CN114874092A - Method for preparing sodium salicylate through sodium phenolate carboxylation reaction - Google Patents

Method for preparing sodium salicylate through sodium phenolate carboxylation reaction Download PDF

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CN114874092A
CN114874092A CN202210664795.0A CN202210664795A CN114874092A CN 114874092 A CN114874092 A CN 114874092A CN 202210664795 A CN202210664795 A CN 202210664795A CN 114874092 A CN114874092 A CN 114874092A
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sodium
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carbon dioxide
carboxylation reaction
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许文林
黄英姿
孙驰
王雅琼
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Yangzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F21/00—Dissolving
    • B01F21/02—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention relates to a method for preparing sodium salicylate by carboxylation reaction of sodium phenate, which takes acetone as a solvent and sodium phenate and carbon dioxide as raw materials, the sodium phenate is dissolved in the acetone to prepare sodium phenate solution, the sodium phenate and the carbon dioxide generate carboxylation reaction in an efficient gas-liquid dispersion mixing reactor, and the sodium salicylate is obtained by decompression flash evaporation and gas-solid separation of the reacted materials. Acetone is used as a solvent for the carboxylation reaction of the sodium phenolate, so that the carboxylation reaction of the sodium phenolate and carbon dioxide is changed from the traditional gas-solid multiphase reaction into the gas-liquid multiphase reaction, and meanwhile, the gas-liquid ratio is improved and the conversion per pass is also improved by adopting a high-efficiency gas-liquid dispersion mixing reactor. The unit operation processes of the invention are all sealed circulation systems, the whole process is safe and environment-friendly, and the solvent can be recycled, thus the invention is a clean production process for continuously producing sodium salicylate.

Description

一种苯酚钠羧化反应制水杨酸钠的方法A kind of method for preparing sodium salicylate by carboxylation of sodium phenolate

技术领域technical field

本发明涉及一种丙酮溶液中苯酚钠羧化反应制水杨酸钠的方法，是以苯酚钠和二氧化碳为原料制备水杨酸钠的工艺技术。首先将苯酚钠溶解在溶剂丙酮中配制成苯酚钠溶液，然后将得到的苯酚钠溶液在高效气-液分散混合反应器中与二氧化碳进行气-液相羧化反应，反应后物料进行减压闪蒸分离得到水杨酸钠。属于精细化工及化学工程技术领域。The invention relates to a method for preparing sodium salicylate by carboxylation of sodium phenolate in an acetone solution, and a process technology for preparing sodium salicylate by using sodium phenolate and carbon dioxide as raw materials. First, the sodium phenate was dissolved in the solvent acetone to prepare a sodium phenate solution, and then the obtained sodium phenate solution was subjected to a gas-liquid phase carboxylation reaction with carbon dioxide in a high-efficiency gas-liquid dispersion mixing reactor. After the reaction, the material was flashed under reduced pressure. Evaporate to obtain sodium salicylate. It belongs to the technical field of fine chemicals and chemical engineering.

背景技术Background technique

1.水杨酸钠1. Sodium Salicylate

水杨酸钠，又称邻羟基苯甲酸钠，2-羟基苯甲酸单钠盐，水杨酸钠和柳酸钠等，分子式为C7H5NaO3，分子量为160.1，熔点为160～166℃，白色鳞片状结晶或粉末。无气味，见光后变为粉红色。易溶于水、乙醇、甘油，1g水杨酸钠溶于0.9ml水、9.2ml乙醇、4ml甘油。几乎不溶于醚、氯仿和苯。水溶液呈微酸性，pH为5～6。Sodium salicylate, also known as sodium o-hydroxybenzoate, 2-hydroxybenzoic acid monosodium salt, sodium salicylate and sodium salicylate, etc., the molecular formula is C 7 H 5 NaO 3 , the molecular weight is 160.1, and the melting point is 160～166℃ , white scaly crystal or powder. Odorless, turns pink when exposed to light. Soluble in water, ethanol and glycerol, 1g sodium salicylate dissolves in 0.9ml water, 9.2ml ethanol and 4ml glycerol. Almost insoluble in ether, chloroform and benzene. The aqueous solution is slightly acidic, with a pH of 5-6.

