CN114956980B - Method for synthesizing crotonic acid - Google Patents

Method for synthesizing crotonic acid Download PDF

Info

Publication number
CN114956980B
CN114956980B CN202210552431.3A CN202210552431A CN114956980B CN 114956980 B CN114956980 B CN 114956980B CN 202210552431 A CN202210552431 A CN 202210552431A CN 114956980 B CN114956980 B CN 114956980B
Authority
CN
China
Prior art keywords
reaction
liquid
crotonaldehyde
crotonic acid
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210552431.3A
Other languages
Chinese (zh)
Other versions
CN114956980A (en
Inventor
周益峰
杨汝静
黄晋培
李勇翔
彭强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hangzhou Ledun Micro Technology Co ltd
China Jiliang University
Original Assignee
Hangzhou Ledun Micro Technology Co ltd
China Jiliang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hangzhou Ledun Micro Technology Co ltd, China Jiliang University filed Critical Hangzhou Ledun Micro Technology Co ltd
Priority to CN202210552431.3A priority Critical patent/CN114956980B/en
Publication of CN114956980A publication Critical patent/CN114956980A/en
Application granted granted Critical
Publication of CN114956980B publication Critical patent/CN114956980B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093Microreactors, e.g. miniaturised or microfabricated reactors
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/47Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • 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
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for synthesizing crotonic acid, which comprises the following steps: the crotonaldehyde and oxygen-containing gas are subjected to a first-stage high-temperature high-pressure reaction in a micro-reactor, and the obtained reaction liquid is subjected to gas-liquid separation and then enters a tubular reactor to realize the process of converting the peracid intermediate into crotonic acid at a lower temperature, namely a second-stage reaction. The synthesis and resolution of the crotonic acid are divided into two reaction stages, and the mixing and reaction of gas-liquid two phases in the gas oxidation process are enhanced through the characteristics of the microreactor, so that the reaction efficiency and the safety are improved; and secondly, through tubular reaction, the reaction temperature is reduced, the residence time is prolonged, and the conversion selectivity of the peracid serving as a reaction intermediate is improved, so that the generation of byproducts is obviously reduced. The continuous crotonic acid synthesis process effectively solves the problems of difficult control of reaction temperature, low production efficiency, unstable products and the like in the existing kettle type process, has the advantages of short production period, high selectivity and intrinsic safety, and is suitable for industrial production.

Description

一种合成巴豆酸的方法A kind of method of synthetic crotonic acid

技术领域technical field

本发明属于精细化工原料合成技术领域,具体涉及一种合成巴豆酸的方法。The invention belongs to the technical field of synthesis of fine chemical raw materials, and in particular relates to a method for synthesizing crotonic acid.

背景技术Background technique

巴豆酸(CAS号:107-93-7)是一种不饱和脂肪酸,在工业上具有广泛的用途,主要用于合成各种树脂、表面涂料等,同时也是重要的医药中间体、农药中间体。Crotonic acid (CAS No.: 107-93-7) is an unsaturated fatty acid, which has a wide range of uses in industry, mainly used in the synthesis of various resins, surface coatings, etc., and is also an important pharmaceutical intermediate and pesticide intermediate .

目前文献中报道的巴豆酸制备方法主要有氧气氧化、金属氧化物氧化以及过氧化物氧化。氧气作为一种绿色环保的氧化剂,具有成本低、后处理简单、易分离等优点。张勇等人(精细石油化工进展,2007,卷号:22-24)以三氧化二铝为催化剂,通入氧气并借助电化学方法将巴豆醛氧化,该方法虽然产率达到80%,但是设备昂贵且效率较低,难以工业化。程绍国等人(CN1415594A)选用贵金属银作催化剂,用空气在氧化塔中氧化巴豆醛,收率为75%,但是该工艺催化剂成本较高,操作步骤较为繁琐,反应周期较长。林静等人(厦门大学学报:自然科学版;1993,卷号:745-748)分别测试了以活性二氧化锰、醋酸铜-醋酸钴和钴的希夫碱络合物为催化剂,用氧气或空气氧化巴豆醛制备巴豆酸的效果,结果表明活性二氧化锰和醋酸铜-醋酸会加剧原料巴豆醛的聚合副反应,严重降低反应选择性。The preparation methods of crotonic acid reported in the literature mainly include oxygen oxidation, metal oxide oxidation and peroxide oxidation. Oxygen, as a green and environmentally friendly oxidant, has the advantages of low cost, simple post-treatment, and easy separation. People such as Zhang Yong (progress in fine petrochemical industry, 2007, volume number: 22-24) are catalyzer with aluminum oxide, pass into oxygen and oxidize crotonaldehyde by electrochemical method, although this method reaches 80% productive rate, but The equipment is expensive and inefficient, making it difficult to industrialize. Cheng Shaoguo et al. (CN1415594A) selected precious metal silver as catalyst, oxidized crotonaldehyde with air in oxidation tower, and the yield was 75%, but the catalyst cost of this process was higher, the operation steps were more loaded down with trivial details, and the reaction cycle was longer. Lin Jing et al. (Journal of Xiamen University: Natural Science Edition; 1993, Volume No.: 745-748) tested respectively the Schiff base complexes of active manganese dioxide, copper acetate-cobalt acetate and cobalt as catalysts, and oxygen Or the effect of air oxidation of crotonaldehyde to prepare crotonic acid. The results show that active manganese dioxide and copper acetate-acetic acid will aggravate the polymerization side reaction of raw material crotonaldehyde and seriously reduce the reaction selectivity.

