  • the reaction pressure is normal pressure
  • the 3-pentanol load WWH of the catalyst is 2.5-5.5 hr -1
  • the catalytic dehydrogenation distillation reaction adopts the granular Raney nickel type.
  • the particle size of the catalyst is generally from 0.01 to 0.1 mm.
  • the product of the catalytic dehydrogenation distillation reaction is discharged in a gas phase, and the gas phase reaction product directly enters a rectification column having a theoretical plate of 50 for rectification and purification to obtain a high purity of the 3-pentanone product, and the rectification is controlled by rectification.
  • the reflux ratio is from 1:1 to 10:1.
  • the above reaction is carried out in a reactive rectification unit consisting of a dehydrogenation reactor and a rectification column.
  • the reactor is a 1000ml glass reactor.
  • the reactor is equipped with a mechanical stirring device, a thermometer, a feed port and a rectification column.
  • the external heating device has a theoretical plate number of 60 on the rectification column and a zone on the top of the rectification column.
  • 700 g of 3-pentanol was first added, and then 50 g of a Raney nickel catalyst having a particle size of 0.03 to 0.05 mm was introduced into the reactor.
  • the reactor was heated to 113 to 118 ° C, and then maintained at this temperature.
  • 3-pentanol was continuously pumped into the reactor for reaction.
  • the reaction pressure is normal pressure
  • the catalyst has a 3-pentanol loading WWH of 2.5 to 5.5 hr -1
  • the number of theoretical plates of the rectification column is 50
  • the reflux ratio of the controlled rectification is 1:1 to 10:1.
  • the hydrogen produced by the dehydrogenation is discharged through the vent at the top of the rectification column, and the outlet material at the top of the rectification column is collected as a product.
  • the 3-pentanol feed amount and the product discharge amount should be controlled to balance each other to maintain the stability of the system.
  • the compositions of the catalysts of Examples 21 to 30, specific reaction conditions, 3-pentanol conversion and 3-pentanone selectivity of the dehydrogenation reaction, and the purity of the product are shown in Tables 3 and 4.
  • Example 25 99.9 100 6:1 99.9
  • Example 26 99.8 100 5:1 99.9
  • Example 27 99.9 100 4:1 99.8
  • Example 28 99.7 100 3:1 99.8
  • Example 29 99.9 100 3:1 99.8
  • Example 30 99.8 100 5:1 99.8

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Abstract

Disclosed is a method for preparing 3-pentanone from 2-pentene. The method comprises the following steps: 1) 2-pentene and acetic acid are mixed and an addition reaction takes place in a liquid phase through a catalyst bed, and special conditions are controlled so as to convert the 2-pentene and the acetic acid into amyl acetate; 2) the reaction liquid is rectified, unreacted 2-pentene and acetic acid are firstly recovered under normal pressure, and then amyl acetate with a mass fraction of 99.50% is obtained under reduced pressure; 3) methanol and the amyl acetate are subjected to a catalytic rectification reaction to obtain a mixture of 2-pentanol and 3-pentanol; 4) the mixture of 2-pentanol and 3-pentanol is rectified to obtain 3-pentanol with a mass percentage content of 99.5%; and 5) the 3-pentanol is subjected to a catalytic dehydrogenation and rectification reaction, so as to directly prepare 3-pentanone with a high purity. Compared with existing processes, the method has the advantages of a high conversion rate and a good selectivity; and the method not only has a production cost which is greatly reduced, but is also a green and environmentally friendly production process.

Description

一种由2-戊烯制备3-戊酮的方法Method for preparing 3-pentanone from 2-pentene 技术领域Technical field
本发明涉及一种由2-戊烯制备3-戊酮的方法,特别涉及通过加成、酯交换和脱氢反应由2-戊烯制备3-戊酮的方法。The present invention relates to a process for the preparation of 3-pentanone from 2-pentene, and in particular to a process for the preparation of 3-pentanone from 2-pentene by addition, transesterification and dehydrogenation.
背景技术Background technique
3-戊酮是一种重要的精细化工产品中间体,主要用于制备农药、医药等产品。3-戊酮可以由丙酸经高温脱羧反应制得。但由于该反应是分子量减小的过程且需在非常高的温度下进行反应,反应条件苛刻,生产效率不甚理想。另外,以石油裂解制乙烯副产的碳五馏份中加工制得的2-戊烯为原料,通过水合反应也可以生产3-戊醇,其中包括2-戊烯间接水合和直接水合两种工艺,虽然间接水合具有转化率高、选择性好的优势,但由于制备过程中需使用硫酸,对设备的耐腐蚀要求极高,且环境污染仍较为严重,而直接水合工艺则不存在这些问题,是一条环境友好的技术路线,但该方法的不足在于反应转化率过低,原料2-戊烯的循环量极大。目前尚未见到有关由3-戊醇脱氢制备3-戊酮的报导。3-pentanone is an important intermediate in fine chemical products, mainly used in the preparation of pesticides, pharmaceuticals and other products. 3-pentanone can be obtained by high temperature decarboxylation of propionic acid. However, since the reaction is a process of reducing the molecular weight and it is required to carry out the reaction at a very high temperature, the reaction conditions are severe and the production efficiency is not satisfactory. In addition, 2-pentene obtained by processing petroleum to produce ethylene by-produced carbon five fractions as a raw material can also produce 3-pentanol by hydration reaction, including 2-pentene indirect hydration and direct hydration. Process, although indirect hydration has the advantages of high conversion rate and good selectivity, due to the need to use sulfuric acid in the preparation process, the corrosion resistance of the equipment is extremely high, and the environmental pollution is still serious, but the direct hydration process does not have these problems. It is an environmentally friendly technical route, but the shortcoming of this method is that the reaction conversion rate is too low, and the circulation amount of the raw material 2-pentene is extremely large. There have been no reports on the preparation of 3-pentanone by dehydrogenation of 3-pentanol.
发明内容Summary of the invention
本发明提供了一种由2-戊烯制备3-戊酮的方法,它要解决的技术问题是试图通过加成、酯交换和脱氢反应由2-戊烯制备3-戊酮的方法。The present invention provides a process for producing 3-pentanone from 2-pentene, which solves the technical problem of attempting to prepare 3-pentanone from 2-pentene by addition, transesterification and dehydrogenation.