2.现有气-固相羧化反应合成水杨酸钠工艺及存在的主要问题2. Existing gas-solid phase carboxylation synthesis process and main problems of sodium salicylate

现有的以苯酚钠和二氧化碳为原料制备水杨酸钠的工艺是采用Koble-Skhmitt反应，苯酚钠固体与二氧化碳气体在反应温度控制在130℃以下以及加压条件下进行气-固相羧化反应工艺技术。The existing technology for preparing sodium salicylate with sodium phenate and carbon dioxide as raw materials adopts Koble-Skhmitt reaction, and sodium phenate solid and carbon dioxide gas are controlled at reaction temperature below 130 DEG C and carry out gas-solid phase carboxylation under pressurized conditions. Reaction process technology.

该羧化反应主要存在以下几方面的问题：This carboxylation reaction mainly has the following problems:

(1)羧化反应速率和选择性之间的矛盾：羧化反应为放热反应，Koble-Skhmit羧化反应速率随着反应温度升高，而反应温度升高生成对羟基苯甲酸钠等副反应速率也加快。因此，存在羧化反应速率和选择性的矛盾，如何实现在高选择性条件下气相反应物二氧化碳与苯酚钠反应的快速、有效进行是一共性技术难题。(1) Contradiction between carboxylation reaction rate and selectivity: The carboxylation reaction is an exothermic reaction, the Koble-Skhmit carboxylation reaction rate increases with the reaction temperature, and the reaction temperature increases to generate side reactions such as sodium p-hydroxybenzoate The rate is also accelerated. Therefore, there is a contradiction between the rate and selectivity of the carboxylation reaction, and how to realize the rapid and effective reaction of the gas-phase reactants carbon dioxide and sodium phenolate under the condition of high selectivity is a common technical problem.

(2)气-固相反应系统：在苯酚钠和二氧化碳发生羧化反应生成水杨酸钠过程中，二氧化碳为气相物料，苯酚钠为固相物料，为气-固相反应系统，必然存在反应速率小、反应时间长、反应过程中的移热困难、容易局部过热产生副产物等问题。(2) Gas-solid phase reaction system: in the process of carboxylation of sodium phenate and carbon dioxide to generate sodium salicylate, carbon dioxide is a gas phase material, and sodium phenate is a solid phase material, which is a gas-solid phase reaction system, and there must be a reaction Problems such as small rate, long reaction time, difficulty in heat transfer during the reaction process, and easy local overheating to generate by-products.

(3)反应选择性低，导致产品质量差：反应过程中易生成对羟基苯甲酸钠等副产物，而且产品分离精制困难，很难将水杨酸钠制得到高品质的水杨酸。(3) The reaction selectivity is low, resulting in poor product quality: in the reaction process, by-products such as sodium p-hydroxybenzoate are easily generated, and the separation and purification of the product is difficult, and it is difficult to prepare high-quality salicylic acid from sodium salicylate.

(4)细颗粒苯酚钠的制备问题：为了提高苯酚钠和二氧化碳发生羧化反应生成水杨酸钠的速率，采用减小苯酚钠颗粒的方法是提高羧化反应速度和转化率最有效的方法，为了制备细颗粒苯酚钠，必然存在细颗粒苯酚钠制备技术难题。(4) The preparation problem of fine-grained sodium phenate: In order to improve the rate at which sodium phenate and carbon dioxide undergo carboxylation to generate sodium salicylate, the method of reducing sodium phenate particles is the most effective method to improve the rate of carboxylation and conversion. , In order to prepare fine particle sodium phenate, there must be technical difficulties in the preparation of fine particle sodium phenate.

