WO2017181517A1 - 制备1,2-二氯六氟环戊烯的方法 - Google Patents

制备1,2-二氯六氟环戊烯的方法 Download PDF

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WO2017181517A1
WO2017181517A1 PCT/CN2016/086825 CN2016086825W WO2017181517A1 WO 2017181517 A1 WO2017181517 A1 WO 2017181517A1 CN 2016086825 W CN2016086825 W CN 2016086825W WO 2017181517 A1 WO2017181517 A1 WO 2017181517A1
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reaction
chromium
molar ratio
cyclopentadiene
dichlorohexafluorocyclopentene
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权恒道
刘冬鹏
周晓猛
贾晓卿
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Beijing Yuji Science and Technology Co Ltd
Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02—Monocyclic halogenated hydrocarbons
    • C07C23/08—Monocyclic halogenated hydrocarbons with a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene

Definitions

  • the present invention relates to a process for preparing 1,2-dichlorohexafluorocyclopentene, in particular to a method for first-time pyrolysis of cyclopentadiene by cyclopentadiene, followed by chlorination to obtain tetrachlorocyclopentane, and finally Further, a method of preparing 1,2-dichlorohexafluorocyclopentene by gas phase catalytic reaction with a mixed gas of hydrogen fluoride and chlorine gas is carried out.
  • 1,2-Dichlorohexafluorocyclopentene is an important class of intermediates with high industrial value. It can prepare etchant octafluorocyclopentene and cleaning agent 1,2,2,3,3,4 , 4-heptafluorocyclopentane, and the like.
  • anhydrous hydrogen fluoride It is anhydrous hydrogen fluoride.
  • a fluorination catalyst such as a SbCl 5 catalyst (see documents WO9743233, WO9600707 and US6218586) or a catalyst containing ruthenium and iron (see document US Pat. No. 5,180,861).
  • the above preparation process has the following disadvantages: first, the starting material is difficult to obtain, and secondly, when the fluorinating agent is a fluorine-containing and/or chlorine-based cerium compound, such a fluorinating agent is highly corrosive and easily hydrolyzed to release hydrogen fluoride or hydrogen chloride gas, resulting in It is difficult to handle and control in use; meanwhile, when the fluorinating agent is anhydrous hydrogen fluoride, the fluorination catalyst has low activity and is easily deactivated.
  • the fluorinating agent is a fluorine-containing and/or chlorine-based cerium compound
  • the technical problem to be solved by the present invention is to solve the deficiencies in the background art, and to provide a raw material which is easy to obtain, has high activity of fluorination catalyst and high stability, and is suitable for large-scale preparation of 1,2-dichlorohexafluorocyclopentene. method.
  • the fluorination catalyst is a chromium-based catalyst.
  • the chromium-based catalyst is obtained by blending a chromium compound and a metal powder and baking at a high temperature, and the mass percentage composition of the chromium compound and the metal powder is 95% to 99.9%: 0.1% to 5%.
  • the chromium compound is chromium trioxide or chromium hydroxide
  • the metal powder is one or more of tungsten powder and molybdenum powder.
  • the high-temperature baking condition is: baking at 300 ° C to 500 ° C for 6 to 15 hours in a nitrogen atmosphere.
  • the chromium-based catalyst is subjected to an activation treatment prior to use, and the activation treatment is carried out at 60 to 450 ° C for 6 to 15 hours in a mixed gas of nitrogen and HF at a molar ratio of 10:1.
  • the molar ratio of the tetrachlorocyclopentane, hydrogen fluoride and chlorine is 1:5 to 20:5, the reaction pressure is 0.1 to 1.5 Ma, the reaction temperature is 300 to 500 ° C, and the contact time is 2 to 30 s.
  • the molar ratio of the chlorine gas to the cyclopentadiene is from 1 to 3:1, the reaction temperature is from 0 to 40 ° C, and the reaction time is from 1 to 10 h.
  • the cyclopentadiene is prepared by using dicyclopentadiene as a raw material, using nitrogen or another inert gas as a diluent, and thermally cracking to obtain cyclopentadiene.
  • the molar ratio of the diluent to dicyclopentadiene is 1:0.5-3, the reaction pressure is 0.1-1.5 Ma, the reaction temperature is 300-450 ° C, and the contact time is 5 s to 30 s.