以下是本发明解决上述技术问题的技术方案:The following is a technical solution of the present invention to solve the above technical problems:
一种由2-戊烯制备3-戊酮的方法,其特征在于该方法包括以下步骤:A method for preparing 3-pentanone from 2-pentene, characterized in that the method comprises the steps of:
1)将2-戊烯加入醋酸,然后以液相通过催化剂床层进行加成反应,以使2-戊烯和醋酸转化成醋酸戊酯,获得反应液;所述的醋酸与2-戊烯的摩尔比为2~5:1,所述加成反应的质量空速为1~3hr-1,反应温度为80~100℃,反应压力为0.8~2.0MPa,所述催化剂床层中的催化剂为磺酸基阳离子交换树脂,磺酸基阳离子交换树脂的质量交换容量为3~5.5mmol/g;1) adding 2-pentene to acetic acid, and then performing an addition reaction in a liquid phase through a catalyst bed to convert 2-pentene and acetic acid into amyl acetate to obtain a reaction liquid; the acetic acid and 2-pentene The molar ratio is 2 to 5:1, the mass space velocity of the addition reaction is 1 to 3 hr -1 , the reaction temperature is 80 to 100 ° C, the reaction pressure is 0.8 to 2.0 MPa, and the catalyst in the catalyst bed Is a sulfonic acid cation exchange resin, the mass exchange capacity of the sulfonic acid cation exchange resin is 3 to 5.5 mmol / g;
2)步骤1)获得的反应液在一理论板为30的精馏塔中进行精馏;先在常压下回收未反应的2-戊烯、醋酸;再在减压下得到质量分数在99.50%的醋酸戊酯;得到的2-戊烯和醋酸循环使用。2) The reaction liquid obtained in the step 1) is subjected to rectification in a rectification column having a theoretical plate of 30; first, unreacted 2-pentene and acetic acid are recovered under normal pressure; and the mass fraction is obtained at 99.50 under reduced pressure. % of amyl acetate; the obtained 2-pentene and acetic acid are recycled.
3)将甲醇和步骤2)获得的醋酸戊酯经催化酯交换精馏反应制得2-戊醇和3-戊醇的混合物;酯交换反应温度为62~80℃,甲醇与醋酸戊酯的摩尔比为2.0~5.0:1;催化剂为甲醇钠,催化剂加入量为醋酸戊酯质量的0.3~2%,酯交换反应副产物醋酸甲酯从精馏塔的塔顶分离,控制精馏的回流比为1∶1~4∶1;3) The methanol and the amyl acetate obtained in the step 2) are subjected to catalytic transesterification to obtain a mixture of 2-pentanol and 3-pentanol; the transesterification reaction temperature is 62-80 ° C, and the molar ratio of methanol to amyl acetate The ratio is 2.0 to 5.0:1; the catalyst is sodium methoxide, the catalyst is added in an amount of 0.3 to 2% by mass of the amyl acetate, and the methyl acetate as a by-product of the transesterification is separated from the top of the rectification column to control the reflux ratio of the rectification column. 1:1 to 4:1;
4)将步骤3)获得的2-戊醇和3-戊醇的混合物进行精馏,精馏在一理论板为70的精馏塔中进行;在塔釜温度为118~125℃,回流比为10~20∶1时,从塔顶收集115~116℃的馏份, 得到含量为99.5%的3-戊醇;当塔釜温度为126~130℃,回流比为10~20∶1时,从塔顶收集118~119℃的馏份,产品为含量为99.5%的2-戊醇。4) The mixture of 2-pentanol and 3-pentanol obtained in the step 3) is subjected to rectification, and the rectification is carried out in a rectification column having a theoretical plate of 70; the temperature in the column is 118 to 125 ° C, and the reflux ratio is At 10 to 20:1, a fraction of 115 to 116 ° C is collected from the top of the column. A 3-pentanol having a content of 99.5% is obtained; when the temperature of the column is 126-130 ° C and the reflux ratio is 10-20: 1, a fraction of 118-119 ° C is collected from the top of the column, and the product is 99.5%. 2-pentanol.
5)将步骤4)获得的3-戊醇通过催化脱氢精馏反应直接制得高纯度的3-戊酮;催化脱氢反应温度为113~118℃,反应压力为常压,催化剂的3-戊醇负荷WWH为2.5~5.5hr-1,脱氢反应采用颗粒状Raney镍型金属合金作为催化剂,其组成为:5) The 3-pentanol obtained in the step 4) is directly subjected to catalytic dehydrogenation distillation to obtain high-purity 3-pentanone; the catalytic dehydrogenation reaction temperature is 113-118 ° C, the reaction pressure is normal pressure, and the catalyst 3 - The pentanol loading WWH is 2.5-5.5 hr -1 , and the dehydrogenation reaction uses a granular Raney nickel-type metal alloy as a catalyst, and its composition is:
Al-Ni-AAl-Ni-A
其中A为选自Ce、Bi中的一种;脱氢反应产物以气相出料,该气相反应产物直接进入理论板为50的精馏塔提纯得到高纯度的3-戊酮产品,控制精馏的回流比为1∶1~10∶1。Wherein A is one selected from the group consisting of Ce and Bi; the dehydrogenation reaction product is discharged in a gas phase, and the gas phase reaction product is directly purified into a rectification column having a theoretical plate of 50 to obtain a high-purity 3-pentanone product, and the rectification is controlled. The reflux ratio is from 1:1 to 10:1.
本发明步骤5)中所述催化剂的组成为:Al-Ni-A,其中A为选自Ce、Bi中的一种,各组分的重量比为:Al∶Ni∶A=1∶(0.8~0.94)∶(0.03~0.2);所述催化剂的颗粒度为0.01~0.1mm。The composition of the catalyst in the step 5) of the present invention is: Al-Ni-A, wherein A is one selected from the group consisting of Ce and Bi, and the weight ratio of each component is: Al:Ni:A=1:(0.8 ~0.94): (0.03 to 0.2); the catalyst has a particle size of 0.01 to 0.1 mm.
本发明步骤5)中所述催化脱氢反应的催化剂中的组分A选用Ce;步骤5)中所述催化剂的颗粒度为0.02~0.08mm。The component A in the catalyst for the catalytic dehydrogenation reaction in the step 5) of the present invention is selected from Ce; and the catalyst in the step 5) has a particle size of 0.02 to 0.08 mm.