巴豆醛被氧气氧化成巴豆酸的机理是巴豆醛先结合一分子氧形成过氧巴豆酸中间体,然后过氧巴豆酸中间体与一分子巴豆醛作用,生成两分子巴豆酸。The mechanism of crotonaldehyde being oxidized to crotonic acid by oxygen is that crotonaldehyde first combines with one molecule of oxygen to form peroxycrotonic acid intermediate, and then the peroxycrotonic acid intermediate reacts with one molecule of crotonaldehyde to generate two molecules of crotonic acid.

现有气体氧化法制巴豆酸的生产工艺以釜式为主,釜式反应设备在进行巴豆醛氧化过程时,实际操作难度大,安全系数低,过程可控性差,并且反应选择性较低。微反应器在气液反应传质、传热方面有着突出优势,开发巴豆醛氧化微反应工艺可以很好地解决釜式工艺中的存在的诸多问题,从而实现过程强化。本发明基于对巴豆酸氧化机理的充分认识,提出了一种新型的微化工连续氧化工艺,通过微反应设备的特性增强气液两相的混合,提高反应效率和安全性;通过分两阶段反应,提高反应选择性;反应过程中无催化剂使用,绿色环保。The existing production process of crotonic acid by gas oxidation method is mainly kettle-type. When the kettle-type reaction equipment is used for the oxidation of crotonaldehyde, the actual operation is difficult, the safety factor is low, the process controllability is poor, and the reaction selectivity is low. Microreactor has outstanding advantages in gas-liquid reaction mass transfer and heat transfer. The development of crotonaldehyde oxidation micro-reaction process can well solve many problems existing in the kettle process, so as to realize process intensification. Based on the full understanding of the oxidation mechanism of crotonic acid, the present invention proposes a novel micro-chemical continuous oxidation process, which enhances the mixing of gas-liquid two-phase through the characteristics of micro-reaction equipment, and improves the reaction efficiency and safety; through two-stage reaction , improve the reaction selectivity; no catalyst is used in the reaction process, which is green and environmentally friendly.

发明内容Contents of the invention

本发明的目的是提供一种连续制备巴豆酸的方法,能够有效提高生产效率和反应选择性,降低三废处理压力,并且保证过程可控性和安全性,实现过程强化。The purpose of the present invention is to provide a method for continuously preparing crotonic acid, which can effectively improve production efficiency and reaction selectivity, reduce the pressure of waste treatment, ensure process controllability and safety, and realize process strengthening.

本发明技术方案如下:Technical scheme of the present invention is as follows:

一种连续制备巴豆酸的方法,包括以下步骤:A method for continuously preparing crotonic acid, comprising the following steps:

(1)将含巴豆醛的物料A与含氧气物料B连续通入微反应器内进行第一阶段反应,得到反应液C。(1) The material A containing crotonaldehyde and the material B containing oxygen are continuously passed into the microreactor to carry out the first-stage reaction to obtain the reaction liquid C.

(2)从微反应器内出来的反应液C经泄压后进入气液分离单元,通过在该单元连续鼓入氮气去除液体中残留的氧气,所得液体D直接导入管式反应器中进行第二阶段反应,得到反应液E。(2) The reaction liquid C coming out of the microreactor enters the gas-liquid separation unit after depressurization, and the residual oxygen in the liquid is removed by continuously blowing nitrogen into the unit, and the obtained liquid D is directly introduced into the tubular reactor for the second step. Two-stage reaction to obtain reaction solution E.

(3)管式反应器流出的反应液E进入蒸发器,未反应的原料与溶剂通过蒸发器与产品分离,后续经精馏后回收利用,蒸发器底部得到粗品料液F。(3) The reaction liquid E flowing out of the tubular reactor enters the evaporator, and the unreacted raw materials and solvent are separated from the product through the evaporator, and then recycled after rectification, and the crude material liquid F is obtained at the bottom of the evaporator.