  • the reaction conditions of the present invention are preferably such that the molar ratio of the diluent to the dicyclopentadiene is 1:1 to 2, the reaction temperature is 330 ° C to 370 ° C, the reaction pressure is 0.1 to 1.5 MPa, and the contact time is 10 s to 20 s.
  • the molar ratio of the chlorine gas to the cyclopentadiene is from 1 to 1.5:1, the reaction temperature is from 20 to 30 ° C, and the reaction time is from 3 to 7 h.
  • the molar ratio of the tetrachlorocyclopentane, hydrogen fluoride and chlorine is 1:10 to 15:5, the reaction pressure is 0.1 to 1.5 MPa, the reaction temperature is 370 to 450 ° C, and the contact time is 10 to 20 s.
  • the cyclopentadiene of the invention is used as a raw material, and the cyclopentadiene is often present in the form of a dimer, and the dicyclopentadiene is partially decomposed into cyclopentadiene when heated, and the fractionation column is topped when distilled under normal pressure.
  • the temperature above is maintained at 41 to 42 ° C, which can be safely converted to cyclopentadiene.
  • the method of the invention is employed.
  • 1,2-dichlorohexafluorocyclopentene is obtained by gas phase pyrolysis, liquid phase chlorination and gas phase catalytic chlorofluorination.
  • the main reactions are as follows:
  • the reactor type of the present invention is not critical, and the reactor of the first step reaction and the third step reaction may use a tubular reactor, a fluidized bed reactor or the like. Further, an adiabatic reactor or an isothermal reactor can also be used, preferably a tubular reactor.
  • the second step reaction can be carried out in a glass material, a stainless steel material or a polytetrafluoroethylene reactor, preferably a glass autoclave.
  • the precursor of the chromium-based catalyst used in the present invention is composed of a blend of a chromium compound and a metal powder, and has a mass percentage composition of 95% to 99.9%: 0.1% to 5%, wherein the chromium compound is chromium oxide or chromium hydroxide.
  • the chromium hydroxide is used, and the metal powder is one or more of tungsten powder and molybdenum powder.
  • the fluorination catalyst is obtained by the following preparation method: the chromium compound and the metal powder are uniformly mixed in a mass percentage, and press-molded to obtain a catalyst precursor; and the obtained catalyst precursor is calcined at 300 to 500 ° C under a nitrogen atmosphere for 6 to 15 In an hour, it is further activated at 60 ° C to 450 ° C for 6 to 15 hours in a mixed gas atmosphere of HF and nitrogen having a molar ratio of 1:10 to obtain a fluorination catalyst.
  • any other known fluorination catalyst can also be used in the present invention, for example: chromium oxide, chromium fluoride, fluorinated chromium oxide, aluminum fluoride, fluorinated alumina, supported on activated carbon.
  • Different fluorination catalysts are used, and the reaction conditions are different, including reaction temperature, reaction pressure, contact time, and material molar ratio, resulting in different yields of 1,2-dichlorohexafluorocyclopentene.
  • the invention adopts a blending method to prepare a chromium-based catalyst, and a chromium compound and a metal powder are mixed according to a certain ratio to obtain a catalyst precursor.
  • the catalyst precursor is calcined at a high temperature, the chromium compound exists in the form of chromium oxide, and the metal powder continues. It exists in elemental form and then enters the activation phase of a mixed gas composed of nitrogen and fluorine gas.
  • metal powders such as tungsten powder, molybdenum powder and indium powder are mixed with HF and chlorine.
  • the above-mentioned fluorides are mostly separated from the catalyst structure by means of gas, so that not only the pores of the catalyst can be provided, but also the specific surface area and pore volume of the catalyst are increased, and the activity of the catalyst is increased, while the metal elements which are not lost are mainly simple or small.
  • the form of the fluoride remains in the catalyst, and the carbon deposition of the catalyst at a high temperature can be effectively suppressed.
  • the fluorination catalyst prepared by the above scheme has high use temperature and high catalytic activity.
  • the technical method provided by the invention not only has easy availability of raw materials, high activity of fluorination catalyst and high stability, but also is suitable for large-scale preparation of 1,2-dichlorohexafluorocyclopentene.