本发明步骤1)中所述的醋酸与2-戊烯的摩尔比为2.5~3.5:1,所述加成反应的质量空速为1.5~2.5hr-1;反应温度为85~90℃;反应压力为0.9~1.5Mpa。The molar ratio of acetic acid to 2-pentene in the step 1) of the present invention is 2.5 to 3.5:1, the mass space velocity of the addition reaction is 1.5 to 2.5 hr -1 ; and the reaction temperature is 85 to 90 ° C; The reaction pressure is 0.9 to 1.5 MPa.
本发明步骤1)中所述的催化剂磺酸基阳离子交换树脂的质量交换容量为4~5mmol/g。The catalyst sulfonic acid cation exchange resin described in the step 1) of the present invention has a mass exchange capacity of 4 to 5 mmol/g.
本发明步骤3)中所述的酯交换反应温度为65~75℃,甲醇与醋酸戊酯的摩尔比为3.0~4.0:1。The transesterification reaction temperature in the step 3) of the present invention is 65 to 75 ° C, and the molar ratio of methanol to amyl acetate is 3.0 to 4.0:1.
本发明步骤3)中所述的催化剂甲醇钠加入量为醋酸戊酯质量的0.5~1%。The catalyst sodium methoxide described in the step 3) of the present invention is added in an amount of 0.5 to 1% by mass of the amyl acetate.
本发明步骤3)中所述的精馏的回流比为2∶1~3∶1。The reflux ratio of the rectification described in the step 3) of the present invention is from 2:1 to 3:1.
本发明步骤5)中所述的催化剂的3-戊醇负荷WWH为3~4hr-1The catalyst described in the step 5) of the present invention has a 3-pentanol loading WWH of from 3 to 4 hr -1 .
本发明步骤5)中所述的精馏的回流比为2∶1~6∶1。The reflux ratio of the rectification described in the step 5) of the present invention is from 2:1 to 6:1.
上述步骤1)所述的醋酸与2-戊烯的摩尔比,最好为2.5~3.5:1;磺酸基阳离子交换树脂的质量交换容量最好为4~5mmol/g;质量空速最好为1.5~2.5hr-1;反应温度最好为85~90℃;反应压力最好为0.9~1.5MPa。The molar ratio of acetic acid to 2-pentene in the above step 1) is preferably 2.5 to 3.5:1; the mass exchange capacity of the sulfonic acid cation exchange resin is preferably 4 to 5 mmol/g; The reaction temperature is preferably from 1.5 to 2.5 hr -1 ; the reaction temperature is preferably from 85 to 90 ° C; and the reaction pressure is preferably from 0.9 to 1.5 MPa.
上述步骤3)所述的甲醇与醋酸戊酯的摩尔比,最好为3.0~4.0:1;反应温度最好为65~75℃;催化剂加入量最好为醋酸戊酯质量的0.5~1%;精馏的回流比最好为2∶1~3∶1。The molar ratio of methanol to amyl acetate in the above step 3) is preferably from 3.0 to 4.0:1; the reaction temperature is preferably from 65 to 75 ° C; and the amount of the catalyst is preferably from 0.5 to 1% by mass of the amyl acetate. The reflux ratio of the rectification is preferably from 2:1 to 3:1.
上述步骤4)所述的精馏可以采用连续操作或者间歇操作方式,所获得的2-戊醇同样是一种附加值较高的精细化工中间体。The rectification described in the above step 4) can be carried out in a continuous operation or a batch operation, and the obtained 2-pentanol is also a fine chemical intermediate having a higher added value.
上述步骤5)脱氢反应催化剂中的组分A最好选用Ce;催化剂的颗粒度最好为0.02~0.08mm;催化剂的3-戊醇负荷WWH为3~4hr-1;精馏的回流比最好为2∶1~6∶1。 In the above step 5), the component A in the dehydrogenation catalyst is preferably selected from Ce; the particle size of the catalyst is preferably 0.02 to 0.08 mm; the 3-pentanol load WWH of the catalyst is 3 to 4 hr -1 ; It is preferably from 2:1 to 6:1.
上述步骤1)中的磺酸基阳离子交换树脂表面含有磺酸基,在催化2-戊烯与醋酸的加成反应时,它将优先吸附醋酸并在催化剂表面形成一层醋酸分子液膜,2-戊烯分子扩散至液膜表面后,必须穿过液膜并以化学吸附形态在催化剂表面吸附,再生成正碳离子与醋酸发生亲电加成反应。对于加成反应,醋酸比水的反应活性强,使得反应的转化率和选择性明显提高。The surface of the sulfonic acid cation exchange resin in the above step 1) contains a sulfonic acid group. When catalyzing the addition reaction of 2-pentene with acetic acid, it preferentially adsorbs acetic acid and forms a liquid crystal film of acetic acid on the surface of the catalyst. After the pentenene molecule diffuses to the surface of the liquid film, it must pass through the liquid film and adsorb on the surface of the catalyst in a chemical adsorption state, and then an electrophilic addition reaction of the positive carbon ion with the acetic acid occurs. For the addition reaction, acetic acid is more reactive than water, so that the conversion and selectivity of the reaction are significantly improved.
上述步骤1)中的加成反应中,2-戊烯与醋酸的加成反应产物是醋酸仲戊酯和醋酸(3-戊)酯混合物,其中醋酸仲戊酯约占总质量的30%,醋酸(3-戊)酯为70%。In the addition reaction in the above step 1), the addition reaction product of 2-pentene and acetic acid is a mixture of sec-amyl acetate and (3-pentyl) acetate, wherein sec-amyl acetate accounts for about 30% of the total mass. The (3-pentyl) acetate was 70%.
上述步骤3)催化精馏反应可以在一个催化精馏设备中进行,催化精馏设备包括上下两个部分,上部为精馏部分,下部为反应部分。反应副产物醋酸甲酯气化后上升至上部的精馏塔中进行精馏分离,塔顶得到醋酸甲酯,未反应的甲醇从精馏部分回流到酯交换反应部分继续反应。酯交换产生的醋酸甲酯可作为副产物进行处理。The above step 3) catalytic distillation reaction can be carried out in a catalytic rectification plant comprising two upper and lower portions, the upper part being a rectification part and the lower part being a reaction part. The reaction by-product methyl acetate is vaporized and then raised to the upper rectification column for rectification separation, methyl acetate is obtained at the top, and unreacted methanol is refluxed from the rectification portion to the transesterification reaction portion to continue the reaction. The methyl acetate produced by transesterification can be treated as a by-product.
