WO2022134882A1 - 一种1,4-环己二酮的纯化方法 - Google Patents

一种1,4-环己二酮的纯化方法 Download PDF

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WO2022134882A1
WO2022134882A1 PCT/CN2021/128670 CN2021128670W WO2022134882A1 WO 2022134882 A1 WO2022134882 A1 WO 2022134882A1 CN 2021128670 W CN2021128670 W CN 2021128670W WO 2022134882 A1 WO2022134882 A1 WO 2022134882A1
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cyclohexanedione
product
petroleum ether
purification method
sublimation
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PCT/CN2021/128670
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English (en)
French (fr)
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陶俊苗
卫冰
康改倩
许龙龙
康辉
张振国
王文幼
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西安向阳航天材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention belongs to the technical field of organic chemical industry, and relates to a purification method of 1,4-cyclohexanedione.
  • 1,4-cyclohexanedione English name 1,4-cyclohexanedione, molecular formula C6H8O2, is an important chemical intermediate, which can be used in the production of drugs, pesticides, liquid crystal materials, organic optoelectronic materials, superconducting materials, etc.
  • the other is: such as Chinese patents CN100486950C and CN109942388A and other processes using hydroquinone as raw materials, 1,4-cyclohexanediol is obtained by hydrogenation, and then 1,4-cyclohexanedione is generated under the action of an oxidant.
  • This process also has the characteristics of harsh reaction conditions, long reaction route, many by-products and difficult to separate, and needs to use a variety of expensive catalysts, generates more waste water and residue, and also keeps the production cost high.
  • Dimethyl succinyl succinate has a wide range of domestic sources, and the price is much lower than that of diethyl succinyl succinate (DESS). It is prepared by hydrolysis process using dimethyl succinyl succinate as raw material 1,4-cyclohexanedione has the advantages of sufficient raw material sources and low cost. In this process, dimethyl succinyl succinate is hydrolyzed and extracted with an organic solvent such as chloroform to obtain a crude 1,4-cyclohexanedione, but the obtained crude product contains certain impurities, usually yellow or red To brown, purification treatment is required to obtain qualified products.
  • an organic solvent such as chloroform
  • the purification step can refer to the distillation process in the diethyl succinyl succinate process, but the energy consumption of the distillation process is high, and the distilled liquid product forms hard lumps after cooling, which is difficult to take out and break, and needs to be cooled in petroleum ether.
  • the process is complicated, and the product purity is not high, usually the product is light yellow. How to purify the obtained crude product is one of the key steps to realize the industrialization of this process.
  • the object of the present invention is to provide a kind of purification method of 1,4-cyclohexanedione, which solves the problem that the distillation process existing in the prior art has high energy consumption, is easy to block the valve pipeline, and the distilled liquid product forms hard lumps after cooling. It is difficult to take out and break and the product purity is not high.
  • the technical scheme adopted in the present invention is, a kind of purification method of 1,4-cyclohexanedione, comprising the following steps:
  • Step 1 pour the crude 1,4-cyclohexanedione into petroleum ether and heat to reflux;
  • Step 2 after heating and refluxing in Step 1, cooling, filtering and drying are performed in sequence to obtain a semi-finished product of 1,4-cyclohexanedione;
  • step 3 the semi-finished 1,4-cyclohexanedione obtained in step 2 is subjected to vacuum sublimation to obtain white needle-like crystals, that is, the 1,4-cyclohexanedione product.
  • the boiling range of petroleum ether is 60-90°C.
  • the amount of petroleum ether is 3 to 10 times the weight of the crude 1,4-cyclohexanedione.
  • the reflux time of the crude 1,4-cyclohexanedione in petroleum ether is 30min-2h.
  • the conditions for vacuum sublimation are that the degree of vacuum is below -0.095MPa, the temperature of the system is 50-110°C, and the sublimation time is 3-50h.
  • the degree of vacuum is -0.098MPa ⁇ -0.095MPa.
  • the temperature of the system is 55-105°C.
  • the sublimation time is 5-48h.
  • the technological process of the present invention is simple and convenient to operate, and high-purity products can be directly obtained through extraction, washing and sublimation operations.
  • 1,4-cyclohexanedione being insoluble in petroleum ether, it is first refluxed in petroleum ether to remove low-boiling impurities such as methanol and extractant, and petroleum ether itself is easy to remove during the drying process.
  • the product obtained by the present invention is a white needle-like crystal, does not agglomerate, is convenient for collection, and can be directly packaged after collection. If a distillation process is adopted, the steamed product will form a whole after cooling, and it is hard and difficult to break. Pour the product into petroleum ether to cool and filter to prevent caking.
  • 1,4-cyclohexanedione has a high boiling point and is difficult to sublime under normal pressure, so the present invention adopts the measures of vacuum sublimation to ensure the smooth progress of the sublimation process.
  • the production cost of the present invention is low, and it is easy to scale up in industrialized production.
  • a kind of purification method of 1,4-cyclohexanedione of the present invention is specifically implemented according to the following steps:
  • Step 1 pour the crude 1,4-cyclohexanedione into petroleum ether and heat to reflux;
  • step 2 after heating and refluxing in step 1, cooling, filtration and drying are performed in sequence to obtain a semi-finished product of 1,4-cyclohexanedione; through this step, it is beneficial to remove low-boiling impurities and improve the obtained 1,4-cyclohexanedione Purity of ketones.
  • step 3 the semi-finished 1,4-cyclohexanedione obtained in step 2 is subjected to vacuum sublimation to obtain white needle-like crystals, that is, the 1,4-cyclohexanedione product.
  • the boiling range of petroleum ether is 60 ⁇ 90°C.
  • the amount of petroleum ether is 3 to 10 times the weight of the crude 1,4-cyclohexanedione.
  • the reflux time of crude 1,4-cyclohexanedione in petroleum ether is 30min ⁇ 2h.
  • the sublimation conditions are that the vacuum degree is below -0.095MPa, the system temperature is 55-105°C, and the sublimation time is 5-48h. Since 1,4-cyclohexanedione has a high boiling point, it is difficult to sublime under normal pressure. By setting the vacuum degree to be below -0.095 MPa and the system temperature to 55 to 105°C, the sublimation of 1,4-cyclohexanedione is favorable.
  • the purity of the obtained 1,4-cyclohexanedione product is not less than 99.5%.
  • the purification method of 1,4-cyclohexanedione provided by the present invention has the following beneficial effects:
  • the technological process of the present invention is simple and convenient to operate, and high-purity products can be directly obtained through extraction, washing and sublimation operations.
  • 1,4-cyclohexanedione being insoluble in petroleum ether, it is first refluxed in petroleum ether to remove low-boiling impurities such as methanol and extractant, and petroleum ether itself is easy to remove during the drying process.
  • the product obtained by the present invention is a white needle-like crystal, does not agglomerate, is convenient for collection, and can be directly packaged after collection. If a distillation process is adopted, the steamed product will form a whole after cooling, and it is hard and difficult to break. Pour the product into petroleum ether to cool and filter to prevent caking.
  • 1,4-cyclohexanedione has a higher boiling point and is difficult to sublime under normal pressure, so the present invention adopts the measure of vacuum sublimation to ensure the smooth progress of the sublimation process.
  • the production cost of the present invention is low, and it is easy to scale up in industrialized production.
  • the present invention firstly utilizes the feature that 1,4-cyclohexanedione is insoluble in petroleum ether, washes the obtained product with petroleum ether to remove part of volatile impurities, and then carries out vacuum sublimation to 1,4-cyclohexanedione.
  • the purification method has the advantages of simple operation, low cost, easy industrial scale-up, and the purity of the obtained product can reach more than 99.5%. question.