  • Gas chromatographic analysis method high purity nitrogen and hydrogen are used as carrier gases.
  • the detection conditions were a vaporization chamber temperature of 250 ° C, an auxiliary furnace 2 temperature of 250 ° C, a detector temperature of 250 ° C, a column furnace initial temperature of 40 ° C, a hold of 10 minutes, a heating rate of 15 ° C / min, and a final temperature of 230 ° C for 3 minutes.
  • Example 1 The same operation as in Example 1 except that the contact time was changed to 2 s, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the contact time was changed to 10 s, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the contact time was changed to 20 s, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the contact time was changed to 30 s, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the molar ratio of nitrogen to dicyclopentadiene was changed to 1:0.5, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the molar ratio of nitrogen to dicyclopentadiene was changed to 1:1, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the molar ratio of nitrogen to dicyclopentadiene was changed to 1:2, and the results are shown in Table 1.
  • Example 1 The same operation as in Example 1 except that the molar ratio of nitrogen gas to dicyclopentadiene was changed to 1:3, and the results are shown in Table 1.
  • the cyclopentadiene and chlorine gas were simultaneously added to the autoclave, the molar ratio of cyclopentadiene to chlorine gas was 1:1.5, the autoclave temperature was 20 ° C, the reaction time was 5 h, and the product was washed with water, alkali washed, and then 4A.
  • the molecular sieve was dried and sampled for GC detection. The experimental results are shown in Table 2.
  • Example 17 The same operation as in Example 17 except that the molar ratio of cyclopentadiene to chlorine was changed to 1:1, and the results are shown in Table 2.
  • Example 17 The same operation as in Example 17 except that the molar ratio of cyclopentadiene to chlorine was changed to 1:2, and the results are shown in Table 2.
  • Example 17 The same operation as in Example 17 except that the molar ratio of cyclopentadiene to chlorine was changed to 1:3, and the results are shown in Table 2.
  • the chromium nitrate is dissolved in water, ammonia water is added at 60 ° C, the pH of the solution is controlled between 7.5 and 8.5, and the precipitate is fully precipitated under stirring, and the formed slurry is filtered, washed with deionized water until neutral, and then Drying at 150 ° C for 12 hours gave chromium hydroxide.
  • the obtained chromium hydroxide and the metal powder are uniformly mixed according to the mass percentage composition of 95% to 99.9%: 0.1% to 5%, and press-molded to obtain a catalyst precursor, and then The catalyst precursor was calcined at 450 ° C for 10 hours in a nitrogen atmosphere, and then activated at 60-450 ° C for 12 hours in a mixed gas atmosphere of HF and nitrogen at a molar ratio of 1:10 to prepare a chromium-based catalyst.
  • a tubular reactor made of Incon alloy having an inner diameter of 1/2 inch and a length of 30 cm 10 ml of a chromium-based catalyst was prepared, and the chromium-based catalyst precursor was composed of chromium hydroxide and tungsten powder in a mass percentage of 97%: 3 % mixed and pressed, the activation temperature is 300 ° C.
  • the reactor was heated to 370 ° C while introducing anhydrous hydrogen fluoride, tetrachlorocyclopentane and chlorine gas, and the molar ratio of anhydrous hydrogen fluoride, tetrachlorocyclopentane and chlorine was controlled to 12:1:5, and the contact time was 15 seconds.
  • the reaction pressure was 0.1 MPa, and after reacting for 20 hours, the reaction product was washed with water and alkali, and the organic matter was separated. After drying and water removal, the composition of the organic matter was analyzed by gas chromatography. The results are shown in Table 3.
  • Example 25 The same operation as in Example 25 except that the chromium-based catalyst precursor was prepared by mixing and pressing a chromium hydroxide and indium powder in a mass percentage composition of 97%:3%, and changing the reaction temperature to 300 ° C. The results are shown in Table 3.
  • Example 25 The same operation as in Example 25 except that the chromium-based catalyst precursor was prepared by mixing and pressing a chromium hydroxide and tungsten powder according to a mass percentage composition of 99.9%:0.1%, and changing the reaction temperature to 330 °C. The results are shown in Table 3.