(5)连续稳态操作控制困难：因为二氧化碳与苯酚钠为气-固相放热反应系统，必然存在反应操作过程控制、反应器操作失稳问题。因此，目前主要采用间歇操作模式。(5) Difficulty in continuous steady-state operation control: Because carbon dioxide and sodium phenolate are a gas-solid exothermic reaction system, there must be problems in the control of the reaction operation process and the instability of the reactor operation. Therefore, the intermittent operation mode is mainly used at present.

(6)过程安全可靠性差：反应物苯酚钠脱水成为干粉后易燃烧和爆炸，细颗粒苯酚钠制备过程存在燃烧和爆炸的安全隐患。(6) Poor process safety and reliability: the reactant sodium phenolate is easily flammable and explosive after being dehydrated into dry powder, and the preparation process of fine-grained sodium phenolate has potential safety hazards of combustion and explosion.

因此，研发苯酚钠与二氧化碳连续羧化反应制取水杨酸钠的新工艺技术是亟待解决的技术问题。Therefore, it is an urgent technical problem to develop a new process technology for the continuous carboxylation of sodium phenate and carbon dioxide to prepare sodium salicylate.

发明内容SUMMARY OF THE INVENTION

本发明提供一种丙酮溶液中苯酚钠羧化反应制水杨酸钠的方法，在高效气-液分散混合反应器中，苯酚钠与二氧化碳发生气-液相羧化反应得到水杨酸钠。The invention provides a method for preparing sodium salicylate by carboxylation reaction of sodium phenate in acetone solution. In a high-efficiency gas-liquid dispersion mixing reactor, sodium phenate and carbon dioxide undergo gas-liquid phase carboxylation reaction to obtain sodium salicylate.

实现上述目的技术方案是：一种苯酚钠羧化反应制水杨酸钠的方法，以丙酮为溶剂，苯酚钠和二氧化碳为原料，采用高效气-液分散混合反应器，苯酚钠与二氧化碳发生气-液相羧化反应得到水杨酸钠，具体步骤如下：The technical solution for achieving the above object is: a method for preparing sodium salicylate by carboxylation of sodium phenate, using acetone as a solvent, sodium phenate and carbon dioxide as raw materials, using a high-efficiency gas-liquid dispersion mixing reactor, and generating gas from sodium phenate and carbon dioxide. - liquid-phase carboxylation reaction obtains sodium salicylate, and concrete steps are as follows:

(1)溶液配制：在苯酚钠溶液配制设备中，将苯酚钠溶解于有机溶剂丙酮制得苯酚钠溶液；(1) solution preparation: in the sodium phenolate solution preparation equipment, sodium phenolate is dissolved in the organic solvent acetone to obtain a sodium phenolate solution;

(2)羧化反应：在高效气-液分散混合反应器中，苯酚钠溶液与二氧化碳进行气-液分散混合，苯酚钠与二氧化碳发生羧化反应生成水杨酸钠，反应后物料进入下一步；(2) Carboxylation reaction: in the high-efficiency gas-liquid dispersion mixing reactor, the sodium phenate solution and carbon dioxide are mixed by gas-liquid dispersion, and the sodium phenate and carbon dioxide undergo a carboxylation reaction to generate sodium salicylate, and the material enters the next step after the reaction. ;

(3)减压闪蒸：在减压闪蒸设备中，将上一步羧化反应后的物料进行减压闪蒸操作，减压闪蒸得到的气相物料经过冷凝、气-液分离后得到的丙酮和二氧化碳循环利用，其他物料进入下一步；(3) Decompression flashing: in the decompression flashing equipment, the material after the carboxylation reaction in the previous step is subjected to a decompression flashing operation, and the gas-phase material obtained by the decompression flashing is obtained after condensation and gas-liquid separation. Acetone and carbon dioxide are recycled, and other materials go to the next step;

(4)气-固分离：在气-固分离设备中，将上一步得到的物料进行气-固分离，其固相物料即为水杨酸钠。(4) Gas-solid separation: in the gas-solid separation equipment, the material obtained in the previous step is subjected to gas-solid separation, and the solid phase material is sodium salicylate.