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

Abstract

本发明公开了一种1,4-环己二酮的纯化方法，具体按照如下步骤实施：步骤1，将1,4-环己二酮粗品倒入石油醚中，加热回流；步骤2，经步骤1加热回流后依次进行冷却、过滤、烘干，得到1,4-环己二酮半成品；步骤3，将步骤2得到的1,4-环己二酮半成品进行真空升华，得白色针状晶体，即就是1,4-环己二酮产品。本发明的一种1,4-环己二酮的纯化方法，解决了现有技术中存在的蒸馏工艺过程能耗高，蒸馏出的液态产品冷却后结成硬块难于取出及破碎以及产品纯度不高的问题。

Description

一种1,4-环己二酮的纯化方法 技术领域
本发明属于有机化工技术领域，涉及一种1,4-环己二酮的纯化方法。
背景技术
1,4-环己二酮，英文名称1,4-cyclohexanedione,分子式为C6H8O2，是一种重要的化工中间体，可用于生产药物、农药、液晶材料、有机光电材料、超导材料等。
国内外目前公开的资料中，主要有两种制备工艺，一是以丁二酸二乙酯为原料，通过酯缩合、水解、中和、萃取、蒸馏及后续处理得到纯品，文献《环境友好的1，4-环二酮的合成研究》(宁慧森，2011，河北大学硕士论文)详细描述了该工艺的过程，仅丁二酰丁二酸二乙酯水解工艺就需要5天时间，该工艺存在原料价格高、产品收率低、反应时间长的缺点，目前已基本淘汰。另外一种是：如中国专利CN100486950C及CN109942388A等对苯二酚为原料的工艺，通过加氢得到1,4-环己二醇，然后在氧化剂作用下生成1,4-环己二酮。该工艺同样存在反应条件苛刻、反应路线长、副产物多且难于分离的特点，且需要用到多种昂贵的催化剂，产生较多的废水废渣，也使生产成本居高不下。
丁二酰丁二酸二甲酯(DMSS)国内来源广泛，价格远低于丁二酰丁二酸二乙酯(DESS)，以丁二酰丁二酸二甲酯为原料通过水解工艺来制备1,4-环己二酮，具有原料来源充足、成本低的优点。该工艺中，丁二酰丁二酸二 甲酯水解后，使用氯仿等有机溶剂进行萃取，可以得到1,4-环己二酮粗品，但所得粗品中含有一定的杂质，通常呈黄色、红色至棕色，需要提纯处理才能得到合格产品。提纯步骤可以参考丁二酰丁二酸二乙酯工艺中的蒸馏工艺，但蒸馏过程能耗高，蒸馏出的液态产品冷却后结成硬块，难于取出及破碎，需要在石油醚中进行冷却，工艺复杂，而且产品纯度不高，通常产品呈浅黄色。如何对所得粗品进行提纯是实现该工艺工业化的关键步骤之一。
发明内容
本发明的目的是提供一种1,4-环己二酮的纯化方法，解决了现有技术中存在的蒸馏工艺过程能耗高，容易堵塞阀门管线，蒸馏出的液态产品冷却后结成硬块难于取出及破碎以及产品纯度不高的问题。
本发明所采用的技术方案是，一种1,4-环己二酮的纯化方法，包括如下步骤：
步骤1，将1,4-环己二酮粗品倒入石油醚中，加热回流；
步骤2，经步骤1加热回流后依次进行冷却、过滤、烘干，得到1,4-环己二酮半成品；
步骤3，将步骤2得到的1,4-环己二酮半成品进行真空升华，得白色针状晶体，即就是1,4-环己二酮产品。
作为一种实施方式，石油醚的沸程为60～90℃。
作为一种实施方式，石油醚用量为1,4-环己二酮粗品重量的3～10倍。
作为一种实施方式，1,4-环己二酮粗品在石油醚中的回流时间为30min～2h。
作为一种实施方式，进行真空升华的条件为真空度为-0.095MPa以下，体系温度为50～110℃，升华时间为3～50h。
作为一种实施方式，真空度为-0.098MPa～-0.095MPa。
作为一种实施方式，所述体系温度为55～105℃。
作为一种实施方式，所述升华时间为5～48h。
本发明的有益效果是：
1.本发明工艺流程简单，操作方便，通过萃取、洗涤、升华操作可以直接得到高纯度的产品。
2.利用1,4-环己二酮不溶于石油醚的特点，首先在石油醚中回流，可以将甲醇、萃取剂等低沸点杂质去除，石油醚本身在烘干过程中易于除去。
3.使用蒸馏工艺时，由于1,4-环己二酮熔点为78℃，在传输过程中极易堵塞阀门、管道，给生产带来极大不便，本发明采用升华工艺，避免了堵塞现象的发生。