在酯交换反应时,没有发现异构化反应,生成的2-戊醇和3-戊醇比例不变,3-戊醇含量仍然为70%。2-戊醇的沸点为118.8℃,3-戊醇为115.3℃,利用两者间的沸点差,可以分别得到含量在99.5%以上的2-戊醇和3-戊醇产品。In the transesterification reaction, no isomerization reaction was found, and the ratio of 2-pentanol to 3-pentanol produced was unchanged, and the 3-pentanol content was still 70%. The boiling point of 2-pentanol is 118.8 ° C, and the 3-pentanol is 115.3 ° C. By using the difference in boiling point between the two, 2-pentanol and 3-pentanol products having a content of 99.5% or more can be obtained, respectively.
上述步骤5)催化精馏反应同样可以在一个催化精馏设备中进行,催化精馏设备包括上下两个部分,上部为精馏部分,下部为反应部分。反应部分为一个液相淤浆床反应器,精馏部分可以是塔板精馏塔。反应产物气化后上升至上部的精馏塔中进行精馏,塔顶得到高纯度的3-戊酮产品,未反应的3-戊醇直接从精馏部分回流到脱氢反应部分继续反应。The above step 5) catalytic rectification reaction can also be carried out in a catalytic rectification plant comprising two upper and lower portions, the upper part being a rectification part and the lower part being a reaction part. The reaction portion is a liquid phase slurry bed reactor, and the rectification portion may be a tray rectification column. After the reaction product is vaporized, it is raised to the upper rectification column for rectification, and a high-purity 3-pentanone product is obtained at the top of the column, and the unreacted 3-pentanol is directly refluxed from the rectification portion to the dehydrogenation reaction portion to continue the reaction.
上述步骤5)中,在3-戊醇脱氢反应中选择了一种性能良好的Al-Ni-Ce或Bi催化剂,由于催化剂活性高,可以使反应在更低的温度下进行,且催化剂的处理能力显著提高,同时产物选择性达到100%,这保证了反应物中不含有任何的副产物,3-戊醇的转化率与产品的纯度相同。In the above step 5), a good performance Al-Ni-Ce or Bi catalyst is selected in the 3-pentanol dehydrogenation reaction, and the reaction can be carried out at a lower temperature due to the high catalyst activity, and the catalyst is The treatment capacity is significantly improved while the product selectivity reaches 100%, which ensures that the reactants do not contain any by-products, and the conversion of 3-pentanol is the same as the purity of the product.
本发明的关键是开发了一种由2-戊烯制备3-戊酮的方法。与现有的工艺相比较,它具有转化率高和选择性好的优点,不仅生产成本大为降低,而且是一种绿色环保的生产工艺。The key to the present invention is the development of a process for the preparation of 3-pentanone from 2-pentene. Compared with the existing process, it has the advantages of high conversion rate and good selectivity, which not only greatly reduces the production cost, but also is a green production process.
具体实施方式detailed description
下面结合具体实施例进一步阐述本发明,应理解,这些实施例仅用于说明本发明而不用于限制本发明的保护范围。The invention is further illustrated by the following examples, which are intended to illustrate the invention and not to limit the scope of the invention.
在各实施例中,加成反应、酯交换反应和脱氢反应的转化率、选择性分别由下式计算。本发明的酯交换反应即为催化酯交换精馏反应,脱氢反应即为催化脱氢精馏反应。 In each of the examples, the conversion and selectivity of the addition reaction, the transesterification reaction, and the dehydrogenation reaction were respectively calculated by the following formula. The transesterification reaction of the present invention is a catalytic transesterification distillation reaction, and the dehydrogenation reaction is a catalytic dehydrogenation rectification reaction.
Figure PCTCN2015095258-appb-000001
Figure PCTCN2015095258-appb-000001
上述各式中加成反应、酯交换反应和脱氢反应的转化率、选择性中的原料和产品指发生相应反应的原料和直接产品,上述各式中加成反应、酯交换反应和脱氢反应的转化率、选择性中所涉及到的原料、中间产物、产品以及催化剂等均以质量计。The conversion rate of the addition reaction, the transesterification reaction and the dehydrogenation reaction, the raw materials and products in the above-mentioned various formulas refer to the raw materials and direct products in which the corresponding reactions occur, and the addition reaction, transesterification reaction and dehydrogenation in the above various formulas The raw materials, intermediate products, products, and catalysts involved in the conversion and selectivity of the reaction are all by mass.
【实施例1~10】[Examples 1 to 10]
加成反应:Addition reaction:
加成反应:2-戊烯与醋酸混合后以液相通过催化剂床层进行加成反应,以使2-戊烯和醋酸反应转化成醋酸戊酯,获得反应液;其中,所述醋酸与2-戊烯的摩尔比为2~5:1,所述加成反应的质量空速为1~3hr-1,反应温度为80~100℃,反应压力为0.8~2.0MPa,所述催化剂床层中的催化剂为磺酸基阳离子交换树脂,且磺酸基阳离子交换树脂树脂的质量交换容 量为3~5.5mmol/g。Addition reaction: 2-pentene is mixed with acetic acid and then subjected to an addition reaction in a liquid phase through a catalyst bed to convert 2-pentene and acetic acid into amyl acetate to obtain a reaction liquid; wherein the acetic acid and 2 The molar ratio of pentene is 2 to 5:1, the mass space velocity of the addition reaction is 1 to 3 hr -1 , the reaction temperature is 80 to 100 ° C, and the reaction pressure is 0.8 to 2.0 MPa. The catalyst in the sulfonic acid-based cation exchange resin has a mass exchange capacity of 3 to 5.5 mmol/g.
将上述获得的反应液在理论板为30的精馏塔中进行精馏,先在常压下回收未反应的2-戊烯和醋酸,再在减压下得到质量百分含量为99.50%以上的醋酸戊酯。The reaction liquid obtained above is subjected to rectification in a rectification column having a theoretical plate of 30, and unreacted 2-pentene and acetic acid are first recovered under normal pressure, and then the mass percentage is 99.50% or more under reduced pressure. Amyl acetate.