(4)步骤(3)所得粗品料液F经后处理精制得到产品巴豆酸。(4) The crude product feed liquid F obtained in step (3) is refined after post-treatment to obtain the product crotonic acid.

所述步骤(1)物料A为纯巴豆醛或含巴豆醛的有机溶液,所述有机溶液中的有机溶剂为烃类溶剂,优选为C5~C10烷烃溶剂、C5~C10环烷烃溶剂、C6~C10芳香烃溶剂;进一步优选为甲苯、环己烷、正己烷、正庚烷等惰性溶剂,最优选为甲苯。The material A in the step (1) is pure crotonaldehyde or an organic solution containing crotonaldehyde, and the organic solvent in the organic solution is a hydrocarbon solvent, preferably a C 5 -C 10 alkane solvent, a C 5 -C 10 cycloalkane Solvent, C 6 -C 10 aromatic hydrocarbon solvent; more preferably inert solvents such as toluene, cyclohexane, n-hexane, n-heptane, and most preferably toluene.

作为优选,所述的巴豆醛与有机溶剂的体积用量比为1:1~4。Preferably, the volume ratio of the crotonaldehyde to the organic solvent is 1:1-4.

所述步骤(1)物料B为纯氧或是氮气和氧气的混合气体。The material B in the step (1) is pure oxygen or a mixed gas of nitrogen and oxygen.

所述步骤(1)中通入微反应器中物料A所含巴豆醛和物料B所含氧气的摩尔比为1:(0.3~2.0)。In the step (1), the molar ratio of the crotonaldehyde contained in the material A and the oxygen contained in the material B passed into the microreactor is 1: (0.3-2.0).

所述步骤(1)中微反应器通道直径为0.5~4.0mm,优选为0.5~2.0mm,进一步优选为1.5~2.0mm;反应温度为50~100℃,进一步优选为50~70℃;停留时间为30~180s,反应压力为1~3MPa。The diameter of the microreactor channel in the step (1) is 0.5~4.0mm, preferably 0.5~2.0mm, more preferably 1.5~2.0mm; the reaction temperature is 50~100°C, further preferably 50~70°C; The time is 30-180s, and the reaction pressure is 1-3MPa.

所述步骤(2)管式反应器的反应温度为20~50℃,反应液D在反应器内停留时间为10~60min。The reaction temperature of the tubular reactor in the step (2) is 20-50° C., and the residence time of the reaction liquid D in the reactor is 10-60 min.

所述步骤(3)蒸发器为薄膜蒸发器或精馏塔。The evaporator in the step (3) is a thin film evaporator or a rectification tower.

所述步骤(4)后处理工序包括活性炭脱色和重结晶,该后处理可按照现有工艺进行。The post-treatment process of step (4) includes activated carbon decolorization and recrystallization, and the post-treatment can be carried out according to the existing process.

本发明与现有技术相比,具有以下优点及突出性的技术效果:Compared with the prior art, the present invention has the following advantages and outstanding technical effects:

本发明中,通过引入微反应器,实现巴豆醛和氧气的气液两相高效混合与反应,解决了传统釜氏反应过程中气液反应效率低下的问题。连续工艺通过将反应拆分为高温高压和低温常压两个阶段,将巴豆醛氧化过程中过酸的形成、转化两个反应阶段基本分开,既保证了气体氧化的效率,又提高了过酸转化的选择性。另外,在两反应阶段之间加入气液分离单元,有效缓解了气体存在对于第二阶段反应器体积的压力,降低设备成本,提高工艺安全性。整个工艺以氧气作为氧化剂,原子利用率高,绿色环保,并且氧气参与的第一阶段反应在微反应器内进行,安全可控。由于该反应选择性会随着巴豆醛的转化率的上升而降低,通过精确控制各阶段的反应时间和反应温度,可以有效保证巴豆醛在合适的转化率,提高工艺的稳定性。In the present invention, by introducing a micro-reactor, the gas-liquid two-phase efficient mixing and reaction of crotonaldehyde and oxygen is realized, and the problem of low gas-liquid reaction efficiency in the traditional kettle reaction process is solved. The continuous process divides the reaction into two stages of high temperature and high pressure and low temperature and normal pressure, and basically separates the two reaction stages of the formation and conversion of peracid in the crotonaldehyde oxidation process, which not only ensures the efficiency of gas oxidation, but also improves the efficiency of peracid production. Transformation selectivity. In addition, a gas-liquid separation unit is added between the two reaction stages, which effectively relieves the pressure of the gas on the second-stage reactor volume, reduces equipment costs, and improves process safety. The whole process uses oxygen as the oxidant, which has a high atom utilization rate and is environmentally friendly, and the first-stage reaction in which oxygen participates is carried out in a microreactor, which is safe and controllable. Since the reaction selectivity will decrease with the increase of the conversion rate of crotonaldehyde, by accurately controlling the reaction time and reaction temperature of each stage, the appropriate conversion rate of crotonaldehyde can be effectively guaranteed and the stability of the process can be improved.

