WO2018227779A1 - 一种二氟乙醇的生产工艺 - Google Patents

一种二氟乙醇的生产工艺 Download PDF

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WO2018227779A1
WO2018227779A1 PCT/CN2017/099971 CN2017099971W WO2018227779A1 WO 2018227779 A1 WO2018227779 A1 WO 2018227779A1 CN 2017099971 W CN2017099971 W CN 2017099971W WO 2018227779 A1 WO2018227779 A1 WO 2018227779A1
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difluoroethanol
water
catalyst
difluoroethylene
supplied
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PCT/CN2017/099971
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English (en)
French (fr)
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闫宗刚
椿范立
杨瑞芹
邢闯
葛繁龙
黄小磊
李志明
茅嘉龙
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南通宝凯化工有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds

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  • the invention belongs to the field of chemical industry, and particularly relates to a production process of difluoroethanol.
  • Difluoroethanol is an important aliphatic fluoro intermediate. Due to its special structure, it has different chemical properties than other alcohols. It can participate in a variety of organic synthesis reactions, especially in fluorochemicals. It has a wide range of uses in medicine, fluoropolymers and cleaning agents.
  • the application of difluoroethanol in pesticides is mainly the synthesis of penoxsulam, and its demand at home and abroad is gradually increasing. At present, China's research on difluoroethanol is still at the primary level, and the development and production prospects are very broad.
  • the preparation methods of difluoroethanol are: 1) metal hydride reduction method.
  • the use of a metal hydride as a reducing agent to reduce a hydroxy compound is a commonly used method for synthesizing a fluoroalcohol.
  • One type of metal hydride reducing agent studied is sodium borohydride, which can reduce aldehydes and ketones to alcohols, and the reaction conditions are mild.
  • 2) Liquid phase catalytic hydrogenation reduction method It is prepared by catalytic hydrogenation using fluorine-containing acid halide or methyl difluoroacetate or ethyl difluoroacetate as raw materials.
  • Gas phase catalytic hydrogenation reduction method which is prepared by catalytic hydrogenation using difluoroacetate or difluoroacetyl halide as raw materials.
  • base-catalyzed transesterification method using 1-bromo-2,2-difluoroethane or 1-chloro-2,2-difluoroethane as a raw material, by reacting with a hydroxy acid salt to form a fluorine-containing ester, and then It is obtained by transesterification of an alcohol with an alkali catalyst.
  • the object of the present invention is to solve the deficiencies in the prior art, and to provide a finished difluoroethanol by using an addition reaction of difluoroethylene as a raw material, and the preparation process thereof is reasonable, and the absorption rate and total revenue are obtained. High-precision, low-energy consumption, low by-products, clean, environmentally friendly, safe and reliable synthetic production process of difluoroethanol.
  • the preparation process of a difluoroethanol according to the present invention comprises the following steps:
  • the catalyst can be cleaned and supplied to the step (1) for repeated use.
  • the number of revolutions of the slurry bed reactor in the step (1) is 400-1000 rpm.
  • the catalyst described in the step (1) is 1 g of a Beta molecular sieve and a solid phosphoric acid catalyst, and is treated at 500 ° C for 3 hours.
  • the amount of water introduced in the step (2) is 20 g.
  • the elevated temperature described in the step (2) is raised to 200-250 ° C, and the pressurization is to increase the pressure to 3-6 MPa.
  • reaction time of the difluoroethylene and the water in the step (3) is 3-6 hours.
  • the invention adopts a slurry bed reactor to produce difluoroethanol, which has high selectivity, high conversion rate, high production capacity, high product purity, simple operation, low energy consumption, and easy availability of reagents, and the solid catalyst used can be used. Reuse, clean and environmentally friendly, safe and reliable, product purity ⁇ 99%, conversion rate ⁇ 85%, and the catalyst can be used continuously, improving the efficiency of the enterprise.
  • Figure 1 is a schematic overall flow diagram of the present invention.
  • the preparation process of a difluoroethanol as shown in FIG. 1 includes the following steps:
  • the catalyst can be cleaned and supplied to the step (1) for repeated use.
  • the number of revolutions of the slurry bed reactor described in the step (1) was 400 rpm.
  • the catalyst described in the step (1) was 1 g of a Beta molecular sieve and a solid phosphoric acid catalyst, and was treated at 500 ° C for 3 hours.
  • the amount of water introduced in the step (2) was 20 g.
  • step (2) The elevated temperature described in step (2) is increased to 250 ° C and the pressurization is increased to 3 MPa.
  • the reaction time of the difluoroethylene and the water described in the step (3) is 6 hours.
  • the preparation process of a difluoroethanol as shown in FIG. 1 includes the following steps:
  • the catalyst can be cleaned and supplied to the step (1) for repeated use.
  • the number of revolutions of the slurry bed reactor described in the step (1) was 1000 rpm.
  • the catalyst described in the step (1) was 1 g of a Beta molecular sieve and a solid phosphoric acid catalyst, and was treated at 500 ° C for 3 hours.
  • the amount of water introduced in the step (2) was 20 g.
  • step (2) The elevated temperature described in step (2) is increased to 200 ° C and the pressurization is increased to 6 MPa.
  • the reaction time of the difluoroethylene and the water described in the step (3) is 3 hours.
  • the preparation process of a difluoroethanol as shown in FIG. 1 includes the following steps:
  • the catalyst can be cleaned and supplied to the step (1) for repeated use.
  • the number of revolutions of the slurry bed reactor described in the step (1) was 500 rpm.
  • the catalyst described in the step (1) was 1 g of a Beta molecular sieve and a solid phosphoric acid catalyst, and was treated at 500 ° C for 3 hours.
  • the amount of water introduced in the step (2) was 20 g.
  • step (2) The elevated temperature described in step (2) is increased to 220 ° C and the pressurization is increased to 5 MPa.
  • the reaction time of the difluoroethylene and the water described in the step (3) is 4 hours.
  • the invention adopts a slurry bed reactor to produce difluoroethanol, which has high selectivity, high conversion rate, high production capacity, high product purity, simple operation, low energy consumption, and easy availability of reagents, and the solid catalyst used can be reused. Clean and environmentally friendly, safe and reliable, the product purity is ⁇ 99%, the conversion rate is ⁇ 85%, and the catalyst can be used continuously, which improves the efficiency of the enterprise.