上述加成反应在尺寸为φ25mm×1500mm的管式固定床反应器中进行。反应器中装入粒径为0.40~1.25mm的球形磺酸基阳离子交换树脂催化剂100克构成固定床催化剂床层,树脂的质量交换容量为3~5.5mmol/g。反应器外部装循环热水温控夹套,在催化剂床层的上、中、下分别安装测温铂电阻。反应进料量由进料泵控制,系统压力由背压阀调节。The above addition reaction was carried out in a tubular fixed bed reactor having a size of φ25 mm × 1500 mm. The reactor was charged with 100 g of a spherical sulfonic acid cation exchange resin catalyst having a particle diameter of 0.40 to 1.25 mm to constitute a fixed bed catalyst bed, and the mass exchange capacity of the resin was 3 to 5.5 mmol/g. The reactor is equipped with a circulating hot water temperature control jacket, and a temperature measuring platinum resistor is installed on the upper, middle and lower sides of the catalyst bed. The reaction feed is controlled by the feed pump and the system pressure is regulated by the back pressure valve.
反应原料按设定的进料量通过固定床反应,并按上述设定的反应条件进行加成反应。实施例1-10分别得到的加成反应产物分别采用色谱分析法进行成分分析,并分别计算各实施例加成反应的转化率和产物选择性。各实施例的反应条件和结果见表1。The reaction raw material is reacted through a fixed bed at a set feed amount, and an addition reaction is carried out under the reaction conditions set as described above. The addition reaction products obtained in each of Examples 1-10 were subjected to component analysis by a chromatographic method, and the conversion ratio and product selectivity of the addition reactions of the respective examples were respectively calculated. The reaction conditions and results of the respective examples are shown in Table 1.
表1Table 1
Figure PCTCN2015095258-appb-000002
Figure PCTCN2015095258-appb-000002
【实施例11~20】[Examples 11 to 20]
酯交换反应Transesterification
酯交换反应:将甲醇分别和实施例1~10获得的醋酸戊酯分别经催化酯交换精馏反应制得2-戊醇和3-戊醇的混合物;其中,所述甲醇与醋酸戊酯的摩尔比为2.0~5.0:1,所述催化酯交换精馏反应的反应温度为62~80℃,催化剂为甲醇钠,且催化剂的加入量为所述醋酸戊酯质量的0.3~2%;所述催化酯交换精馏反应的副产物醋酸甲酯以气相出料,该气相反应产物直接进入理论板为30的精馏塔从精馏塔的塔顶分离,控制精馏的回流比为1∶1~4∶1。Transesterification reaction: a mixture of methanol and pentyl acetate obtained in Examples 1 to 10, respectively, is subjected to catalytic transesterification to obtain a mixture of 2-pentanol and 3-pentanol; wherein the molar ratio of methanol to amyl acetate a ratio of 2.0 to 5.0:1, a reaction temperature of the catalytic transesterification reaction is 62 to 80 ° C, a catalyst is sodium methoxide, and a catalyst is added in an amount of 0.3 to 2% by mass of the amyl acetate; The methyl acetate, a by-product of the catalytic transesterification distillation reaction, is discharged in a vapor phase, and the gas phase reaction product directly enters the distillation column of the theoretical plate of 30 and is separated from the top of the rectification column, and the reflux ratio of the controlled rectification is 1:1. ~4:1.
将获得的2-戊醇和3-戊醇的混合物分别在理论板为70的精馏塔中进行精馏。其中,在塔釜温度为118~125℃,回流比为10~20∶1时,从塔顶收集115~116℃的馏份,得到含量为 99.5%的3-戊醇;当塔釜温度为126~130℃,回流比为10~20∶1时,从塔顶收集118~119℃的馏份,馏分产品即为质量百分含量为99.5%以上的2-戊醇。The obtained mixture of 2-pentanol and 3-pentanol was separately subjected to rectification in a rectification column having a theoretical plate of 70. Wherein, when the temperature of the column is 118 to 125 ° C and the reflux ratio is 10 to 20:1, the fraction of 115 to 116 ° C is collected from the top of the column to obtain a content of 99.5% 3-pentanol; when the temperature of the column is 126-130 ° C and the reflux ratio is 10-20:1, the fraction of 118-119 ° C is collected from the top of the column, and the fraction product is 99.5 by mass. More than % of pentaerythritol.
上述酯交换反应在一个反应精馏装置中进行,反应精馏装置由酯交换反应器和精馏柱两部分组成。反应器为1000毫升的玻璃反应器。反应器顶部连接精馏柱,精馏柱的理论塔板数为30,精馏柱顶部安置一带出料口的冷凝回流装置。The above transesterification reaction is carried out in a reactive rectification unit consisting of a transesterification reactor and a rectification column. The reactor was a 1000 ml glass reactor. The top of the reactor is connected to the rectification column. The number of theoretical plates of the rectification column is 30, and a condensing reflux device with a discharge port is arranged at the top of the rectification column.
在反应器中加入130克醋酸戊酯及一定量的甲醇,再将甲醇钠催化剂加入反应器。反应器加热升温进行反应,控制精馏的回流比。反应所产生的醋酸甲酯通过收集精馏柱顶部出口物料来移出。待精馏柱顶部出口基本收集不到醋酸甲酯时,反应结束。将反应液冷却至室温,液体物料经精馏后分别得到含量在99.5%以上的2-戊醇和3-戊醇。3-戊醇可作为脱氢制备3-戊酮的原料。130 grams of amyl acetate and a quantity of methanol were added to the reactor, and a sodium methoxide catalyst was added to the reactor. The reactor is heated and heated to carry out a reaction, and the reflux ratio of the rectification is controlled. The methyl acetate produced by the reaction is removed by collecting the outlet material at the top of the rectification column. When the methyl acetate was not collected at the top outlet of the rectification column, the reaction was completed. The reaction solution was cooled to room temperature, and the liquid material was subjected to rectification to obtain 2-pentanol and 3-pentanol in an amount of 99.5% or more, respectively. 3-pentanol can be used as a raw material for the preparation of 3-pentanone by dehydrogenation.
实施例11~20得到的酯交换反应产物分别采用色谱分析法进行成分分析,并计算反应的转化率和产物选择性。各实施例11~20的反应条件和结果见表2。The transesterification reaction products obtained in Examples 11 to 20 were subjected to component analysis by chromatography, and the conversion of the reaction and the selectivity of the product were calculated. The reaction conditions and results of the respective Examples 11 to 20 are shown in Table 2.