附图说明Description of drawings

图1为本发明合成巴豆酸的工艺流程图。Fig. 1 is the process flow sheet of the present invention's synthetic crotonic acid.

具体实施方式Detailed ways

本发明提供一种连续制备巴豆酸的方法,图1为本发明的工艺流程图,具体包括:The present invention provides a kind of method for continuously preparing crotonic acid, and Fig. 1 is a process flow diagram of the present invention, specifically comprises:

将含巴豆醛的物料A与含氧气的物料B连续通入微反应器内进行第一阶段反应,得到的反应液C经泄压后进入气液分离单元,通过在该单元连续鼓入氮气去除液体中残留的氧气,所得液体D直接导入管式反应器中进行第二阶段反应,得到反应液E进入蒸发器,未反应的原料与溶剂通过蒸发器与产品分离,后续经精馏单元回收利用,蒸发器底部得到粗品料液F,经后处理精制得到产品巴豆酸。The material A containing crotonaldehyde and the material B containing oxygen are continuously fed into the microreactor for the first-stage reaction, and the obtained reaction liquid C enters the gas-liquid separation unit after pressure relief, and the liquid is removed by continuously blowing nitrogen into the unit Oxygen remaining in the liquid, the obtained liquid D is directly introduced into the tubular reactor for the second-stage reaction, and the obtained reaction liquid E enters the evaporator, and the unreacted raw materials and solvents are separated from the product through the evaporator, and are subsequently recycled by the rectification unit. The crude feed liquid F is obtained at the bottom of the evaporator, and the product crotonic acid is obtained through post-processing and refining.

下面结合实施例对本发明做进一步说明。The present invention will be further described below in conjunction with embodiment.

实施例1Example 1

称取300g巴豆醛,溶于正己烷并定容至800mL,作为物料A;氧气钢瓶中出来的氧气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,型号TMC-01,内部尺寸1.6mm,材质316L,通道总体积20mL)内,反应器温度为70℃,压力为2MPa,物料A流量为5mL/min,物料B流量0.2~0.4SLM(每分钟标准升)。经泄压阀泄压,气液分离后所得液体以5mL/min流量通入316L反应盘管(外径3mm内径2mm,总长度50m,常压),盘管外水浴温度为40℃。盘管流出的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛140g,反应转化率53%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品160g,GC纯度>99%,以消耗的巴豆醛计算,收率为81.4%。Weigh 300g of crotonaldehyde, dissolve it in n-hexane and set the volume to 800mL as material A; the oxygen from the oxygen cylinder without any treatment is used as material B. Material A and material B were transported to a microchannel reactor (Shenshi, model TMC-01, internal size 1.6mm, material 316L, total channel volume 20mL) using a high-pressure advection pump and a gas mass flow controller, respectively. The temperature is 70°C, the pressure is 2MPa, the flow rate of material A is 5mL/min, and the flow rate of material B is 0.2-0.4SLM (standard liter per minute). The pressure is released through the pressure relief valve, and the liquid obtained after gas-liquid separation is passed into a 316L reaction coil (outer diameter 3mm inner diameter 2mm, total length 50m, normal pressure) at a flow rate of 5mL/min, and the temperature of the water bath outside the coil is 40°C. The reaction solution flowing out from the coil was distilled under reduced pressure to separate the reaction solution from the raw material and the solvent, and the external standard calculation by gas chromatography contained 140 g of crotonaldehyde in the separation solution, and the reaction conversion rate was 53%. The remaining crude product liquid was decolorized and recrystallized by activated carbon to obtain 160 g of pure crotonic acid with a GC purity of >99%. The yield was 81.4% based on the consumed crotonaldehyde.