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

Abstract

一种二氟乙醇的制备工艺，该制备工艺包括：在浆态床反应器中投入固体催化剂，然后通入水，升高温度并加压。再通入二氟乙烯进行水合反应，反应完全后冷却至室温，对于液体进行精馏，最终得到产物二氟乙醇。该二氟乙醇的制备工艺采用二氟乙烯为原料，制备过程简单且产品纯度高，产品纯度≥99％，转化率≥85％，且催化剂可以连续使用，提高了企业效率。

Description

一种二氟乙醇的生产工艺 技术领域
本发明属于化工领域，具体涉及一种二氟乙醇的生产工艺。
背景技术
二氟乙醇是一种重要的脂肪族含氟中间体，由于含有二氟甲基的特殊结构，使其化学性质不同于其他的醇类，可以参与多种有机合成反应，尤其是在含氟农药、医药、氟聚合物和清洗剂等方面具有广泛的用途。二氟乙醇在农药中的应用主要是合成五氟磺草胺，国内外对其需求逐渐增多。目前我国对于二氟乙醇的研究仍处于初级水平，开发与生产前景非常广阔。
目前，二氟乙醇的制备方法有：1)金属氢化物还原法。以金属氢化物为还原剂还原羟基化合物，是常用的合成氟醇的方法。研究较多的一类金属氢化物还原剂为硼氢化钠，它可以将醛和酮还原为醇，反应条件温和。2)液相催化加氢还原法。以含氟酰卤或者二氟乙酸甲酯或者二氟乙酸乙酯为原料，催化加氢制得。3)气相催化加氢还原法，以二氟乙酸酯或者二氟乙酰卤为原料，催化加氢制得。4)碱催化酯交换法，以1-溴-2，2-二氟乙烷或者1-氯-2，2-二氟乙烷为原料，通过与羟酸盐反应生成含氟酯，再在碱催化剂作用下与醇进行酯交换反应制得。
发明内容
发明目的：本发明的目的是为了解决现有技术中的不足，提供一种采用二氟乙烯为原料，通过加成反应制得成品二氟乙醇，其制备工艺设计合理，其吸收率和总收率高，且能耗低，副产物少，清洁环保、安全可靠的二氟乙醇的合成生产工艺。
技术方案：本发明所述的一种二氟乙醇的的制备工艺，包括如下步骤：
(1)将一定质量的催化剂经过预处理，然后投入到浆态床反应器内；
(2)把水通入到反应器内，升高温度到固定值，同时加压；
(3)把二氟乙烯通入到浆态反应器内，与水接触发生反应；
(4)反应后冷却，未反应的二氟乙烯气体排出提供给(3)重复使用，对剩下的物质进行精馏，得到二氟乙醇和水，水可以提供给(2)继续使用；
(5)对于催化剂可以清洗，提供给步骤(1)重复使用。
进一步的，所述步骤(1)所述的浆态床反应器的转数是400-1000rpm。
进一步的，所述步骤(1)所述的催化剂是1g的Beta分子筛和固体磷酸催化剂，并在500℃下处理3小时。
进一步的，所述步骤(2)所述的通入水的量是20g。
进一步的，所述步骤(2)所述的升高温度是升高到200-250℃，加压是增加压力到3-6MPa。
进一步的，所述步骤(3)所述的二氟乙烯与水反应时间为3-6小时。
有益效果：本发明采用浆态床反应器生产得出二氟乙醇，选择性高、转化率高、生产能力高、产品纯度高、操作简便、能耗低，且试剂易得，所用固体催化剂可重复利用，清洁环保，安全可靠，产品纯度≥99％，转化率≥85％，且催化剂可以连续使用，提高了企业效率。
附图说明
图1为本发明的整体流程示意图。
具体实施方式
下面结合附图和具体实施例对本发明的内容作进一步详细说明：
实施例1
如图1所示的一种二氟乙醇的制备工艺，包括如下步骤：
(1)将一定质量的催化剂经过预处理，然后投入到浆态床反应器内；
(2)把水通入到反应器内，升高温度到固定值，同时加压；
(3)把二氟乙烯通入到浆态反应器内，与水接触发生反应；
(4)反应后冷却，未反应的二氟乙烯气体排出提供给(3)重复使用，对剩下的物质进行精馏，得到二氟乙醇和水，水可以提供给(2)继续使用；
(5)对于催化剂可以清洗，提供给步骤(1)重复使用。
步骤(1)所述的浆态床反应器的转数为400rpm。
步骤(1)所述的催化剂是1g的Beta分子筛和固体磷酸催化剂，并在500℃下处理3小时。
步骤(2)所述的通入水的量是20g。
步骤(2)所述的升高温度是升高到250℃，加压是增加压力到3MPa。
步骤(3)所述的二氟乙烯与水反应时间为6小时。
实施例2
如图1所示的一种二氟乙醇的制备工艺，包括如下步骤：
(1)将一定质量的催化剂经过预处理，然后投入到浆态床反应器内；
(2)把水通入到反应器内，升高温度到固定值，同时加压；
(3)把二氟乙烯通入到浆态反应器内，与水接触发生反应；
(4)反应后冷却，未反应的二氟乙烯气体排出提供给(3)重复使用，对剩下的物质进行精馏，得到二氟乙醇和水，水可以提供给(2)继续使用；
(5)对于催化剂可以清洗，提供给步骤(1)重复使用。
步骤(1)所述的浆态床反应器的转数为1000rpm。
步骤(1)所述的催化剂是1g的Beta分子筛和固体磷酸催化剂，并在500℃下处理3小时。
步骤(2)所述的通入水的量是20g。
步骤(2)所述的升高温度是升高到200℃，加压是增加压力到6MPa。
步骤(3)所述的二氟乙烯与水反应时间为3小时。
实施例3
如图1所示的一种二氟乙醇的制备工艺，包括如下步骤：
(1)将一定质量的催化剂经过预处理，然后投入到浆态床反应器内；
(2)把水通入到反应器内，升高温度到固定值，同时加压；
(3)把二氟乙烯通入到浆态反应器内，与水接触发生反应；
(4)反应后冷却，未反应的二氟乙烯气体排出提供给(3)重复使用，对剩下的物质进行精馏，得到二氟乙醇和水，水可以提供给(2)继续使用；
(5)对于催化剂可以清洗，提供给步骤(1)重复使用。
步骤(1)所述的浆态床反应器的转数为500rpm。
步骤(1)所述的催化剂是1g的Beta分子筛和固体磷酸催化剂，并在500℃下处理3小时。
步骤(2)所述的通入水的量是20g。
步骤(2)所述的升高温度是升高到220℃，加压是增加压力到5MPa。
步骤(3)所述的二氟乙烯与水反应时间为4小时。
本发明采用浆态床反应器生产得出二氟乙醇，选择性高、转化率高、生产能力高、产品纯度高、操作简便、能耗低，且试剂易得，所用固体催化剂可重复利用，清洁环保，安全可靠，产品纯度≥99％，转化率≥85％，且催化剂可以连续使用，提高了企业效率。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (6)