表2Table 2
Figure PCTCN2015095258-appb-000003
Figure PCTCN2015095258-appb-000003
【实施例21~30】[Examples 21 to 30]
脱氢反应Dehydrogenation reaction
脱氢反应:将实施例11~20获得的3-戊醇分别通过催化脱氢精馏反应直接制得高纯度的所述3-戊酮。其中催化脱氢精馏反应的反应温度为113~118℃,反应压力为常压,催化剂的3-戊醇负荷WWH为2.5~5.5hr-1,催化脱氢精馏反应采用颗粒状Raney镍型金属合金作为催化剂, 其组成为:Al-Ni-A,其中A为Ce、Bi中的一种,各组分的重量比为:Al∶Ni∶A=1∶(0.8~0.94)∶(0.03~0.2)。催化剂的颗粒度一般为0.01~0.1mm。Dehydrogenation reaction: The 3-pentanol obtained in Examples 11 to 20 was directly subjected to a catalytic dehydrogenation distillation reaction to obtain a high purity of the 3-pentanone. The reaction temperature of the catalytic dehydrogenation distillation reaction is 113-118 ° C, the reaction pressure is normal pressure, the 3-pentanol load WWH of the catalyst is 2.5-5.5 hr -1 , and the catalytic dehydrogenation distillation reaction adopts the granular Raney nickel type. The metal alloy is used as a catalyst, and its composition is: Al-Ni-A, wherein A is one of Ce and Bi, and the weight ratio of each component is: Al:Ni:A=1:(0.8-0.94):(0.03 ~0.2). The particle size of the catalyst is generally from 0.01 to 0.1 mm.
催化脱氢精馏反应的产物以气相出料,该气相反应产物直接进入理论板为50的精馏塔进行精馏提纯得到高纯度的所述3-戊酮产品,精馏时控制精馏的回流比为1∶1~10∶1。The product of the catalytic dehydrogenation distillation reaction is discharged in a gas phase, and the gas phase reaction product directly enters a rectification column having a theoretical plate of 50 for rectification and purification to obtain a high purity of the 3-pentanone product, and the rectification is controlled by rectification. The reflux ratio is from 1:1 to 10:1.
上述反应在一个反应精馏装置中进行,反应精馏装置由脱氢反应器和精馏柱两部分组成。反应器为1000ml的玻璃反应器,在反应器上装有机械搅拌装置、温度计、进料口和精馏柱,外部有加热设备,精馏柱的理论塔板数为60,精馏柱顶部安置一带有放空口和出料口的冷凝回流装置。反应器中先加入700克3-戊醇,再将50克颗粒度为0.03~0.05mm的Raney镍催化剂加入反应器。反应器加热升温至113~118℃,然后维持该温度3-戊醇用泵连续打入反应器进行反应。反应压力为常压,控制催化剂的3-戊醇负荷WWH为2.5~5.5hr-1,精馏柱的理论塔板数为50,控制精馏的回流比为1∶1~10∶1。脱氢所产生的氢气通过精馏柱顶部的放空口排出,收集精馏柱顶部出口物料为产品。需要注意的是,应控制3-戊醇进料量与产物出料量相互平衡,以维持系统的稳定性。各实施例21~30催化剂的组成、具体的反应条件、脱氢反应的3-戊醇转化率和3-戊酮选择性以及产物的纯度见表3和表4所列。The above reaction is carried out in a reactive rectification unit consisting of a dehydrogenation reactor and a rectification column. The reactor is a 1000ml glass reactor. The reactor is equipped with a mechanical stirring device, a thermometer, a feed port and a rectification column. The external heating device has a theoretical plate number of 60 on the rectification column and a zone on the top of the rectification column. There is a condensing return device for the vent and the discharge port. In the reactor, 700 g of 3-pentanol was first added, and then 50 g of a Raney nickel catalyst having a particle size of 0.03 to 0.05 mm was introduced into the reactor. The reactor was heated to 113 to 118 ° C, and then maintained at this temperature. 3-pentanol was continuously pumped into the reactor for reaction. The reaction pressure is normal pressure, the catalyst has a 3-pentanol loading WWH of 2.5 to 5.5 hr -1 , the number of theoretical plates of the rectification column is 50, and the reflux ratio of the controlled rectification is 1:1 to 10:1. The hydrogen produced by the dehydrogenation is discharged through the vent at the top of the rectification column, and the outlet material at the top of the rectification column is collected as a product. It should be noted that the 3-pentanol feed amount and the product discharge amount should be controlled to balance each other to maintain the stability of the system. The compositions of the catalysts of Examples 21 to 30, specific reaction conditions, 3-pentanol conversion and 3-pentanone selectivity of the dehydrogenation reaction, and the purity of the product are shown in Tables 3 and 4.
表3.table 3.
  催化剂组份Catalyst component 各组份的重量比Weight ratio of each component 反应温度temperature reflex WWH(hr-1)WWH(hr -1 )
实施例21Example 21 Al-Ni-CeAl-Ni-Ce 1:0.8:0.21:0.8:0.2 113113 2.52.5
实施例22Example 22 Al-Ni-BiAl-Ni-Bi 1:0.94:0.031:0.94:0.03 118118 5.55.5
实施例23Example 23 Al-Ni-CeAl-Ni-Ce 1:0.94:0.051:0.94:0.05 114114 3.63.6
实施例24Example 24 Al-Ni-CeAl-Ni-Ce 1:0.94:0.071:0.94:0.07 115115 3.83.8
实施例25Example 25 Al-Ni-BiAl-Ni-Bi 1:0.94:0.11:0.94:0.1 116116 3.23.2
实施例26Example 26 Al-Ni-CeAl-Ni-Ce 1:0.94:0.131:0.94:0.13 117117 3.03.0
实施例27Example 27 Al-Ni-BiAl-Ni-Bi 1:0.8:0.181:0.8:0.18 116116 3.53.5
实施例28Example 28 Al-Ni-BiAl-Ni-Bi 1:0.94:0.061:0.94:0.06 117117 4.04.0
实施例29Example 29 Al-Ni-BiAl-Ni-Bi 1:0.8:0.171:0.8:0.17 118118 3.53.5
实施例30Example 30 Al-Ni-BiAl-Ni-Bi 1:0.8:0.151:0.8:0.15 116116 3.03.0
表4.Table 4.