进一步，第一步制备的苯酚钠溶液中，苯酚钠的质量与丙酮的体积比为1.0kg:4.0L～1.0kg:10.0L。Further, in the sodium phenate solution prepared in the first step, the mass ratio of sodium phenate to the volume of acetone is 1.0kg:4.0L～1.0kg:10.0L.

进一步，第二步苯酚钠羧化反应过程中所述的高效气-液分散混合设备为静态混合器、喷射式混合器、文丘里混合器中的任一种，羧化反应中苯酚钠与二氧化碳的摩尔比为1.0:1.2～1.0:2.0，反应压强为0.4MPa～0.8MPa，反应温度为80℃～120℃。Further, the high-efficiency gas-liquid dispersion mixing equipment described in the second step sodium phenolate carboxylation reaction process is any one of static mixer, jet mixer, venturi mixer, and sodium phenolate and carbon dioxide in the carboxylation reaction. The molar ratio is 1.0:1.2～1.0:2.0, the reaction pressure is 0.4MPa～0.8MPa, and the reaction temperature is 80℃～120℃.

进一步，第三步减压闪蒸所述的设备是闪蒸罐或闪蒸冷却器或闪蒸塔中的任意一种，操作的绝对压强为0.02MPa～0.08MPa。Further, the equipment described in the third step of flashing under reduced pressure is any one of a flash tank, a flash cooler or a flash tower, and the absolute pressure of the operation is 0.02 MPa to 0.08 MPa.

本发明中制取水杨酸钠主要依据以下特性：In the present invention, the preparation of sodium salicylate is mainly based on the following characteristics:

(1)充分利用丙酮为苯酚钠良溶剂的特性：苯酚钠在丙酮中有一定的溶解度，而且随着温度的升高，苯酚钠在丙酮中的溶解度增大，在常压回流条件下，其溶解度约为22.0g/100ml。利用苯酚钠易溶于丙酮的特点，在羧化反应过程中，采用气-液反应提高羧化反应的速率和选择性。(1) Make full use of the characteristics of acetone as a good solvent for sodium phenate: sodium phenate has a certain solubility in acetone, and with the increase of temperature, the solubility of sodium phenate in acetone increases, under normal pressure reflux conditions, its The solubility is about 22.0g/100ml. Taking advantage of the characteristics of sodium phenolate being easily soluble in acetone, in the process of carboxylation reaction, gas-liquid reaction is used to improve the rate and selectivity of carboxylation reaction.

(2)充分利用高效气-液混合器的高效分散、混合特性：静态混合器、喷射式混合器、文丘里混合器等可以有效实现非均相物系的混合。采用这些高效的分散混合技术可以提高二氧化碳与苯酚钠反应的气液比，实现气相与液相的微观混合，提高气液接触比表面积，形成具有一定稳定性的微泡和液滴，从动力学上显著地提高气-液分散混合的速率和效率。(2) Make full use of the high-efficiency dispersion and mixing characteristics of high-efficiency gas-liquid mixers: static mixers, jet mixers, Venturi mixers, etc. can effectively realize the mixing of heterogeneous systems. The use of these efficient dispersing and mixing technologies can increase the gas-liquid ratio of the reaction between carbon dioxide and sodium phenolate, realize the micro-mixing of gas and liquid phases, increase the specific surface area of gas-liquid contact, and form microbubbles and droplets with certain stability. It can significantly improve the speed and efficiency of gas-liquid dispersion mixing.

(3)充分利用减压闪蒸设备具有热、质同时传递且传递速率快的特性：减压闪蒸过程具有热、质同时传递的特性，而且热、质的传递速率都很快。(3) Make full use of the characteristics of simultaneous heat and mass transfer and fast transfer rate of vacuum flash evaporation equipment: the vacuum flash evaporation process has the characteristics of simultaneous heat and mass transfer, and both heat and mass transfer rates are fast.