4.本发明所得产品为白色针状晶体，不结块，方便收集，收集后可以直接包装，若采用蒸馏工艺，蒸出产品在冷却后会结成一整块，坚硬难于破碎，需要将蒸出产品倒入石油醚中冷却、过滤来防止结块。
5、1,4-环己二酮沸点较高，在常压下难于升华，因此本发明采用了真空升华的措施，保证了升华过程的顺利进行。
6.本发明生产成本低，易于工业化放大生产。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明一种1,4-环己二酮的纯化方法，具体按照如下步骤实施：
步骤1，将1,4-环己二酮粗品倒入石油醚中，加热回流；
步骤2，经步骤1加热回流后依次进行冷却、过滤、烘干，得到1,4-环己二酮半成品；通过该步骤，有利于去除低沸点杂质，提高获得的1,4-环己 二酮的纯度。
步骤3，将步骤2得到的1,4-环己二酮半成品进行真空升华，得白色针状晶体，即就是1,4-环己二酮产品。
石油醚的沸程为60～90℃。
石油醚用量为1,4-环己二酮粗品重量的3～10倍。
1,4-环己二酮粗品在石油醚中的回流时间为30min～2h。
升华条件为真空度为-0.095MPa以下，体系温度为55～105℃，升华时间为5～48h。由于1,4-环己二酮沸点高，常压下难于升华，通过将真空度设为-0.095MPa以下，体系温度设为55～105℃，有利于1,4-环己二酮升华。
通过本发明提供的1,4-环己二酮的纯化方法，得到的1,4-环己二酮产品的纯度不小于99.5％。
本发明提供的1,4-环己二酮的纯化方法，具有以下有益效果：
1.本发明工艺流程简单，操作方便，通过萃取、洗涤、升华操作可以直接得到高纯度的产品。
2.利用1,4-环己二酮不溶于石油醚的特点，首先在石油醚中回流，可以将甲醇、萃取剂等低沸点杂质去除，石油醚本身在烘干过程中易于除去。
3.使用蒸馏工艺时，由于1,4-环己二酮熔点为78℃，在传输过程中极易堵塞阀门、管道，给生产带来极大不便，本发明采用升华工艺，避免了堵塞现象的发生。
4.本发明所得产品为白色针状晶体，不结块，方便收集，收集后可以直接包装，若采用蒸馏工艺，蒸出产品在冷却后会结成一整块，坚硬难于破碎，需要将蒸出产品倒入石油醚中冷却、过滤来防止结块。
5、1,4-环己二酮沸点较高，在常压下难于升华，因此本发明采用了真空 升华的措施，保证了升华过程的顺利进行。
6.本发明生产成本低，易于工业化放大生产。
实施例1
称取50g 1,4-环己二酮粗品，加入150g石油醚，加热回流30min；冷却后过滤、洗涤、烘干以除去石油醚；然后在真空度-0.096MPa下，温度55℃条件下升华48h，得白色1,4-环己二酮产品48.5g，色谱检测纯度为99.7％。
实施例2
称取50g 1,4-环己二酮粗品，加入220g石油醚，加热回流1h；冷却后过滤、洗涤、烘干以除去石油醚；然后在真空度-0.096MPa下，温度70℃条件下升华36h，得白色1,4-环己二酮产品48.8g，色谱检测纯度为99.7％。
实施例3
称取50g 1,4-环己二酮粗品，加入320g石油醚，加热回流2h；冷却后过滤、洗涤、烘干以除去石油醚；然后在真空度-0.096MPa下，温度80℃条件下升华24h，得白色1,4-环己二酮产品48.4g，色谱检测纯度为99.7％。
实施例4
称取50g 1,4-环己二酮粗品，加入500g石油醚，加热回流2h；冷却后过滤、洗涤、烘干以除去石油醚；然后在真空度-0.097MPa下，温度95℃条件下升华12h，得白色1,4-环己二酮产品48.0g，色谱检测纯度为99.7％。
实施例5
称取50g 1,4-环己二酮粗品，加入250g石油醚，加热回流2h；冷却后过滤、洗涤、烘干以除去石油醚；然后在真空度-0.097MPa下，温度105℃条件下升华5h，得白色1,4-环己二酮产品48.8g，色谱检测纯度为99.7％。
本发明首先利用1,4-环己二酮不溶于石油醚的特点，对所得产品用石油醚进行洗涤，除去部分易挥发杂质，然后通过真空升华的工艺对1,4-环己二酮进行提纯，操作简单、成本低廉，易于工业化放大，所得产品纯度可以达到99.5％以上，解决了利用丁二酰丁二酸二甲酯为原料通过水解工艺制备1,4-环己二酮产品的提纯问题。