  3-戊醇转化率(%)3-pentanol conversion rate (%) 3-戊酮选择性(%)3-pentanone selectivity (%) 回流比Reflux ratio 3-戊酮纯度(%)3-pentanone purity (%)
实施例21Example 21 99.999.9 100100 1:11:1 99.899.8
实施例22Example 22 99.899.8 100100 10:110:1 99.799.7
实施例23Example 23 99.999.9 100100 2:12:1 99.999.9
实施例24Example 24 99.899.8 100100 3:13:1 99.899.8
实施例25Example 25 99.999.9 100100 6:16:1 99.999.9
实施例26Example 26 99.899.8 100100 5:15:1 99.999.9
实施例27Example 27 99.999.9 100100 4:14:1 99.899.8
实施例28Example 28 99.799.7 100100 3:13:1 99.899.8
实施例29Example 29 99.999.9 100100 3:13:1 99.899.8
实施例30Example 30 99.899.8 100100 5:15:1 99.899.8

Claims (10)

  1. 一种由2-戊烯制备3-戊酮的方法,其特征在于该方法包括以下步骤:A method for preparing 3-pentanone from 2-pentene, characterized in that the method comprises the steps of:
    1)将2-戊烯加入醋酸,然后以液相通过催化剂床层进行加成反应,以使2-戊烯和醋酸转化成醋酸戊酯,获得反应液;所述的醋酸与2-戊烯的摩尔比为2~5:1,所述加成反应的质量空速为1~3hr-1,反应温度为80~100℃,反应压力为0.8~2.0MPa,所述催化剂床层中的催化剂为磺酸基阳离子交换树脂,磺酸基阳离子交换树脂的质量交换容量为3~5.5mmol/g;1) adding 2-pentene to acetic acid, and then performing an addition reaction in a liquid phase through a catalyst bed to convert 2-pentene and acetic acid into amyl acetate to obtain a reaction liquid; the acetic acid and 2-pentene The molar ratio is 2 to 5:1, the mass space velocity of the addition reaction is 1 to 3 hr -1 , the reaction temperature is 80 to 100 ° C, the reaction pressure is 0.8 to 2.0 MPa, and the catalyst in the catalyst bed Is a sulfonic acid cation exchange resin, the mass exchange capacity of the sulfonic acid cation exchange resin is 3 to 5.5 mmol / g;
    2)步骤1)获得的反应液在一理论板为30的精馏塔中进行精馏;先在常压下回收未反应的2-戊烯、醋酸;再在减压下得到质量分数在99.50%的醋酸戊酯;得到的2-戊烯和醋酸循环使用。2) The reaction liquid obtained in the step 1) is subjected to rectification in a rectification column having a theoretical plate of 30; first, unreacted 2-pentene and acetic acid are recovered under normal pressure; and the mass fraction is obtained at 99.50 under reduced pressure. % of amyl acetate; the obtained 2-pentene and acetic acid are recycled.
    3)将甲醇和步骤2)获得的醋酸戊酯经催化酯交换精馏反应制得2-戊醇和3-戊醇的混合物;酯交换反应温度为62~80℃,甲醇与醋酸戊酯的摩尔比为2.0~5.0:1;催化剂为甲醇钠,催化剂加入量为醋酸戊酯质量的0.3~2%,酯交换反应副产物醋酸甲酯以气相出料,该气相反应产物直接进入精馏塔从精馏塔的塔顶分离,控制精馏的回流比为1∶1~4∶1;3) The methanol and the amyl acetate obtained in the step 2) are subjected to catalytic transesterification to obtain a mixture of 2-pentanol and 3-pentanol; the transesterification reaction temperature is 62-80 ° C, and the molar ratio of methanol to amyl acetate The ratio is 2.0 to 5.0:1; the catalyst is sodium methoxide, the catalyst is added in an amount of 0.3 to 2% by mass of the amyl acetate, and the methyl acetate as a by-product of the transesterification is discharged in the vapor phase, and the gas phase reaction product directly enters the distillation column. The top of the distillation column is separated, and the reflux ratio of the controlled rectification is 1:1 to 4:1;
    4)将步骤3)获得的2-戊醇和3-戊醇的混合物进行精馏,精馏在一理论板为70的精馏塔中进行;在塔釜温度为118~125℃,回流比为10~20∶1时,从塔顶收集115~116℃的馏份,得到含量为99.5%的3-戊醇;当塔釜温度为126~130℃,回流比为10~20∶1时,从塔顶收集118~119℃的馏份,产品为含量为99.5%的2-戊醇。4) The mixture of 2-pentanol and 3-pentanol obtained in the step 3) is subjected to rectification, and the rectification is carried out in a rectification column having a theoretical plate of 70; the temperature in the column is 118 to 125 ° C, and the reflux ratio is When 10 to 20:1, a fraction of 115 to 116 ° C is collected from the top of the column to obtain 3-pentanol having a content of 99.5%; when the temperature of the column is 126 to 130 ° C and the reflux ratio is 10 to 20:1, A fraction of 118 to 119 ° C was collected from the top of the column, and the product was a 2-pentanol having a content of 99.5%.
    5)将步骤4)获得的3-戊醇通过催化脱氢精馏反应直接制得高纯度的3-戊酮;催化脱氢反应温度为113~118℃,反应压力为常压,催化剂的3-戊醇负荷WWH为2.5~5.5hr-1,脱氢反应采用颗粒状Raney镍型金属合金作为催化剂,其组成为:5) The 3-pentanol obtained in the step 4) is directly subjected to catalytic dehydrogenation distillation to obtain high-purity 3-pentanone; the catalytic dehydrogenation reaction temperature is 113-118 ° C, the reaction pressure is normal pressure, and the catalyst 3 - The pentanol loading WWH is 2.5-5.5 hr -1 , and the dehydrogenation reaction uses a granular Raney nickel-type metal alloy as a catalyst, and its composition is:
    Al-Ni-AAl-Ni-A
    其中A为选自Ce、Bi中的一种;脱氢反应产物以气相出料,该气相反应产物直接进入理论板为50的精馏塔提纯得到高纯度的3-戊酮产品,控制精馏的回流比为1∶1~10∶1。Wherein A is one selected from the group consisting of Ce and Bi; the dehydrogenation reaction product is discharged in a gas phase, and the gas phase reaction product is directly purified into a rectification column having a theoretical plate of 50 to obtain a high-purity 3-pentanone product, and the rectification is controlled. The reflux ratio is from 1:1 to 10:1.