实现本发明需要的主要工艺设备为：高效气-液分散混合反应器、减压闪蒸设备、气-固分离设备等。The main process equipments required to realize the present invention are: high-efficiency gas-liquid dispersion mixing reactor, vacuum flash evaporation equipment, gas-solid separation equipment and the like.

本发明的优点体现在：The advantages of the present invention are reflected in:

(1)采用丙酮为苯酚钠羧化反应的溶剂，使苯酚钠和二氧化碳的羧化反应从传统的气-固多相反应变为气-液多相反应，具有反应效率和反应转化效率高的显著优点，从根本上解决了苯酚钠细颗粒的制备问题。(1) Using acetone as the solvent for the carboxylation reaction of sodium phenate, so that the carboxylation reaction of sodium phenate and carbon dioxide is changed from a traditional gas-solid heterogeneous reaction to a gas-liquid heterogeneous reaction, which has the remarkable advantages of high reaction efficiency and reaction conversion efficiency. Advantages, fundamentally solve the problem of the preparation of sodium phenolate fine particles.

(2)采用静态混合器、喷射式混合器、文丘里混合器等高效气-液分散混合设备，从动力学角度解决了提高气液比和提高单程转化率之间的矛盾，从根本上解决了提高气液比和提高单程转化率之间的矛盾。(2) The use of high-efficiency gas-liquid dispersion mixing equipment such as static mixers, jet mixers, and Venturi mixers solves the contradiction between increasing the gas-liquid ratio and improving the single-pass conversion rate from a dynamic point of view, and fundamentally solves the problem. The contradiction between increasing the gas-liquid ratio and increasing the single-pass conversion rate is solved.

(3)采用减压闪蒸设备为反应后物料的快速冷却和溶剂的快速脱除创造了有利条件，从根本上解决了工业规模反应器的设计以及连续操作中的反应后物料的快速冷却和溶剂的快速脱除技术难题。(3) The use of vacuum flash evaporation equipment creates favorable conditions for the rapid cooling of the reacted material and the rapid removal of the solvent, which fundamentally solves the design of the industrial-scale reactor and the rapid cooling and rapid cooling of the reacted material in continuous operation. The rapid removal of solvents is a technical problem.

(4)易实现连续操作。所采用的气-液分散混合、减压闪蒸、固-液分离技术均可以连续操作，而连续操作与间歇操作相比，其突出的优点就是产物品质稳定且易于控制，从而为后期分离精制创造了有利条件。(4) It is easy to realize continuous operation. The adopted gas-liquid dispersion mixing, vacuum flash evaporation, and solid-liquid separation technology can be operated continuously. Compared with intermittent operation, the outstanding advantage of continuous operation is that the product quality is stable and easy to control. Create favorable conditions.

(5)实现了溶剂的循环利用。采用丙酮溶解苯酚钠，不仅使苯酚钠和二氧化碳的羧化反应从传统的气-固多相反应变为气-液多相反应，而且溶剂丙酮可以分离回收，实现了溶剂丙酮的循环利用。(5) The recycling of the solvent is realized. Using acetone to dissolve sodium phenate not only changes the carboxylation reaction of sodium phenate and carbon dioxide from the traditional gas-solid heterogeneous reaction to a gas-liquid heterogeneous reaction, but also the solvent acetone can be separated and recovered, realizing the recycling of the solvent acetone.

(6)采用了高效气-液分散混合反应器、减压闪蒸设备等高效设备，实现了热、质的快速传递。(6) High-efficiency equipment such as high-efficiency gas-liquid dispersion mixing reactor and vacuum flash evaporation equipment are used to achieve rapid heat and mass transfer.

本发明的单元操作过程均为密封循环系统，整个工艺安全环保，符合清洁生产要求及绿色化工理念，是一种适合于连续化生产水杨酸钠的绿色化新方法。The unit operation process of the invention is a sealed circulation system, the whole process is safe and environmentally friendly, meets the requirements of clean production and the concept of green chemical industry, and is a new green method suitable for continuous production of sodium salicylate.