  • Example 25 The same operation as in Example 25 was carried out except that the tungsten powder in the chromium-based catalyst precursor was changed to molybdenum powder, the activation temperature was changed to 60 ° C, and the reaction temperature was changed to 410 ° C.
  • the results are shown in Table 3.

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Abstract

本发明涉及一种制备1,2-二氯六氟环戊烯的方法，一种制备1,2-二氯六氟环戊烯的方法，包括如下反应步骤：(1)、以环戊二烯为原料，在液相条件下与氯气发生反应得到四氯环戊烷；(2)、以四氯环戊烷为原料，在氟化催化剂存在的条件下，与氟化氢和氯气发生气相氯氟化反应而得到1,2-二氯六氟环戊烯，所述氟化催化剂为铬基催化剂。本发明提供的技术方法，不但原料易得、氟化催化剂活性高且稳定性高，而且适用于大规模制备1,2-二氯六氟环戊烯。

Description

制备1,2-二氯六氟环戊烯的方法 技术领域
本发明涉及一种制备1,2-二氯六氟环戊烯的方法，尤其涉及一种通过双环戊二烯先加热裂解成环戊二烯，再经氯化得到四氯环戊烷，最后再与氟化氢与氯气的混合气进行气相催化反应制备得到1,2-二氯六氟环戊烯的方法。
背景技术
1,2-二氯六氟环戊烯是一类重要的中间体，具有很高的工业价值，可以制备刻蚀剂八氟环戊烯、清洗剂1,2,2,3,3,4,4-七氟环戊烷等。
截至目前，很多文献报道1,2-二氯六氟环戊烯的制备方法。大多是由六氯环戊二烯或八氯环戊烯为起始原料进行合成，使用的氟化试剂可以是SbF5(见文献US2459783和Ind.Eng.Chem.,1947,39(3),415–417.)、SbF3Cl2(见文献J.Am.Chem.Soc.,1954,76(2),610–612.)、SbFxCl5-x(0<x<5)(见文献J.Am.Chem.Soc.,1945,67,1235-1237.)或者SbF3与SbF3Cl2组成的混合物(见文献Journal Indian Chem.Soc.,1953,30,525-528.)，还可以是无水氟化氢。采用无水氟化氢作为氟化试剂必须在氟化催化剂如SbCl5催化剂(见文献WO9743233、WO9600707和US6218586)或含铋、铁的催化剂(见文献US5180861)条件下进行反应。
上述制备工艺存在以下缺点：首先起始原料难以获得,其次，氟化试剂是含氟和/或氯的锑化合物时，这类氟化试剂高腐蚀性、易水解释放出氟化氢或氯化氢气体，导致其在使用中难以操作和控制；同时，当氟化试剂是无水氟化氢时，氟化催化剂的活性低，且容易失活。
发明内容
本发明所要解决的技术问题在于解决背景技术中的不足，提供一种不仅原料易得、氟化催化剂活性高且稳定性高、适用于大规模制备1,2-二氯六氟环戊烯的方法。
一种制备1,2-二氯六氟环戊烯的方法，包括如下反应步骤：
(1)、以环戊二烯为原料，在液相条件下与氯气发生反应得到四氯环戊烷；
(2)、以四氯环戊烷为原料，在氟化催化剂存在的条件下，与氟化氢和氯气发生气相氯氟化反应而得到1,2-二氯六氟环戊烯。
所述氟化催化剂为铬基催化剂。
所述铬基催化剂由铬化合物和金属粉共混后高温焙烧而成，其铬化合物和金属粉的质量百分组成为95％～99.9％：0.1％～5％。
其中铬化合物为三氧化二铬或氢氧化铬，金属粉为钨粉、钼粉中的一种或数种。