实施例2Example 2

称取300g巴豆醛,溶于正己烷并定容至800mL,作为物料A;空气钢瓶中出来的空气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,型号TMC-02,内部尺寸2mm,材质316L,通道总体积为90mL)内,反应器温度为70℃,压力为2.5MPa,物料A流量为5mL/min,物料B流量为1.3~1.5SLM。经泄压阀泄压,气液分离后所得液体以5mL/min流量通入316L反应盘管(外径3mm内径2mm,总长度50m,常压),盘管外水浴温度为40℃。盘管流出的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛150g,反应转化率50%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品155g,GC纯度>99%,以消耗的巴豆醛计算,收率为84.1%。Weigh 300g of crotonaldehyde, dissolve it in n-hexane and set the volume to 800mL as material A; the air coming out of the air cylinder without any treatment is used as material B. Material A and material B are transported to a microchannel reactor (Shenshi, model TMC-02, internal size 2mm, material 316L, total channel volume is 90mL) using a high-pressure advection pump and a gas mass flow controller, respectively. The temperature is 70°C, the pressure is 2.5MPa, the flow rate of material A is 5mL/min, and the flow rate of material B is 1.3~1.5SLM. The pressure is released through the pressure relief valve, and the liquid obtained after gas-liquid separation is passed into a 316L reaction coil (outer diameter 3mm inner diameter 2mm, total length 50m, normal pressure) at a flow rate of 5mL/min, and the temperature of the water bath outside the coil is 40°C. The reaction liquid flowing out of the coil tube is separated from the raw material and the solvent by distillation under reduced pressure, and the external standard calculation by gas chromatography contains 150 g of crotonaldehyde in the separated liquid, and the reaction conversion rate is 50%. The remaining crude product liquid was decolorized by activated carbon and recrystallized to obtain 155 g of crotonic acid pure product with a GC purity of >99%. The yield was 84.1% based on the consumed crotonaldehyde.

实施例3Example 3

称取300g巴豆醛,不加任何溶剂作为物料A;空气钢瓶中出来的空气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,型号TMC-02,内部尺寸2mm,材质316L,通道总体积为90mL)内,反应器温度为70℃,压力为2MPa,物料A流量为5mL/min,物料B流量为1.3~1.5SLM。经泄压阀泄压,气液分离后所得液体以5mL/min流量通入316L反应盘管(外径3mm内径2mm,总长度50m,常压),盘管外水浴温度为40℃。盘管流出的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛130g,反应转化率57%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品158g,GC纯度>99%,以消耗的巴豆醛计算,收率为75.7%。Take by weighing 300g crotonaldehyde, do not add any solvent as material A; The air that comes out in the air cylinder is not processed in any way, as material B. Material A and material B are transported to a microchannel reactor (Shenshi, model TMC-02, internal size 2mm, material 316L, total channel volume is 90mL) using a high-pressure advection pump and a gas mass flow controller, respectively. The temperature is 70°C, the pressure is 2MPa, the flow rate of material A is 5mL/min, and the flow rate of material B is 1.3~1.5SLM. The pressure is released through the pressure relief valve, and the liquid obtained after gas-liquid separation is passed into a 316L reaction coil (outer diameter 3mm inner diameter 2mm, total length 50m, normal pressure) at a flow rate of 5mL/min, and the temperature of the water bath outside the coil is 40°C. The reaction solution flowing out of the coil was distilled under reduced pressure to separate the reaction solution from the raw material and the solvent, and the external standard calculation by gas chromatography contained 130 g of crotonaldehyde in the separation solution, and the reaction conversion rate was 57%. The remaining crude product liquid was decolorized and recrystallized by activated carbon to obtain 158 g of pure crotonic acid with a GC purity of >99%. The yield was 75.7% based on the consumed crotonaldehyde.

实施例4Example 4

称取300g巴豆醛,溶于甲苯并定容至800mL,作为物料A;空气钢瓶中出来的空气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,TMC-02,内部尺寸2mm,材质316L,通道总体积为90mL)内,反应器温度为70℃,压力为2MPa,物料A流量为5mL/min,物料B流量为1.3~1.5SLM。经泄压阀泄压,气液分离后所得液体以5mL/min流量通入316L反应盘管(外径3mm内径2mm,总长度50m,常压),盘管外水浴温度为40℃。盘管流出的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛145g,反应转化率52%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品173g,GC纯度>99%,以消耗的巴豆醛计算,收率为90.1%。Weigh 300g of crotonaldehyde, dissolve it in toluene and set the volume to 800mL as material A; the air coming out of the air cylinder without any treatment is used as material B. Material A and material B were delivered to a microchannel reactor (Shenshi, TMC-02, internal size 2mm, material 316L, total channel volume 90mL) using a high-pressure advection pump and a gas mass flow controller, respectively, and the reactor temperature was 70°C, pressure 2MPa, material A flow rate 5mL/min, material B flow rate 1.3-1.5SLM. The pressure is released through the pressure relief valve, and the liquid obtained after gas-liquid separation is passed into a 316L reaction coil (outer diameter 3mm inner diameter 2mm, total length 50m, normal pressure) at a flow rate of 5mL/min, and the temperature of the water bath outside the coil is 40°C. The reaction solution flowing out of the coil tube is separated from the raw material and the solvent by distillation under reduced pressure, and the external standard calculation by gas chromatography contains 145g of crotonaldehyde in the separation solution, and the reaction conversion rate is 52%. After decolorization and recrystallization of the remaining crude product liquid by activated carbon, 173 g of pure crotonic acid was obtained, the GC purity was >99%, and the yield was 90.1% based on the consumed crotonaldehyde.