具体实施方式Detailed ways

下面结合实施例对本发明作进一步详细的说明。The present invention will be described in further detail below in conjunction with the embodiments.

实施例一Example 1

一种苯酚钠羧化反应制水杨酸钠的方法，以丙酮为溶剂，苯酚钠和二氧化碳为原料，采用高效气-液分散混合反应器，苯酚钠与二氧化碳发生气-液相羧化反应得到水杨酸钠，具体方法步骤如下：A method for preparing sodium salicylate by carboxylation of sodium phenate, using acetone as a solvent, sodium phenate and carbon dioxide as raw materials, using a high-efficiency gas-liquid dispersion mixing reactor, and performing a gas-liquid phase carboxylation reaction of sodium phenate and carbon dioxide to obtain Sodium salicylate, the concrete method steps are as follows:

(1)溶液配制：在搅拌釜中，将苯酚钠溶解于丙酮制得到苯酚钠溶液，溶液中苯酚钠的质量与丙酮的体积比为1.0kg:4.0L；(1) solution preparation: in stirred tank, sodium phenate is dissolved in acetone to obtain sodium phenate solution, and in the solution, the mass ratio of sodium phenate to acetone is 1.0kg:4.0L;

(2)羧化反应：在静态混合器中，苯酚钠溶液与二氧化碳进行气-液分散混合，苯酚钠与二氧化碳的摩尔比为1.0:2.0，反应压强为0.8MPa，苯酚钠与二氧化碳在反应温度为120℃下发生羧化反应生成水杨酸钠，反应后的物料进入下一步；(2) Carboxylation reaction: in a static mixer, the sodium phenate solution and carbon dioxide are mixed by gas-liquid dispersion, the molar ratio of sodium phenate and carbon dioxide is 1.0:2.0, the reaction pressure is 0.8MPa, and the sodium phenate and carbon dioxide are at the reaction temperature To generate sodium salicylate by carboxylation reaction at 120°C, the reacted material enters the next step;

(3)减压闪蒸：在闪蒸罐中，将上一步羧化反应后的物料进行减压闪蒸操作，操作的绝对压强为0.08MPa，减压闪蒸得到的气相物料经冷凝、气-液分离后得到的丙酮和二氧化碳循环利用，其他物料进入下一步；(3) Decompression flashing: in the flash tank, the material after the carboxylation reaction in the previous step is subjected to decompression flashing operation, and the absolute pressure of the operation is 0.08MPa, and the gas-phase material obtained by decompression flashing is condensed and decompressed. -The acetone and carbon dioxide obtained after the liquid separation are recycled, and other materials enter the next step;

(4)气-固分离：在气-固分离设备中，将上一步得到的物料进行气-固分离，其固相物料即为水杨酸钠。(4) Gas-solid separation: in the gas-solid separation equipment, the material obtained in the previous step is subjected to gas-solid separation, and the solid phase material is sodium salicylate.

实施例二Embodiment 2

一种苯酚钠羧化反应制水杨酸钠的方法，以丙酮为溶剂，苯酚钠和二氧化碳为原料，采用高效气-液分散混合反应器，苯酚钠与二氧化碳发生气-液相羧化反应得到水杨酸钠，具体方法步骤如下：A method for preparing sodium salicylate by carboxylation of sodium phenate, using acetone as a solvent, sodium phenate and carbon dioxide as raw materials, using a high-efficiency gas-liquid dispersion mixing reactor, and performing a gas-liquid phase carboxylation reaction of sodium phenate and carbon dioxide to obtain Sodium salicylate, the concrete method steps are as follows:

(1)溶液配制：在搅拌釜中，将苯酚钠溶解于丙酮制得到苯酚钠溶液，溶液中苯酚钠的质量与丙酮的体积比为1.0kg:8.0L；(1) solution preparation: in stirred kettle, sodium phenate is dissolved in acetone to obtain sodium phenate solution, and the quality of sodium phenate and the volume ratio of acetone in the solution are 1.0kg:8.0L;

(2)羧化反应：在喷射式混合器中，苯酚钠溶液与二氧化碳进行气-液分散混合，苯酚钠与二氧化碳的摩尔比为1.0:1.6，反应压强为0.6MPa，苯酚钠与二氧化碳在反应温度为100℃下发生羧化反应生成水杨酸钠，反应后的物料进入下一步；(2) Carboxylation reaction: in a jet mixer, the sodium phenate solution and carbon dioxide are mixed by gas-liquid dispersion, the molar ratio of sodium phenate and carbon dioxide is 1.0:1.6, and the reaction pressure is 0.6MPa. The temperature is that the carboxylation reaction occurs at 100 ° C to generate sodium salicylate, and the reacted material enters the next step;

(3)减压闪蒸：在闪蒸冷却器中，将上一步羧化反应后的物料进行减压闪蒸操作，操作的绝对压强为0.06MPa，减压闪蒸得到的气相物料经冷凝、气-液分离后得到的丙酮和二氧化碳循环利用，其他物料进入下一步；(3) Decompression flashing: in the flash cooler, the material after the carboxylation reaction in the previous step is subjected to decompression flashing operation, and the absolute pressure of the operation is 0.06MPa, and the gas-phase material obtained by decompression flashing is condensed, The acetone and carbon dioxide obtained after gas-liquid separation are recycled, and other materials enter the next step;

(4)气-固分离：在气-固分离设备中，将上一步得到的物料进行气-固分离，其固相物料即为水杨酸钠。(4) Gas-solid separation: in the gas-solid separation equipment, the material obtained in the previous step is subjected to gas-solid separation, and the solid phase material is sodium salicylate.

实施例三Embodiment 3

一种苯酚钠羧化反应制水杨酸钠的方法，以丙酮为溶剂，苯酚钠和二氧化碳为原料，采用高效气-液分散混合反应器，苯酚钠与二氧化碳发生气-液相羧化反应得到水杨酸钠，具体方法步骤如下：A method for preparing sodium salicylate by carboxylation of sodium phenate, using acetone as a solvent, sodium phenate and carbon dioxide as raw materials, using a high-efficiency gas-liquid dispersion mixing reactor, and performing a gas-liquid phase carboxylation reaction of sodium phenate and carbon dioxide to obtain Sodium salicylate, the concrete method steps are as follows:

(1)溶液配制：在搅拌釜中，将苯酚钠溶解于丙酮制得到苯酚钠溶液，溶液中苯酚钠的质量与丙酮的体积比为1.0kg:10.0L；(1) solution preparation: in stirred tank, sodium phenate is dissolved in acetone to obtain sodium phenate solution, and the mass ratio of sodium phenate to acetone in the solution is 1.0kg:10.0L;

(2)羧化反应：在文丘里混合器中，苯酚钠溶液与二氧化碳进行气-液分散混合，苯酚钠与二氧化碳的摩尔比为1.0:2.0，反应压强为0.4MPa，苯酚钠与二氧化碳在反应温度为80℃下发生羧化反应生成水杨酸钠，反应后物料进入下一步；(2) Carboxylation reaction: in a venturi mixer, the sodium phenate solution and carbon dioxide are mixed by gas-liquid dispersion. The temperature is that the carboxylation reaction occurs at 80 ° C to generate sodium salicylate, and the material enters the next step after the reaction;

(3)减压闪蒸：在闪蒸塔中，将上一步羧化反应后的物料进行减压闪蒸操作，操作的绝对压强为0.08MPa，减压闪蒸得到的气相物料经冷凝、气-液分离后得到的丙酮和二氧化碳循环利用，其他物料进入下一步；(3) Decompression flashing: in the flash tower, the material after the carboxylation reaction in the previous step is subjected to decompression flashing operation, and the absolute pressure of the operation is 0.08MPa, and the gas-phase material obtained by decompression flashing is condensed, decompressed and evaporated. -The acetone and carbon dioxide obtained after the liquid separation are recycled, and other materials enter the next step;