所述高温焙烧条件为：在氮气氛围下于300℃～500℃进行焙烧6～15小时。
所述铬基催化剂使用前需活化处理，所述活化处理为于60℃～450℃下在摩尔比为10：1的氮气与HF组成的混合气体中活化6～15小时。
所述四氯环戊烷、氟化氢和氯气的摩尔比为1：5～20：5，反应压力0.1～1.5Ma，反应温度为300℃～500℃，接触时间为2s～30s。
所述氯气与环戊二烯的摩尔比1～3：1，反应温度为0～40℃，反应时间为1-10h。
所述环戊二烯的制备是以双环戊二烯为原料，以氮气或其它惰性气体作为稀释剂，加热裂解得到环戊二烯。
所述稀释剂与双环戊二烯的摩尔比为1：0.5～3，反应压力0.1～1.5Ma，反应温度为300℃～450℃，接触时间为5s～30s。
本发明反应条件优选为：稀释剂与双环戊二烯的摩尔比为1：1～2，反应温度为330℃～370℃，反应压力0.1～1.5MPa，接触时间为10s～20s。
所述氯气与环戊二烯的摩尔比1～1.5：1，反应温度为20～30℃，反应时间为3-7h。
所述四氯环戊烷、氟化氢和氯气的摩尔比为1：10～15：5，反应压力0.1～1.5MPa，反应温度为370℃～450℃，接触时间为10s～20s。
本发明环戊二烯为原料，而环戊二烯常以双聚物形式存在，二聚环戊二烯加热时部分分解成环戊二烯，在常压下进行蒸馏时，使分馏柱顶上的温度保持在41～42℃，即可安全转变为环戊二烯。优选采用本发明的方法。
因此以双环戊二烯为起始原料，经过气相高温裂解、液相氯化和气相催化氯氟化反应，得到1,2-二氯六氟环戊烯，其主要反应如下：
Figure PCTCN2016086825-appb-000001
本发明的反应器类型不是关键，第一步反应和第三步反应的反应器可以使用管式反应器、流化床反应器等。另外，绝热反应器或等温反应器亦可用，优选管式反应器。第二步反应可以在玻璃材质、不锈钢材质或聚四氟乙烯材质的反应器中进行，优选玻璃高压釜。
本发明使用的铬基催化剂的前驱体是由铬化合物和金属粉共混组成，其质量百分组成为95％～99.9％：0.1％～5％，其中铬化合物为三氧化二铬或氢氧化铬，优选氢氧化铬，金属粉为钨粉、钼粉中的一种或数种。该氟化催化剂通过如下制备方法得到：将铬化合物和金属粉按质量百分比混合均匀，压制成型，得到催化剂前驱体；所得催化剂前驱体，在氮气氛围下于300℃～500℃进行焙烧6～15小时，再于60℃～450℃在摩尔比为1：10的HF与氮气组成的混合气体氛围下活化6～15小时，制得氟化催化剂。除了上述氟化催化剂外，其他任何已知的氟化催化剂也可用于本发明，例如：氧化铬、氟化铬、氟化的氧化铬、氟化铝、氟化的氧化铝、负载于活性炭的氟化铝、氟化镁上的氧化铬、含有多种金属(如Zn、Co、Ni、Ge、In等)的氧化铬以及活性炭负载五氯化锑或四氯化钛等。采用的氟化催化剂不同，则反应条件不同，包括反应温度、反应压力、接触时间以及物料摩尔比，导致所得到的1,2-二氯六氟环戊烯产率也不同。
本发明采用共混法制备铬基催化剂，将铬化合物和金属粉按照一定的比例混合制得催化剂前驱体，当催化剂前驱体经高温焙烧，铬化合物以氧化铬的形式存在，而金属粉则继续以单质形式存在，然后进入由氮气与氟气组成的混合气体的活化阶段，在氧化铬氟化为氟化铬直至无水汽产生之后，钨粉、钼粉和铟粉等金属粉与HF和氯气发生反应上述氟化物大多以气体的方式脱离催化剂结构，这样不仅可为催化剂提供孔道，同时增加催化剂的比表面积和孔容，提高催化剂的活性，而未流失的金属元素则主要以单质或少量六氟化物的形式留在催化剂中，可以有效抑制高温时催化剂的积碳。整个效果看，由上述方案制备得到的氟化催化剂不但使用温度高，而且催化活性高。
本发明的优点：本发明提供的技术方法，不但原料易得、氟化催化剂活性高且稳定性高，而且适用于大规模制备1,2-二氯六氟环戊烯。
具体实施方式