实施例5Example 5

称取300g巴豆醛,溶于甲苯并定容至800mL,作为物料A;空气钢瓶中出来的空气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,TMC-02,内部尺寸2mm,材质316L,通道总体积为90mL)内,反应器温度为60℃,压力为2MPa,物料A流量为5mL/min,物料B流量为1.3~1.5SLM。经泄压阀泄压,气液分离后所得液体以5mL/min流量通入316L反应盘管(外径3mm内径2mm,总长度50m,常压),盘管外水浴温度为30℃。盘管流出的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛210g,反应转化率30%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品106g,GC纯度>99%,以消耗的巴豆醛计算,收率为95.9%。Weigh 300g of crotonaldehyde, dissolve it in toluene and set the volume to 800mL as material A; the air coming out of the air cylinder without any treatment is used as material B. Material A and material B were delivered to a microchannel reactor (Shenshi, TMC-02, internal size 2mm, material 316L, total channel volume 90mL) using a high-pressure advection pump and a gas mass flow controller, respectively, and the reactor temperature was 60°C, pressure 2MPa, material A flow rate 5mL/min, material B flow rate 1.3-1.5SLM. The pressure is released through the pressure relief valve, and the liquid obtained after gas-liquid separation is passed into a 316L reaction coil (outer diameter 3mm inner diameter 2mm, total length 50m, normal pressure) at a flow rate of 5mL/min, and the temperature of the water bath outside the coil is 30°C. The reaction solution flowing out from the coil was distilled under reduced pressure to separate the reaction solution from the raw material and the solvent, and the external standard calculation by gas chromatography contained 210 g of crotonaldehyde in the separation solution, and the reaction conversion rate was 30%. The remaining crude product liquid was decolorized and recrystallized by activated carbon to obtain 106 g of crotonic acid pure product, with a GC purity of >99%. The yield was 95.9% based on the consumed crotonaldehyde.

实施例6Example 6

称取150g实施例4和5工艺回收的巴豆醛,溶于甲苯并定容至400mL,作为物料A;空气钢瓶中出来的空气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,TMC-02,内部尺寸2mm,材质316L,通道总体积为90mL)内,反应器温度为60℃,压力为2MPa,物料A流量为5mL/min,物料B流量为1.3~1.5SLM。经泄压阀泄压,气液分离后所得液体以5mL/min流量通入316L反应盘管(外径3mm内径2mm,总长度50m,常压),盘管外水浴温度为30℃。盘管流出的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛102g,反应转化率32%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品55g,GC纯度>99%,以消耗的巴豆醛计算,收率为93.3%。Take by weighing 150g of the crotonaldehyde recovered by the process of embodiment 4 and 5, dissolve it in toluene and settle to 400mL, as material A; the air coming out of the air cylinder without any treatment, as material B. Material A and material B were delivered to a microchannel reactor (Shenshi, TMC-02, internal size 2mm, material 316L, total channel volume 90mL) using a high-pressure advection pump and a gas mass flow controller, respectively, and the reactor temperature was 60°C, pressure 2MPa, material A flow rate 5mL/min, material B flow rate 1.3-1.5SLM. The pressure is released through the pressure relief valve, and the liquid obtained after gas-liquid separation is passed into a 316L reaction coil (outer diameter 3mm inner diameter 2mm, total length 50m, normal pressure) at a flow rate of 5mL/min, and the temperature of the water bath outside the coil is 30°C. The reaction solution flowing out from the coil was distilled under reduced pressure to separate the reaction solution from the raw material and the solvent, and the separated solution contained 102 g of crotonaldehyde through gas chromatography analysis and external standard calculation, and the reaction conversion rate was 32%. After decolorization and recrystallization of the remaining crude product liquid by activated carbon, 55 g of pure crotonic acid was obtained, with a GC purity of >99%. The yield was 93.3% based on the consumed crotonaldehyde.