  2. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤5)中所述催化剂的组成为:Al-Ni-A,其中A为选自Ce、Bi中的一种,各组分的重量比为:Al∶Ni∶A=1∶(0.8~0.94)∶(0.03~0.2);所述催化剂的颗粒度为0.01~0.1mm。The method for preparing 3-pentanone from 2-pentene according to claim 1, wherein the composition of the catalyst in the step 5) is: Al-Ni-A, wherein A is selected from the group consisting of Ce, One of Bi, the weight ratio of each component is: Al: Ni: A = 1: (0.8 - 0.94): (0.03 - 0.2); the catalyst has a particle size of 0.01 - 0.1 mm.
  3. 根据权利要求2所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤5)中所述催化脱氢反应的催化剂中的组分A选用Ce;步骤5)中所述催化剂的颗粒度为0.02~0.08mm。The method for preparing 3-pentanone from 2-pentene according to claim 2, wherein component A in the catalyst for catalytic dehydrogenation in step 5) is selected from Ce; in step 5) The catalyst has a particle size of 0.02 to 0.08 mm.
  4. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤1)中所述的醋酸与2-戊烯的摩尔比为2.5~3.5:1,所述加成反应的质量空速为1.5~2.5hr-1;反应温度为85~90℃;反应压力为0.9~1.5Mpa。 The method for preparing 3-pentanone from 2-pentene according to claim 1, wherein the molar ratio of acetic acid to 2-pentene in the step 1) is 2.5 to 3.5:1. The mass space velocity of the addition reaction is 1.5 to 2.5 hr -1 ; the reaction temperature is 85 to 90 ° C; and the reaction pressure is 0.9 to 1.5 MPa.
  5. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤1)中所述的催化剂磺酸基阳离子交换树脂的质量交换容量为4~5mmol/g。The method for preparing 3-pentanone from 2-pentene according to claim 1, wherein the catalyst sulfonic acid cation exchange resin in the step 1) has a mass exchange capacity of 4 to 5 mmol/g. .
  6. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤3)中所述的酯交换反应温度为65~75℃,甲醇与醋酸戊酯的摩尔比为3.0~4.0:1。The method for preparing 3-pentanone from 2-pentene according to claim 1, wherein the transesterification temperature in the step 3) is 65 to 75 ° C, and the molar ratio of methanol to amyl acetate The ratio is 3.0 to 4.0:1.
  7. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤3)中所述的催化剂甲醇钠加入量为醋酸戊酯质量的0.5~1%。The method for preparing 3-pentanone from 2-pentene according to claim 1, wherein the catalyst sodium methoxide in the step 3) is added in an amount of 0.5 to 1% by mass of the amyl acetate.
  8. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤3)中所述的精馏的回流比为2∶1~3∶1。A method for producing 3-pentanone from 2-pentene according to claim 1, wherein the reflux ratio of the rectification in the step 3) is from 2:1 to 3:1.
  9. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤5)中所述的催化剂的3-戊醇负荷WWH为3~4hr-1A method for producing 3-pentanone from 2-pentene according to claim 1, wherein the catalyst in the step 5) has a 3-pentanol loading WWH of from 3 to 4 hr -1 .
  10. 根据权利要求1所述的一种由2-戊烯制备3-戊酮的方法,其特征在于:步骤5)中所述的精馏的回流比为2∶1~6∶1。 A method for producing 3-pentanone from 2-pentene according to claim 1, wherein the reflux ratio of the rectification in the step 5) is from 2:1 to 6:1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111790437A (en) * 2020-07-15 2020-10-20 陕西延长石油(集团)有限责任公司 Strontium-tantalum-titanium trimetal oxide catalyst for preparing 2-pentanone by liquid phase method ethanol and preparation method and application thereof
CN114292184A (en) * 2021-12-31 2022-04-08 昌德新材科技股份有限公司 Preparation method of 3-pentyloxypropionate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529730B (en) * 2014-12-11 2016-08-24 派尔科化工材料(启东)有限公司 A kind of method being prepared propione by 2-amylene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168498A (en) * 2006-10-24 2008-04-30 胡建国 Producing method for pentanone
CN102603506A (en) * 2012-02-26 2012-07-25 上海派尔科化工材料有限公司 Method for preparing cyclopentanone through cyclopentanol dehydrogenation
CN102617290A (en) * 2012-02-26 2012-08-01 上海派尔科化工材料有限公司 Process for preparing cyclopentanol with cyclopentene
CN104529730A (en) * 2014-12-11 2015-04-22 派尔科化工材料(启东)有限公司 Method for preparing 3-pentanone by using 2-pentene

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927954A (en) * 1983-06-28 1990-05-22 Union Carbide Chemicals And Plastics Company, Inc. Continuous process for producing secondary alcohols and carboxylic acid esters
JP2010120784A (en) * 2008-11-17 2010-06-03 Nippon Oil Corp Method for producing molded article of sulfonic acid group-containing carbonaceous material and application of the same
CN103130630B (en) * 2013-03-01 2014-07-02 张若煜 Cyclopentanol green synthetic method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168498A (en) * 2006-10-24 2008-04-30 胡建国 Producing method for pentanone
CN102603506A (en) * 2012-02-26 2012-07-25 上海派尔科化工材料有限公司 Method for preparing cyclopentanone through cyclopentanol dehydrogenation
CN102617290A (en) * 2012-02-26 2012-08-01 上海派尔科化工材料有限公司 Process for preparing cyclopentanol with cyclopentene
CN104529730A (en) * 2014-12-11 2015-04-22 派尔科化工材料(启东)有限公司 Method for preparing 3-pentanone by using 2-pentene

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111790437A (en) * 2020-07-15 2020-10-20 陕西延长石油(集团)有限责任公司 Strontium-tantalum-titanium trimetal oxide catalyst for preparing 2-pentanone by liquid phase method ethanol and preparation method and application thereof
CN111790437B (en) * 2020-07-15 2022-09-20 陕西延长石油(集团)有限责任公司 Strontium-tantalum-titanium trimetal oxide catalyst for preparing 2-pentanone by liquid phase method ethanol and preparation method and application thereof
CN114292184A (en) * 2021-12-31 2022-04-08 昌德新材科技股份有限公司 Preparation method of 3-pentyloxypropionate

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