分析仪器：上海海欣色谱GC-930、氢火焰检测器，色谱柱为毛细管柱Al2O3/S“50m×0.320mm×0.25μm”(中国科学院兰州化学物理研究所色谱技术研究开发中心制造)。
气相色谱分析方法：高纯氮和氢气用作载气。检测条件为汽化室温度250℃，辅助炉2温度250℃，检测器温度250℃，柱炉初始温度40℃，保持10分钟，升温速率15℃/min，终温230℃，保持3分钟。
实施例1
在内径1/2英寸、长30cm的因康合金制的管式反应器中装填30毫升惰性氧化铝，反应器升温至350℃，在反应器中同时通入氮气和双环戊二烯，控制氮气和双环戊二烯的摩尔比为1：1.5，接触时间为15秒，反应压力0.1MPa，反应产物经0℃冰浴冷却后，用气相色谱分析 有机物的组成，结果见表1。
实施例2
与实施例1相同的操作，所不同的是反应温度改为300℃，结果见表1。
实施例3
与实施例1相同的操作，所不同的是反应温度改为330℃，结果见表1。
实施例4
与实施例1相同的操作，所不同的是反应温度改为410℃，结果见表1。
实施例5
与实施例1相同的操作，所不同的是反应温度改为450℃，结果见表1。
实施例6
与实施例1相同的操作，所不同的是接触时间改为2s，结果见表1。
实施例7
与实施例1相同的操作，所不同的是接触时间改为10s，结果见表1。
实施例8
与实施例1相同的操作，所不同的是接触时间改为20s，结果见表1。
实施例9
与实施例1相同的操作，所不同的是接触时间改为30s，结果见表1。
实施例10
与实施例1相同的操作，所不同的是氮气和双环戊二烯的摩尔比改为1：0.5，结果见表1。
实施例11
与实施例1相同的操作，所不同的是氮气和双环戊二烯的摩尔比改为1：1，结果见表1。
实施例12
与实施例1相同的操作，所不同的是氮气和双环戊二烯的摩尔比改为1：2，结果见表1。
实施例13
与实施例1相同的操作，所不同的是氮气和双环戊二烯的摩尔比改为1：3，结果见表1。
实施例14
与实施例1相同的操作，所不同的是反应压力改为0.5MPa，结果见表1。
实施例15
与实施例1相同的操作，所不同的是反应压力改为1.0MPa，结果见表1。
实施例16
与实施例1相同的操作，所不同的是反应压力改为1.5MPa，结果见表1。
表1
Figure PCTCN2016086825-appb-000002
实施例17
在高压釜中同时加入环戊二烯和氯气，控制环戊二烯和氯气的摩尔比为1：1.5，高压釜温度为20℃，反应时间为5h，产物经水洗、碱洗，然后用4A分子筛干燥，取样进行GC检测，实验结果见表2。
实施例18
与实施例17相同的操作，所不同的是环戊二烯和氯气的摩尔比改为1：1，结果见表2。
实施例19
与实施例17相同的操作，所不同的是环戊二烯和氯气的摩尔比改为1：2，结果见表2。
实施例20
与实施例17相同的操作，所不同的是环戊二烯和氯气的摩尔比改为1：3，结果见表2。
实施例21
与实施例17相同的操作，所不同的是反应温度改为0℃，反应时间改为10h，结果见表2。
实施例22
与实施例17相同的操作，所不同的是反应温度改为10℃，反应时间改为7h，结果见表2。
实施例23
与实施例17相同的操作，所不同的是反应温度改为30℃，反应时间改为3h，结果见表2。
实施例24
与实施例17相同的操作，所不同的是反应温度改为40℃，反应时间改为1h，结果见表2。
表2
Figure PCTCN2016086825-appb-000003
实施例25～28中涉及到了铬基催化剂的制备方法如下：
将硝酸铬溶解在水中，在60℃加入氨水，控制溶液pH7.5～8.5范围之间，使其在搅拌条件下充分沉淀，将形成的浆体过滤，用去离子水洗涤至中性，然后在150℃干燥12小时，得到氢氧化铬。