对比例1Comparative example 1

称取300g巴豆醛,溶于正己烷并定容至800mL,作为物料A;氧气钢瓶中出来的氧气未作任何处理,作为物料B。将物料A和物料B分别使用高压平流泵及气体质量流量控制器输送至微通道反应器(沈氏,型号TMC-01,内部尺寸1.6mm,材质316L,通道总体积90mL)内,反应器温度为70℃,压力为2MPa,物料A流量为2mL/min,物料B流量为0.1~0.15SLM。经泄压阀泄压,气液分离后的反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛120g,反应转化率60%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品160g,GC纯度>99%,以消耗的巴豆醛收率为72.3%。Weigh 300g of crotonaldehyde, dissolve it in n-hexane and set the volume to 800mL as material A; the oxygen from the oxygen cylinder without any treatment is used as material B. Material A and material B were transported to a microchannel reactor (Shenshi, model TMC-01, internal size 1.6mm, material 316L, total channel volume 90mL) using a high-pressure advection pump and a gas mass flow controller, respectively. The temperature is 70°C, the pressure is 2MPa, the flow rate of material A is 2mL/min, and the flow rate of material B is 0.1~0.15SLM. Pressure release through the pressure relief valve, the reaction liquid after the gas-liquid separation is separated from the raw material and the solvent by distillation under reduced pressure, and the external standard calculation through gas chromatography contains 120g of crotonaldehyde in the separation liquid, and the reaction conversion rate is 60%. The remaining crude product liquid was decolorized and recrystallized by activated carbon to obtain 160 g of pure crotonic acid with a GC purity of >99%, and the yield of consumed crotonaldehyde was 72.3%.

对比例2Comparative example 2

称取300g巴豆醛,溶于正己烷并定容至700mL加入三颈烧瓶中,置于40℃水浴中,开磁力搅拌,向其中以0.05SLM的流速鼓入空气,48h反应。反应结束后,反应液通过减压蒸馏将原料、溶剂分离出反应液,经气相色谱分析外标计算分离液中含巴豆醛180g,反应转化率40%。剩余粗品料液经活性炭脱色和重结晶后得到巴豆酸纯品96g,GC纯度>99%,以消耗的巴豆醛收率为65.1%。Weigh 300g of crotonaldehyde, dissolve it in n-hexane and set the volume to 700mL, put it into a three-necked flask, place it in a water bath at 40°C, turn on magnetic stirring, blow air into it at a flow rate of 0.05SLM, and react for 48h. After the reaction was finished, the reaction liquid was separated from the raw material and the solvent by distillation under reduced pressure, and the external standard was analyzed by gas chromatography to calculate that the separated liquid contained 180 g of crotonaldehyde, and the reaction conversion rate was 40%. The remaining crude product liquid was decolorized and recrystallized by activated carbon to obtain 96 g of pure crotonic acid with a GC purity of >99%, and the yield of consumed crotonaldehyde was 65.1%.

Claims (5)

1.一种合成巴豆酸的方法,其特征在于,包括以下步骤:1. a method for synthesizing crotonic acid, is characterized in that, comprises the following steps: (1)将含巴豆醛的物料A与含氧气的物料B连续通入微反应器内进行第一阶段反应,得到反应液C;(1) Continuously feed material A containing crotonaldehyde and material B containing oxygen into the microreactor for the first-stage reaction to obtain reaction liquid C; 所述物料A为含巴豆醛的有机溶液,所述有机溶液中的有机溶剂为烃类溶剂;The material A is an organic solution containing crotonaldehyde, and the organic solvent in the organic solution is a hydrocarbon solvent; 步骤(1)中微反应器通道直径0.5~4.0 mm,反应温度为50~100℃;停留时间为30~180s,反应压力为1~3 MPa;Step (1) The channel diameter of the microreactor is 0.5~4.0 mm, the reaction temperature is 50~100°C; the residence time is 30~180s, and the reaction pressure is 1~3 MPa; (2)从微反应器内出来的反应液C经泄压后进入气液分离单元,通过在该单元连续鼓入氮气去除液体中残留的氧气,所得液体D直接导入管式反应器中进行第二阶段反应,得到反应液E;(2) The reaction liquid C coming out of the microreactor enters the gas-liquid separation unit after the pressure is released, and the residual oxygen in the liquid is removed by continuously blowing nitrogen into the unit, and the obtained liquid D is directly introduced into the tubular reactor for the second stage. Two-stage reaction to obtain reaction solution E; 步骤(2)中管式反应器的反应温度为20~50℃,反应液D在反应器内停留时间为10~60min;The reaction temperature of the tubular reactor in step (2) is 20-50°C, and the residence time of the reaction liquid D in the reactor is 10-60min; (3)管式反应器流出的反应液E进入蒸发器,未反应的原料与溶剂通过蒸发器与产品分离,后续经精馏单元回收利用,蒸发器底部得到粗品料液F;(3) The reaction liquid E flowing out of the tubular reactor enters the evaporator, and the unreacted raw materials and solvent are separated from the product through the evaporator, and then recycled through the rectification unit, and the crude material liquid F is obtained at the bottom of the evaporator; (4)步骤(3)所得粗品料液F经后处理精制得到产品巴豆酸(4) The crude product liquid F obtained in step (3) is refined after post-treatment to obtain the product crotonic acid 所述的有机溶剂为甲苯、环己烷、正己烷、正庚烷中的一种或者多种;The organic solvent is one or more of toluene, cyclohexane, n-hexane, and n-heptane; 步骤(1)中,所述物料B为纯氧或是氮气和氧气的混合气体。In step (1), the material B is pure oxygen or a mixed gas of nitrogen and oxygen. 2.根据权利要求1所述的方法,其特征在于,所述的巴豆醛与有机溶剂的体积用量比为1:1~4。2. The method according to claim 1, characterized in that the volume ratio of the crotonaldehyde to the organic solvent is 1:1~4. 3.根据权利要求1所述的方法,其特征在于,步骤(1)中通入微反应器中物料A所含巴豆醛和物料B所含氧气的摩尔比为1:(0.3~2.0)。3. The method according to claim 1, characterized in that the molar ratio of the crotonaldehyde contained in the material A and the oxygen contained in the material B passed into the microreactor in step (1) is 1: (0.3-2.0). 4.根据权利要求1所述的方法,其特征在于,步骤(3)中蒸发器为薄膜蒸发器或精馏塔。4. The method according to claim 1, characterized in that the evaporator in step (3) is a thin film evaporator or a rectification tower. 5.根据权利要求1所述的方法,其特征在于,步骤(4)中,后处理工序包括活性炭脱色和重结晶。5. The method according to claim 1, characterized in that, in step (4), the post-treatment process includes activated carbon decolorization and recrystallization.
CN202210552431.3A 2022-05-20 2022-05-20 Method for synthesizing crotonic acid Active CN114956980B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210552431.3A CN114956980B (en) 2022-05-20 2022-05-20 Method for synthesizing crotonic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210552431.3A CN114956980B (en) 2022-05-20 2022-05-20 Method for synthesizing crotonic acid