  1. 一种二氟乙醇的制备工艺，其特征在于，包括如下步骤：
    (1)将一定质量的催化剂经过预处理，然后投入到浆态床反应器内；
    (2)把水通入到反应器内，升高温度到固定值，同时加压；
    (3)把二氟乙烯通入到浆态反应器内，与水接触发生反应；
    (4)反应后冷却，未反应的二氟乙烯气体排出提供给(3)重复使用，对剩下的物质进行精馏，得到二氟乙醇和水，水可以提供给(2)继续使用；
    (5)对于催化剂可以清洗，提供给步骤(1)重复使用。
  2. 根据权利要求1所述的二氟乙醇的制备工艺，其特征在于：所述步骤(1)中所述的浆态床反应器的转数为400-1000rpm。
  3. 根据权利要求1所述的二氟乙醇的制备工艺，其特征在于：所述步骤(1)中所述的催化剂为1g的Beta分子筛和固体磷酸催化剂，并在500℃下处理3小时。
  4. 根据权利要求1所述的二氟乙醇的制备工艺，其特征在于：所述步骤(2)所述的通入水的量是20g。
  5. 根据权利要求1所述的二氟乙醇的制备工艺，其特征在于：所述步骤(2)所述的升高温度是升高到200-250℃，加压是增加压力到3-6MPa。
  6. 根据权利要求1所述的二氟乙醇的制备工艺，其特征在于：所述步骤(3)中二氟乙烯与水接触反应，反应时间是3-6小时。
PCT/CN2017/099971 2017-06-17 2017-08-31 一种二氟乙醇的生产工艺 WO2018227779A1 (zh)

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US20140243561A1 (en) * 2011-07-19 2014-08-28 Bayer Intellectual Property Gmbh Process for preparing 2,2-difluoroethanol
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