(4)气-固分离：在气-固分离设备中，将上一步经减压闪蒸得到的料进行气-固分离，其固相物料即为水杨酸钠。(4) Gas-solid separation: in the gas-solid separation equipment, the material obtained by flashing under reduced pressure in the previous step is subjected to gas-solid separation, and the solid phase material is sodium salicylate.

除上述各实施例，本发明的实施方案还有很多，凡采用等同或等效替换的技术方案，均在本发明的保护范围之内。In addition to the above-mentioned embodiments, there are still many embodiments of the present invention, and any technical solutions that are equivalent or equivalently replaced are all within the protection scope of the present invention.

Claims (4)

1. A method for preparing sodium salicylate by carboxylation reaction of sodium phenate, which takes acetone as a solvent, sodium phenate and carbon dioxide as raw materials, adopts an efficient gas-liquid dispersion mixing reactor, and the sodium phenate and the carbon dioxide undergo gas-liquid phase carboxylation reaction to obtain the sodium salicylate, and is characterized by comprising the following steps:
(1) solution preparation: in sodium phenolate solution preparation equipment, dissolving sodium phenolate in an organic solvent acetone to prepare a sodium phenolate solution;
(2) and (3) carboxylation reaction: in a high-efficiency gas-liquid dispersion mixing reactor, carrying out gas-liquid dispersion mixing on sodium phenolate solution and carbon dioxide, carrying out carboxylation reaction on the sodium phenolate and the carbon dioxide to generate sodium salicylate, and feeding the reacted materials to the next step;
(3) decompression flash evaporation: in a decompression flash evaporation device, performing decompression flash evaporation operation on the material subjected to the carboxylation reaction in the previous step, condensing and performing gas-liquid separation on a gas-phase material obtained by decompression flash evaporation to obtain acetone and carbon dioxide for recycling, and allowing other materials to enter the next step;
(4) gas-solid separation: and (3) in a gas-solid separation device, carrying out gas-solid separation on the material obtained in the last step, wherein the solid-phase material is the sodium salicylate.
2. The method of claim 1, wherein the carboxylation reaction of sodium phenolate in acetone solution is carried out by: in the sodium phenolate solution prepared in the first step, the volume ratio of the mass of the sodium phenolate to the volume of the acetone is 1.0kg: 4.0L-1.0 kg: 10.0L.
3. The method of claim 1, wherein the carboxylation reaction of sodium phenolate in acetone solution to prepare sodium salicylate comprises: the efficient gas-liquid dispersion mixing equipment in the carboxylation reaction process of the sodium phenolate in the second step is any one of a static mixer, a jet mixer and a Venturi mixer, the molar ratio of the sodium phenolate to the carbon dioxide in the carboxylation reaction is 1.0: 1.2-1.0: 2.0, the reaction pressure is 0.4 MPa-0.8 MPa, and the reaction temperature is 80-120 ℃.
4. The method of claim 1, wherein the carboxylation reaction of sodium phenolate in acetone solution is carried out by: and the third step of decompression flash evaporation, wherein the equipment is any one of a flash tank, a flash cooler or a flash tower, and the absolute pressure of the operation is 0.02 MPa-0.08 MPa.
CN202210664795.0A 2022-06-13 2022-06-13 Method for preparing sodium salicylate through sodium phenolate carboxylation reaction Pending CN114874092A (en)

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CN107141215A (en) * 2017-05-11 2017-09-08 镇江高鹏药业有限公司 A kind of salicylic acid preparation method of environmental protection in high yield
CN110041189A (en) * 2019-04-28 2019-07-23 东南大学 It is a kind of to prepare salicylic technique using microchannel continuous flow reactor
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