Claims (8)

  1. 一种1,4-环己二酮的纯化方法，其特征在于，包括如下步骤：
    步骤1，将1,4-环己二酮粗品倒入石油醚中，加热回流；
    步骤2，经步骤1加热回流后依次进行冷却、过滤、烘干，得到1,4-环己二酮半成品；
    步骤3，将步骤2得到的1,4-环己二酮半成品进行真空升华，得白色针状晶体，即就是1,4-环己二酮产品。
  2. 根据权利要求1所述的一种1,4-环己二酮的纯化方法，其特征在于，所述石油醚的沸程为60～90℃。
  3. 根据权利要求1所述的一种1,4-环己二酮的纯化方法，其特征在于，所述石油醚用量为1,4-环己二酮粗品重量的3～10倍。
  4. 根据权利要求1所述的一种1,4-环己二酮的纯化方法，其特征在于，所述1,4-环己二酮粗品在石油醚中的回流时间为30min～2h。
  5. 根据权利要求1所述的一种1,4-环己二酮的纯化方法，其特征在于，所述步骤3中，进行真空升华的条件为真空度为-0.095MPa以下，体系温度为50～110℃，升华时间为3～50h。
  6. 根据权利要求5所述的一种1,4-环己二酮的纯化方法，其特征在于，所述真空度为-0.098MPa～-0.095MPa。
  7. 根据权利要求5所述的一种1,4-环己二酮的纯化方法，其特征在于，所述体系温度为55～105℃。
  8. 根据权利要求5所述的一种1,4-环己二酮的纯化方法，其特征在于，所述升华时间为5～48h。
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