将所得氢氧化铬与金属粉(金属粉为钨粉、钼粉和铟粉)按照质量百分组成为95％～99.9％：0.1％～5％进行混合均匀，压制成型，得到催化剂前驱体，然后将催化剂前驱体在氮气氛围下450℃进行焙烧10小时后，在60-450℃用摩尔比为1：10的HF与氮气组成的混合气体氛围下的活化12小时，制得铬基催化剂。
实施例25
在内径1/2英寸、长30cm的因康合金制的管式反应器中装填10毫升铬基催化剂，该铬基催化剂前驱体是由氢氧化铬与钨粉按照质量百分组成97％：3％混匀、压制而成，活化温度为300℃。反应器升温至370℃，同时通入无水氟化氢、四氯环戊烷和氯气，控制无水氟化氢、四氯环戊烷和氯气的摩尔比为12：1：5，接触时间为15秒，反应压力0.1MPa，反应20h后，反应产物经水洗、碱洗，分离得到有机物，经干燥、除水后，用气相色谱分析有机物的组成，结果见表3。
实施例26
与实施例25相同的操作，所不同的是铬基催化剂前驱体是由氢氧化铬与铟粉按照质量百分组成97％：3％混匀、压制而成，并将反应温度改为300℃，结果见表3。
实施例27
与实施例25相同的操作，所不同的是铬基催化剂前驱体是由氢氧化铬与钨粉按照质量百分组成99.9％：0.1％混匀、压制而成，并将反应温度改为330℃，结果见表3。
实施例28
与实施例25相同的操作，所不同的是将铬基催化剂前驱体中的钨粉改为钼粉，活化温度改为60℃，并将反应温度改为410℃，结果见表3。
表3
Figure PCTCN2016086825-appb-000004

Claims (13)

  1. 一种制备1,2-二氯六氟环戊烯的方法，包括如下反应步骤：
    (1)、以环戊二烯为原料，在液相条件下与氯气发生反应得到四氯环戊烷；
    (2)、以四氯环戊烷为原料，在氟化催化剂存在的条件下，与氟化氢和氯气发生气相氯氟化反应而得到1,2-二氯六氟环戊烯。
  2. 根据权利要求1所述的方法，所述氟化催化剂为铬基催化剂。
  3. 根据权利要求2所述的方法，所述铬基催化剂由铬化合物和金属粉共混后高温焙烧而成，其铬化合物和金属粉的质量百分组成为95％～99.9％：0.1％～5％。
  4. 根据权利要求3所述的方法，其中铬化合物为三氧化二铬或氢氧化铬，金属粉为钨粉、钼粉中的一种或数种。
  5. 根据权利要求3所述的方法，所述高温焙烧条件为：在氮气氛围下于300℃～500℃进行焙烧6～15小时。
  6. 根据权利要求1所述的方法，所述铬基催化剂使用前需活化处理，所述活化处理为于60℃～450℃下在摩尔比为10：1的氮气与HF组成的混合气体中活化6～15小时。
  7. 根据权利要求1所述的方法，所述四氯环戊烷、氟化氢和氯气的摩尔比为1：5～20：5，反应压力0.1～1.5Ma，反应温度为300℃～500℃，接触时间为2s～30s。
  8. 根据权利要求1所述的方法，所述氯气与环戊二烯的摩尔比1～3：1，反应温度为0～40℃，反应时间为1-10h。
  9. 根据权利要求1所述的方法，所述环戊二烯的制备是以双环戊二烯为原料，以氮气或其它惰性气体作为稀释剂，加热裂解得到环戊二烯。
  10. 根据权利要求9所述的方法，所述稀释剂与双环戊二烯的摩尔比为1：0.5～3，反应压力0.1～1.5Ma，反应温度为300℃～450℃，接触时间为5s～30s。
  11. 根据权利要求10所述的方法，所述稀释剂与双环戊二烯的摩尔比为1：1～2，反应温度为330℃～370℃，反应压力0.1～1.5MPa，接触时间为10s～20s.
  12. 根据权利要求1所述的方法，所述氯气与环戊二烯的摩尔比1～1.5：1，反应温度为20～30℃，反应时间为3-7h。
  13. 根据权利要求1所述的方法，所述四氯环戊烷、氟化氢和氯气的摩尔比为1：10～15：5，反应压力0.1～1.5MPa，反应温度为370℃～450℃，接触时间为10s～20s。
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