Publications (2)

Publication Number Publication Date
CN114956980A CN114956980A (en) 2022-08-30
CN114956980B true CN114956980B (en) 2023-08-04

Family

ID=82985383

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210552431.3A Active CN114956980B (en) 2022-05-20 2022-05-20 Method for synthesizing crotonic acid

Country Status (1)

Country Link
CN (1) CN114956980B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB595170A (en) * 1945-02-02 1947-11-27 Shawinigan Chem Ltd Production of crotonic acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB595170A (en) * 1945-02-02 1947-11-27 Shawinigan Chem Ltd Production of crotonic acid

Also Published As

Publication number Publication date
CN114956980A (en) 2022-08-30

Similar Documents

Publication Publication Date Title
JP2021038231A (en) Process for producing methyl methacrylate
CN104892423B (en) The technique that a kind of methanol oxidative carbonylation prepares dimethyl carbonate
CN101337879B (en) Process and equipment for preparing adipic acid by catalyzing air and oxidizing cyclohexane
CN106518608A (en) A continuous preparing method and apparatus for cyclohexanedimethanol
JP2011507830A (en) Method for producing N-methylpyrrolidone
CN108779054A (en) By the method for 3- methyl -3- butylene alcohol production prenol and isoamyl olefine aldehydr
CN103641740A (en) Method for preparing cyclohexane oxime and caprolactam by oxidizing cyclohexylamine through molecular oxygen in gas phase
WO2014202031A1 (en) Method for co-production of adipic acid and nitrocyclohexane
CN114956980B (en) Method for synthesizing crotonic acid
CN109438216A (en) A kind of preparation method of high-purity isooctyl acid
CN112939765B (en) Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane
CN115160127B (en) Method for preparing long carbon chain dibasic acid through co-oxidation reaction
CN106699507A (en) Preparation method for alpha-phenethanol
CN115282913B (en) Reaction system and method for preparing methyl propionate
CN112661618B (en) Copper catalysis preparation method of cyclopentanone
CN110903181A (en) Method for preparing p-benzoquinone compound by double-catalytic system
CN107032961A (en) A kind of method that phenol and diphenol are prepared by the direct hydroxylating of benzene
CN112661620A (en) Preparation method of cyclopentanone
CN115304471B (en) A method for preparing long carbon chain dicarboxylic acid
CN112661619B (en) Method for preparing cyclopentanone
JP2002128716A (en) Method for producing isopropyl alcohol
JP7629098B2 (en) Method for recovering and reusing selective homogeneous hydrogenation catalysts
CN114436843B (en) Method for continuously producing dimethyl adipate from cyclohexane
CN116023350B (en) System and method for preparing succinic anhydride
CN116023351B (en) A method and system for preparing succinic anhydride

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant