WO2019047447A1 - 一种联产多种卤代烯烃和氟代烷烃的方法 - Google Patents

一种联产多种卤代烯烃和氟代烷烃的方法 Download PDF

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WO2019047447A1
WO2019047447A1 PCT/CN2018/000232 CN2018000232W WO2019047447A1 WO 2019047447 A1 WO2019047447 A1 WO 2019047447A1 CN 2018000232 W CN2018000232 W CN 2018000232W WO 2019047447 A1 WO2019047447 A1 WO 2019047447A1
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reactor
reaction
rectification column
hfo
trans
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PCT/CN2018/000232
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French (fr)
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洪江永
杨波
张彦
余国军
赵阳
欧阳豪
龚海涛
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浙江衢化氟化学有限公司
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Priority to EP18854525.5A priority Critical patent/EP3680225A4/en
Priority to KR1020197000450A priority patent/KR102115770B1/ko
Priority to JP2019502017A priority patent/JP6778812B2/ja
Priority to US16/337,407 priority patent/US10590050B2/en
Publication of WO2019047447A1 publication Critical patent/WO2019047447A1/zh

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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

  • This invention relates to a process for the preparation of fluoroolefins, fluorochloroolefins and fluoroalkanes, and more particularly to a process for the co-production of a plurality of halogenated olefins and fluoroalkanes.
  • HFO-1234ze 1,3,3,3-tetrafluoropropene
  • HFO-1234ze has two types, Z type and E type.
  • Z type has a boiling point of 9 ° C
  • E type has a boiling point of -19 ° C
  • GWP value is 6.
  • Z type can be used as a foaming agent
  • type E can be mixed with other materials as refrigeration. Use of the agent.
  • E type is the first choice for a new generation of environmentally friendly foaming agent. It is suitable for the foaming of polyurethane insulation materials in the fields of household appliances, building insulation, cold chain transportation and industrial insulation. It is CFC, HCFC, HFC. The best alternative blowing agent for other non-fluorocarbon blowing agents.
  • HFC-245fa and cyclopentane Compared with the existing foaming agent system (HFC-245fa and cyclopentane), it has better thermal conductivity and energy consumption than the same type of HFC-245fa and cyclopentane refrigerators. Reduced by 7% (compared to HFC-245fa system) and 12% (compared to cyclopentane system), and reduced overall energy consumption by 3% (compared to HFC-245fa system) and 7% (and Compared to the HFC-245fa system).
  • 1,1,1,3,3-pentafluoropropane is a safe fluorinated hydrocarbon compound for the ozone layer with zero ozone depletion potential (ODP) and low greenhouse effect (GWP).
  • ODP ozone depletion potential
  • GWP low greenhouse effect
  • Non-combustible, low toxicity currently used as a substitute for chlorotrifluoromethane (CFC-11) and 1,1,1-trichlorofluoroethane (HCFC-141b) blowing agent, also widely used in solvents, propellants , fire extinguishing agent and dry etchant.
  • the preparation method of HFO-1233zd is mainly composed of 1,1,1,3,3-pentachloropropane (HCC-240fa) and HF, and is synthesized by gas phase method. After the reaction, there are two types of Z type and E type. Less, so the Z-type is also isomerized to the E-type.
  • the preparation method of HFC-245fa mainly uses 1,1,1,3,3-pentachloropropane and anhydrous hydrogen fluoride as raw materials, mainly in liquid phase method, generally using Sb, Sn or Ti chloride as catalyst, reaction temperature Low, low energy consumption, but the equipment is seriously corroded, intermittent operation, and environmental protection issues are outstanding.
  • HFO-1234ze has two industrial preparation routes: 1,1,1,3,3-pentafluoropropane (HFC-245fa) gas phase de-HF and 1-chloro, 3,3,3-trifluoropropene Add HF method.
  • HFC-245fa 1,1,1,3,3-pentafluoropropane
  • 1-chloro, 3,3,3-trifluoropropene Add HF method 1,1,1,3,3-pentafluoropropane
  • Chinese Patent Publication No. CN103189338A published on July 3, 2013, invented name: joint production of trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoro An integrated process for propylene and 1,1,1,3,3-pentafluoropropane.
  • the invention discloses the combined production of trans-1-chloro-3,3,3-trifluoropropene, trans-1, starting from a single chlorinated hydrocarbon feedstock 1,1,1,3,3-pentachloropropane.
  • the process comprises a liquid or gas phase reaction/purification operation that directly produces a combination of trans-1-chloro-3,3,3-trifluoropropene.
  • trans-1-chloro-3,3,3-trifluoropropene is contacted with hydrogen fluoride (HF) in the presence of a catalyst to produce 1,1 with high conversion and selective reaction. 1,3,3-pentafluoropropane.
  • HF hydrogen fluoride
  • the third reactor is used to produce trans-1,3,3,3-tetrafluoropropene by contacting with a caustic solution in the liquid phase or dehydrofluorination of 245fa using a dehydrofluorination catalyst in the gas phase.
  • One or more purification processes may be performed after this operation to recover the trans-1,3,3,3-tetrafluoropropene product.
  • the shortcomings are liquid phase fluorination and liquid phase dehydrofluorination.
  • the reaction catalyst has a short life span, and the whole process waste liquid is high, and the environmental protection treatment cost is high.
  • the chemical process includes (a) 1,1,1,3,3-pentachloropropane (HCC-240fa) or its selected from 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloro
  • the propylene derivative reacts with excess anhydrous HF in a liquid phase reactor in the presence of a catalyst to produce HFO-1233zd, HFO-1234ze, HCFC-244fa (3-chloro-1, in a first reactor).
  • HFO-1233zd and HFO-1234ze are reacted with excess HCl in the presence of a catalyst in a second reactor to separately convert the two olefins to HCFC- 243fa and HCFC-244fa;
  • HCFC-243fa and HCFC-244fa are reacted in a third reactor on a dehydrochlorination catalyst or in a caustic solution to form HFO-1233zd and HFO-1234ze; and
  • HFO- 1233zd(Z) and HFO-1234ze(Z) were reacted in a fourth reactor in the presence of a catalyst to form HFO-1233zd(E) and HFO-1234ze(E), respectively.
  • the first and second steps of the route adopt a liquid phase reaction, the reaction catalyst has a short life span, and the entire process waste liquid is high, and the environmental protection treatment cost is high.
  • the chemical process involves the steps of: (1) reacting HCC-240fa with excess HF in a liquid phase catalytic reactor in a manner such that HFO-1233zd(E), HCFC-244fa and HCl are primarily combined; (2) The HCFC-244fa stream directly produces any of the three desired products; (3a) the HCFC-244fa stream can be dehydrochlorinated to produce the desired second product HFO-1234ze(E); and/or (3b) if More HFO-1233zd(E) is required to dehydrofluorinate HCFC-244fa to produce HFO-1233zd(E); and/or (3c) to further fluorinate HCFC-244fa to form HFC-245fa.
  • the mixture of the combined products is easily separated by conventional distillation, and then 3-chloro-1,1,1,3-tetrafluoropropane is dehydrochlorinated by contact with a caustic solution in the liquid phase or a dehydrochlorination catalyst in the gas phase. Production of trans-1,3,3,3-tetrafluoropropene.
  • the shortcomings are liquid phase fluorination and liquid phase dehydrofluorination.
  • the reaction catalyst has a short life span, and the whole process waste liquid is high, and the environmental protection treatment cost is high.
  • HFO-1234ze and HFC-245fa were prepared by two-stage gas phase fluorination using 1,1,1,3,3-pentachloropropane (HCC-240fa) and HF as raw materials.
  • the first reactor HCC-240fa reacts with HF to obtain HFC-245fa, HFO-1233zd, HF, HCl.
  • HFO-1234ze Z type and E type, HFO-1233zd, HFC-245fa and HCFC-244fa have been subjected to a series of separations to obtain HFC-245fa and HFO-1234ze.
  • the invention aims at a shortcoming of the prior art, and provides a method for co-production of a plurality of halogenated olefins and fluoroalkanes with simple process, large operation flexibility, low investment and low energy consumption.
  • the technical solution adopted by the present invention is: a method for co-production of a plurality of halogenated olefins and fluoroalkanes, comprising the following steps:
  • the first reactor reaction product obtained in the step (a) is introduced into the first rectification column to obtain a product trans-1-chloro-3,3,3-trifluoropropene and a first rectification column ;
  • step (c) mixing 30 to 70 wt% (wt%, mass%) of trans-1-chloro-3,3,3-trifluoropropene obtained in step (b) with hydrogen fluoride, and then entering the second reactor.
  • the reaction is carried out under the action of a catalyst having a molar ratio of hydrogen fluoride to trans-1-chloro-3,3,3-trifluoropropene of from 8 to 20:1, a reaction temperature of from 180 to 400 ° C, and a space velocity of 300. ⁇ 1000h -1 , obtaining a second reactor reaction product;
  • step (d) separating the second reactor reaction product obtained in the step (c) into a phase separator for separation to obtain an inorganic phase and an organic phase;
  • step (e) introducing the organic phase obtained in the step (d) into the second rectification column to obtain a trans-1,3,3,3-tetrafluoropropene product and a second rectification column bottom liquid;
  • the second rectification column bottom liquid obtained in the step (e) is introduced into the third rectification column to obtain a cis-1,3,3,3-tetrafluoropropene product and a third rectification column bottom liquid ;
  • the third rectification column bottom liquid obtained in the step (f) is introduced into the fourth rectification column to obtain a 1,1,1,3,3-pentafluoropropane product and a fourth rectification column bottom liquid.
  • the first rectification column bottom liquid described in step (b) can be recycled back to the first reactor.
  • the inorganic phase described in step (d) can be recycled back to the second reactor.
  • the fourth rectification column bottom liquid described in the step (g) can be recycled to the second reactor.
  • the reaction temperature in the step (a) is preferably from 250 to 320 ° C, and the space velocity is preferably from 500 to 800 h -1 .
  • the molar ratio of hydrogen fluoride to trans-1-chloro-3,3,3-trifluoropropene in the step (c) is preferably from 10 to 15:1, and the reaction temperature is preferably 200. ⁇ 350 ° C, the space velocity is preferably 500 to 700 h -1 .
  • the first catalyst described in the step (a) is alumina-supported chromium and magnesium, wherein the loading of chromium is preferably from 3 to 8 wt%, and the loading of magnesium is preferably from 1 to 3 wt%.
  • the second catalyst described in the step (c) preferably has a composition of chromium oxide of 73 to 90%, zinc oxide of 9.5 to 25%, and gallium oxide of 0.5 to 2% by mass.
  • the isomerization reaction occurs in the first reactor, and HFO-1233zd(Z) isomerized to HFO-1233zd(E). Since the isomerization is an equilibrium reaction, the conversion rate of temperature to HFO-1233zd(Z) The influence is large, the temperature is high, and the chlorine-containing olefin easily makes the catalyst carbon. Therefore, the reaction conditions in the first reactor of the present invention are controlled such that the reaction temperature is 200 to 400 ° C and the space velocity is 300 to 1000 h -1 ; and the reaction conditions are preferably: the reaction temperature is 250 to 320 ° C, and the space velocity is 500 to 800 h - 1 .
  • HFO-1233zd(E) and hydrogen fluoride (HF) are reacted in a second reactor to obtain a mixture containing HFC-245fa, HFO-1234ze(E) and HFO-1234ze(Z), and the reaction is as follows:
  • CF 3 CH CHF(HFO1234ze)+HF ⁇ CF 3 CH 2 CHF 2 (HFC-245fa)
  • HFO-1234ze is a mixture of Z-type and E-type, and the proportion of products can be adjusted according to market demand.
  • the addition of zinc increases the activity of the catalyst, gallium
  • the addition of the target product is improved to prevent the formation of other by-products, and the carbonation of the catalyst under high temperature conditions can also be suppressed.
  • the molar ratio has a certain influence on the selectivity of the product. The molar ratio increased, the content of HFC-245fa increased, and the content of HFO-1234ze decreased. The molar ratio is high, and excess HF can carry away heat, which is advantageous for prolonging the life of the catalyst.
  • the reaction conditions in the second reactor of the present invention are controlled such that the molar ratio of HF to HFO-1233zd(E) is 8 to 20:1, the reaction temperature is 180 to 400 ° C, and the space velocity is 300 to 1000 h -1 .
  • the conditions are preferably such that the molar ratio of HF to HFO-1233zd(E) is from 10 to 15:1, the reaction temperature is from 200 to 350 ° C, and the space velocity is from 500 to 700 h -1 .
  • the second reactor reaction product contains, in addition to the products HFC-245fa, HFO-1234ze(E) and HFO-1234ze(Z), the unreacted raw material HFO-1233zd(E) and excess HF, the boiling points of these substances. as follows:
  • the present invention designs a phase separator in the separation step to make the inorganic phase HF and The organic phase is effectively separated, and the temperature of the phase separator is controlled to be 0 to -30 ° C. 99% of the HF is separated and returned to the second reactor for recycling.
  • the first reactor catalyst of the present invention is alumina-supported chromium and magnesium, and can be prepared by a dipping method known in the art.
  • the chromium or magnesium metal chloride or nitrate is dissolved in water, and the alumina carrier is immersed to reach a certain level. After the loading, drying, calcination, and fluorination with HF give a catalyst.
  • the second reactor catalyst of the present invention comprises chromium oxide as a main component, and further comprises oxides of zinc and gallium, which can be prepared by a coprecipitation method known in the art: the chloride or nitrate of chromium, zinc and gallium is fixed. The ratio is dissolved in water and added with a precipitant.
  • the precipitant can be selected from a weak base such as ammonia (NH 3 ⁇ H 2 O) or ammonium carbonate ((NH 4 ) 2 ⁇ CO 3 ), then filtered, washed with water, dried, Calcination, granulation, tableting into a precursor, and fluorination to obtain a catalyst.
  • the first reactor and the second reactor in the present invention may be of an isothermal or adiabatic type.
  • the present invention has the following advantages:
  • the process is simple and the efficiency is high.
  • the invention adopts a two-step gas phase reaction, and the reaction efficiency is improved by optimizing the reaction process, the catalyst ratio, the reaction temperature, the space velocity and the like, and the energy consumption is remarkably reduced;
  • the invention adopts the gas phase production process, and the unreacted raw materials and intermediate products can be recycled into the reactor to continue the reaction, which significantly reduces the discharge of the three wastes;
  • a set of equipment can simultaneously produce trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, cis- Four kinds of products, 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, can flexibly adjust the proportion of products according to market needs, and significantly reduce equipment investment.
  • Figure 1 is a process flow diagram of the present invention.
  • 1 is the first reactor
  • 2 is the first rectification column
  • 3 is the second reactor
  • 4 is the phase separator
  • 5 is the second rectification column
  • 6 is the third rectification column
  • 7 For the fourth rectification column, 8 to 22 represent the process line.
  • the process of the present invention is shown in Figure 1.
  • the starting material cis-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(Z)) enters the first reactor 1 through line 8, and the reaction results in the inclusion of HFO- a mixture of 1233zd(E) and unreacted HFO-1233zd(Z), which is passed through line 9 to the first rectification column 2; the top of the first rectification column 2 is passed through line 10 to produce the product HFO-1233zd(E)
  • the unreacted HFO-1233zd (Z) is returned to the first reactor 1 via line 11; 30 to 70 wt% of HFO-1233zd (E) is passed through line 12 to the second reactor 3, and HF is passed through line 13
  • the second reactor after the reaction, obtains a mixture containing HFO-1234ze(E), HFO-1234ze(Z), HFC-245fa, unreacted HFO-1233zd(E), HCL and HF, and enter
  • the top component of the rectification column 5 is the product HFO-1234ze(E), which is produced through a line 17 containing a mixture of HFO-1234ze(Z), HFC-245fa, unreacted HFO-1233zd(E).
  • Line 18 enters third rectification column 6; the top portion of third rectification column 6 is product HFO-1234ze(Z), which is produced via line 19, which contains HFC-245fa and unreacted HFO-1233zd (E). Passing through line 20 to the fourth rectification column 7; the top portion of the fourth rectification column 7 is the product HFC-245fa, which is produced through line 21, and the unreacted HFO-1233zd (E) of the column is returned to the line 22 Second reactor 3.
  • HFO-1234ze(Z) which is produced via line 19, which contains HFC-245fa and unreacted HFO-1233zd (E).
  • the first reactor was heated to the reaction temperature, and HFO-1233zd (Z) was passed through to carry out the reaction, keeping the reactor space velocity at a set value, and after 1 hour of reaction, sampling and analysis from the first reactor outlet.
  • the reaction results at different temperatures and space velocities are shown in Table 1-1.
  • the second reactor is filled with Cr 2 O 3 /ZnO/GaO catalyst (per composition by mass: Cr 2 O 3 : 80%, ZnO: 19%, GaO: 1%), and the temperature is raised to a bed temperature of 350 ° C.
  • the first reactor was heated to the reaction temperature, and HFO-1233zd (Z) was passed through to carry out the reaction, keeping the reactor space velocity at a set value, and after 1 hour of reaction, sampling and analysis from the first reactor outlet.
  • the results of the reactions at different temperatures and space velocities are shown in Table 2-1.
  • the second reactor is filled with Cr 2 O 3 /ZnO/GaO catalyst (per composition by mass: Cr 2 O 3 : 90%, ZnO: 9.5%, GaO: 0.5%), and the temperature is raised to a bed temperature of 350 ° C.
  • HFO-1233zd (E) product having a purity of 99.9% is obtained, and 40 wt% of the HFO-1233zd (E) product is introduced into the second reactor together with the HF, and the reaction is carried out after 1 hour.
  • the second reactor outlet was sampled and analyzed. The results of the reaction at different temperatures, space velocities, hydrogen fluoride and trans-1-chloro-3,3,3-trifluoropropene were as shown in Table 2-2.
  • the first reactor was heated to the reaction temperature, and HFO-1233zd (Z) was passed through to carry out the reaction, keeping the reactor space velocity at a set value, and after 1 hour of reaction, sampling and analysis from the first reactor outlet.
  • the results of the reactions at different temperatures and space velocities are shown in Table 3-1.
  • the second reactor is filled with a Cr 2 O 3 /ZnO/GaO catalyst (per composition: Cr 2 O 3 : 73%, ZnO: 25%, GaO: 2%), and the temperature is raised to a bed temperature of 350 ° C.
  • a Cr 2 O 3 /ZnO/GaO catalyst per composition: Cr 2 O 3 : 73%, ZnO: 25%, GaO: 2%
  • hot spot temperature ⁇ 370 ° C when the hot spot temperature and the bed temperature are no longer elevated, continue to fluorinate for 20 hours, the end of fluorination.
  • the first reactor was heated to the reaction temperature, and HFO-1233zd (Z) was passed through to carry out the reaction, keeping the reactor space velocity at a set value, and after 1 hour of reaction, sampling and analysis from the first reactor outlet.
  • the results of the reactions at different temperatures and space velocities are shown in Table 4-1.
  • the second reactor is filled with a Cr 2 O 3 /ZnO/GaO catalyst (per composition: Cr 2 O 3 : 85%, ZnO: 14%, GaO: 1%), and the temperature is raised to a bed temperature of 350 ° C.
  • a Cr 2 O 3 /ZnO/GaO catalyst per composition: Cr 2 O 3 : 85%, ZnO: 14%, GaO: 1%
  • hot spot temperature ⁇ 370 ° C when the hot spot temperature and the bed temperature are no longer elevated, continue to fluorinate for 20 hours, the end of fluorination.

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Abstract

提供了一种联产多种卤代烯烃和氟代烷烃的方法，将顺式-1-氯-3,3,3-三氟丙烯通入第一反应器，在第一催化剂的作用下发生异构化反应，将反应产物精馏得到产品反式-1-氯-3,3,3-三氟丙烯；及将30～70wt％的反式-1-氯-3,3,3-三氟丙烯与氟化氢混合后进入第二反应器，在第二催化剂的作用下进行反应，得到第二反应器反应产物；将第二反应器反应产物进入相分离器进行分离，将得到的有机相精馏，得到反式-1,3,3,3-四氟丙烯、顺式-1,3,3,3-四氟丙烯和1,1,1,3,3-五氟丙烷产品。所述方法具有工艺简单，效率高，操作弹性大，投资少，能耗低的优点。

Description

一种联产多种卤代烯烃和氟代烷烃的方法 技术领域
本发明涉及含氟烯烃、含氟氯烯烃和含氟烷烃的制备方法，尤其涉及一种联产多种卤代烯烃和氟代烷烃的方法。
背景技术
1，3，3，3-四氟丙烯(HFO-1234ze)，属于氢氟烯烃HFO系列，是重要的第四代制冷剂和发泡剂。HFO-1234ze有Z型和E型两种，Z型沸点为9℃，E型沸点为-19℃，GWP值为6，Z型可作为发泡剂，E型可以和其它物质混配作为制冷剂使用。
1-氯，3，3，3-三氟丙烯(HFO-1233zd)，有Z型和E型两种，E型沸点19℃，Z型沸点为38℃，大气寿命26天，ODP值约为零，GWP值＜5，E型是新一代环保型发泡剂的首选，适用于家用电器、建筑保温、冷链运输和工业保温等领域聚氨酯隔热材料的发泡，是CFC、HCFC、HFC和其它非氟碳发泡剂的最佳替代发泡剂。与现有发泡剂体系(HFC-245fa和环戊烷)相比具有更为优异的导热系数和整机能耗水平，分别比相同型号的HFC-245fa以及环戊烷体系冰箱在导热系数方面降低7％(和HFC-245fa体系相比)和12％(和环戊烷体系相比)，并且在整机能耗方面降低了3％(和HFC-245fa体系相比)和7％(和HFC-245fa体系相比)。
1，1，1，3，3-五氟丙烷(HFC-245fa)是一种对大气臭氧层安全的氟化烃化合物，其臭氧耗损潜能值(ODP)为零，温室效应值(GWP)低，不燃、毒性低，目前主要用作三氟氯甲烷(CFC-11)和1，1，1-三氯氟乙烷(HCFC-141b)发泡剂的替代品，还广泛用在溶剂、喷射剂、灭火剂和干蚀刻剂。
HFO-1233zd的制备方法主要以1，1，1，3，3-五氯丙烷(HCC-240fa)和HF为原料，气相法合成，反应后有Z型和E型两种，目前Z型用途较少，所以还要将Z型异构化成E型。
HFC-245fa的制备方法主要以1，1，1，3，3-五氯丙烷和无水氟化氢为原料，以液相法为主，一般采用Sb、Sn或Ti的氯化物做催化剂，反应温度较低、能耗低，但设备腐蚀严 重，间歇式操作，环保问题突出。
HFO-1234ze具有工业化前景的制备路线主要有两种：1，1，1，3，3-五氟丙烷(HFC-245fa)气相脱HF法和1-氯，3，3，3-三氟丙烯加HF法。
中国专利公开号CN103189338A，公开日2013年7月3日，发明名称：联合生产反式-1-氯-3，3，3-三氟丙烯、反式-1，3，3，3-四氟丙烯和1，1，1，3，3-五氟丙烷的集成方法。该发明公开了自单一氯代烃原料1，1，1，3，3-五氯丙烷起始的联合生产反式-1-氯-3，3，3-三氟丙烯、反式-1，3，3，3-四氟丙烯和1，1，1，3，3-五氟丙烷的集成生产方法。该方法包括直接产生反式-1-氯-3，3，3-三氟丙烯的结合的液相或气相反应/提纯操作。在第二液相氟化反应器中，反式-1-氯-3，3，3-三氟丙烯与氟化氢(HF)在催化剂存在下接触以高转化率和选择性反应产生1，1，1，3，3-五氟丙烷。第三反应器用于通过在液相中与苛性碱液接触或在气相中使用脱氟化氢催化剂进行245fa的脱氟化氢以产生反式-1，3，3，3-四氟丙烯。在该操作后可以进行一个或多个提纯过程以回收该反式-1，3，3，3-四氟丙烯产物。不足之处是液相氟化和液相脱氟化氢，反应催化剂寿命短，整个工艺废液多，环保处理成本高。
中国专利公开号CN103476736A，公开日2013年12月25日，发明名称：联合生产1，1，1，3，3-五氟丙烷、反式-1-氯-3，3，3-三氟丙烯和反式-1，3，3，3-四氟丙烯的集成方法。该发明公开了制备1，1，1，3，3-五氟丙烷(HFC-245fa)、反式-1-氯-3，3，3-三氟丙烯(HFO-1233zd(E))和反式-1，3，3，3-四氟丙烯(HFO-1234ze(E))的充分集成的方法。化学过程包括(a)1，1，1，3，3-五氯丙烷(HCC-240fa)或其选自1，1，3，3-四氯丙烯和1，3，3，3-四氯丙烯的衍生物与过量无水HF在催化剂存在下在液相反应器中以一定方式反应以在第一反应器中联合产生HFO-1233zd、HFO-1234ze、HCFC-244fa(3-氯-1，1，1，3-四氟丙烷)和HFC-245fa；(b)HFO-1233zd和HFO-1234ze与过量HCl在催化剂存在下在第二反应器中反应以将这两种烯烃分别转化为HCFC-243fa和HCFC-244fa；(c)HCFC-243fa和HCFC-244fa在第三反应器中在脱氯化氢催化剂上或在苛性碱溶液中反应以形成HFO-1233zd和HFO-1234ze；和(d)HFO-1233zd(Z)和HFO-1234ze(Z)在催化剂存在下在第四反应器中反应以分别形成HFO-1233zd(E)和HFO-1234ze(E)。该路线第一、第二步采用液相反应，反应催化剂寿命短，整个工艺废液多，环保处理成本高。
中国专利公开号CN103429558A，公开日2013年12月4日，发明名称：联合生产反式-1-氯-3，3，3-三氟丙烯、反式-1，3，3，3-四氟丙烯和1，1，1，3，3-五氟丙烷的集成方法。该联合生产总体上是三步法。该化学过程涉及步骤：(1)使HCC-240fa与过量的HF在液 相催化反应器中反应，反应方式使得主要联合产生HFO-1233zd(E)、HCFC-244fa和HCl；(2)然后使HCFC-244fa料流直接生产三种所需产物中的任意产物；(3a)可以使HCFC-244fa料流脱氯化氢以生产所需第二产物HFO-1234ze(E)；和/或(3b)如果需要更多的HFO-1233zd(E)，可以使HCFC-244fa脱氟化氢以生产HFO-1233zd(E)；和/或(3c)可以使HCFC-244fa进一步氟化形成HFC-245fa。
中国专利公开号CN102918010A，公开日2015年2月25日，发明名称：联合生产反式-1-氯-3，3，3-三氟丙烯和反式-1，3，3，3-四氟丙烯的综合方法。公开的包括结合的液相反应和提纯操作的综合制造方法，其直接生产反式-1-氯-3，3，3-三氟丙烯和3-氯-1，1，1，3-四氟丙烷，其是制造反式-1，3，3，3-四氟丙烯的前体。联合产物的混合物容易地通过常规蒸馏分离，并且随后通过在液相中与苛性碱溶液接触或在气相中使用脱氯化氢催化剂将3-氯-1，1，1，3-四氟丙烷脱氯化氢以生产反式-1，3，3，3-四氟丙烯。不足之处是液相氟化和液相脱氟化氢，反应催化剂寿命短，整个工艺废液多，环保处理成本高。
中国专利公开号CN103880589A，公开日2014年6月25日，发明名称：一种联产制备HFO-1234ze和HFC-245fa的工艺。以1，1，1，3，3-五氯丙烷(HCC-240fa)和HF为原料，经两级气相氟化制备HFO-1234ze和HFC-245fa。第一反应器HCC-240fa和HF反应，得到HFC-245fa、HFO-1233zd、HF、HCl，分离HCl后将混合物流进入第二反应器，得到HFO-1234ze Z型和E型、HFO-1233zd、HFC-245fa和HCFC-244fa，经过一系列的分离得到HFC-245fa和HFO-1234ze。
发明内容
本发明针对现有技术的不足之处，提供一种工艺简单、操作弹性大，投资小、能耗低的联产多种卤代烯烃和氟代烷烃的方法。
为了解决上述技术问题，本发明采用的技术方案为：一种联产多种卤代烯烃和氟代烷烃的方法，包括以下步骤：
(a)将顺式-1-氯-3，3，3-三氟丙烯通入第一反应器，在第一催化剂的作用下发生异构化反应，反应温度为200～400℃，空速为300～1000h -1，得到第一反应器反应产物；
(b)将步骤(a)得到的第一反应器反应产物进入第一精馏塔，得到产品反式-1-氯-3，3，3-三氟丙烯和第一精馏塔塔釜液；
(c)将步骤(b)得到的30～70wt％(wt％，质量百分比)的反式-1-氯-3，3，3-三氟丙烯与氟化氢混合后进入第二反应器，在第二催化剂的作用下进行反应，所述氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比为8～20∶1，反应温度为180～400℃，空速为300～1000h -1，得到第二反应器反应产物；
(d)将步骤(c)得到的第二反应器反应产物进入相分离器进行分离，得到无机相和有机相；
(e)将步骤(d)得到的有机相进入第二精馏塔，得到反式-1，3，3，3-四氟丙烯产品和第二精馏塔塔釜液；
(f)将步骤(e)得到的第二精馏塔塔釜液进入第三精馏塔，得到顺式-1，3，3，3-四氟丙烯产品和第三精馏塔塔釜液；
(g)将步骤(f)得到的第三精馏塔塔釜液进入第四精馏塔，得到1，1，1，3，3-五氟丙烷产品和第四精馏塔塔釜液。
作为本发明的优选实施方式，可将步骤(b)中所述的第一精馏塔塔釜液循环回第一反应器。
作为本发明的优选实施方式，可将步骤(d)中所述的无机相循环回第二反应器。
作为本发明的优选实施方式，可将步骤(g)中所述的第四精馏塔塔釜液循环回第二反应器。
作为本发明的优选实施方式，步骤(a)中所述的反应温度优选为250～320℃，空速优选为500～800h -1。
作为本发明的优选实施方式，步骤(c)中所述的氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比优选为10～15∶1，反应温度优选为200～350℃，空速优选为500～700h -1。
作为本发明的优选实施方式，步骤(a)中所述的第一催化剂为氧化铝负载铬和镁，其中铬的负载量优选为3～8wt％，镁的负载量优选为1～3wt％。
作为本发明的优选实施方式，步骤(c)中所述的第二催化剂按质量百分比，其组成优选为：氧化铬73～90％，氧化锌9.5～25％，氧化镓0.5～2％。
本发明中，第一反应器发生异构化反应，HFO-1233zd(Z)异构化为HFO-1233zd(E)，由于异构化是平衡反应，温度对HFO-1233zd(Z)的转化率影响较大，温度高，含氯烯烃容易使催化剂结碳。因此，本发明第一反应器中反应条件控制为：反应温度为200～400℃，空速为300～1000h -1；反应条件优选为：反应温度250～320℃，空速为 500～800h -1。
本发明中，HFO-1233zd(E)和氟化氢(HF)在第二反应器中反应，得到含HFC-245fa、HFO-1234ze(E)和HFO-1234ze(Z)的混合物，反应如下：
CF 3CH＝CHCl(HFO-1233zd)+HF→CF 3CH＝CHF(HFO-1234ze)+HCl
CF 3CH＝CHF(HFO1234ze)+HF→CF 3CH 2CHF 2(HFC-245fa)
CF 3CH 2CHF 2(HFC-245fa)→CF 3CH＝CHF(HFO-1234ze)+HF
或者CF 3CH＝CHCl和HF反应得到CF 3CH 2CHFCl，然后脱氯化氢(HCl)得到CF 3CH＝CHF，CF 3CH＝CHCl和HF一步反应也可以得到CF 3CH 2CHF 2。
第二反应器中多个反应同时进行，受反应条件的影响较大。温度升高，HFC-245fa的含量下降，HFO-1234ze含量提高。低温对生成HFC-245fa是有利的，在温度210～230℃时，生成HFC-245fa的含量最高。温度升高，对生成HFO-1234ze是有利的，在温度330～350℃时，生成HFO-1234ze的含量最高，HFO-1234ze是Z型和E型的混合物，可根据市场需求调节产品比例。温度高，烯烃原料CF 3CH＝CHCl容易自聚，催化剂结碳而失活较快，催化剂以氧化铬为主要组成，还包括锌和镓的氧化物，锌的加入提高催化剂的活性，镓的加入提高目标产物的选择性，防止其它副产物的产生，还可以抑制高温条件下催化剂的结碳。摩尔比对产物的选择性有一定的影响。摩尔比提高，HFC-245fa的含量升高，HFO-1234ze含量下降。摩尔比高，过量的HF可以带走热量，对延长催化剂的寿命是有利的。因此，本发明第二反应器中反应条件控制为：HF与HFO-1233zd(E)的摩尔比为8～20∶1，反应温度为180～400℃，空速为300～1000h -1，反应条件优选为：HF与HFO-1233zd(E)的摩尔比为10～15∶1，反应温度为200～350℃，空速为500～700h -1。
第二反应器反应产物除了产品HFC-245fa、、HFO-1234ze(E)和HFO-1234ze(Z)外，还含有未反应的原料HFO-1233zd(E)和过量的HF，这几种物质沸点如下：
物质 沸点(℃)
HF 19.5
HFC-245fa 15.3
HFO-1234ze(E) -19
HFO-1234ze(Z) 9
HFO-1233zd(E) 19
由于HF、HFC-245fa和HFO-1233zd(E)的沸点很接近，HF过量较多需要循环利用，给后续的分离带来了难度，本发明在分离环节设计相分离器，使得无机相HF和有机相有效分离，控制相分离器的温度为0～-30℃，99％的HF得到分离，返回到第二反应器循环利用。
本发明第一反应器催化剂为氧化铝负载铬和镁，可采用本领域已知的浸渍法制备，将铬和镁金属的氯化盐或硝酸盐溶于水，浸泡氧化铝载体，达到一定的负载量后，干燥、焙烧、用HF氟化得到催化剂。
本发明第二反应器催化剂以氧化铬为主要组成，还包括锌和镓的氧化物，可采用本领域已知的共沉淀法制备：将铬、锌和镓的氯化盐或硝酸盐按一定的配比溶于水，加入沉淀剂反应，沉淀剂可以选择氨水(NH 3·H 2O)、碳酸铵((NH 4) 2·CO 3)等弱碱，然后经过滤、水洗、干燥、焙烧，造粒、压片成前驱体，氟化后制得催化剂。
本发明中的第一反应器和第二反应器可采用等温或绝热型式。
与现有技术相比，本发明具有以下优点：
1、工艺简单，效率高，本发明采用两步气相法反应，通过优化反应流程、催化剂配比、反应温度、空速等参数提高了反应效率，显著降低了能耗；
2、绿色环保，三废少，本发明采用气相法生产工艺，未反应完全的原料和中间产品可循环进入反应器继续反应，显著降低了三废排放；
3、投资小，操作弹性大，一套装置可同时生产反式-1-氯-3，3，3-三氟丙烯、反式-1，3，3，3-四氟丙烯、顺式-1，3，3，3-四氟丙烯和1，1，1，3，3-五氟丙烷四种产品，可以根据市场需要灵活调整产品比例，显著降低了设备投资。
附图说明
图1为本发明的工艺流程图。
如图所示：1为第一反应器，2为第一精馏塔，3为第二反应器，4为相分离器，5为第二精馏塔，6为第三精馏塔，7为第四精馏塔，8～22代表流程管线。
具体实施方式
本发明流程如图1所示，原料顺式-1-氯-3，3，3-三氟丙烯(HFO-1233zd(Z))通过管线8进入第一反应器1，反应后得到含有HFO-1233zd(E)和未反应的HFO-1233zd(Z)的混合物，将其通过管线9进入第一精馏塔2；第一精馏塔2塔顶通过管线10采出产品HFO-1233zd(E)，塔釜未反应的HFO-1233zd(Z)通过管线11返回到第一反应器1；将30～70wt％的HFO-1233zd(E)通过管线12进入第二反应器3，HF通过管线13进入第二反应器，反应后得到含有HFO-1234ze(E)、HFO-1234ze(Z)、HFC-245fa、未反应的HFO-1233zd(E)、HCL和HF的混合物，通过管线14进入相分离器4；相分离器4上层含有大量HF和少量有机物的无机相通过管线15返回到第二反应器3，下层含有大量有机物和少量HF的有机相通过管线16进入第二精馏塔5，第二精馏塔5塔顶组分为产品HFO-1234ze(E)，通过管线17采出，塔釜含有HFO-1234ze(Z)、HFC-245fa、未反应的HFO-1233zd(E)的混合物通过管线18进入第三精馏塔6；第三精馏塔6塔顶组分为产品HFO-1234ze(Z)，通过管线19采出，塔釜含有HFC-245fa和未反应的HFO-1233zd(E)通过管线20进入第四精馏塔7；第四精馏塔7塔顶组分为产品HFC-245fa，通过管线21采出，塔釜未反应的HFO-1233zd(E)通过管线22返回到第二反应器3。
以下结合实施例对本发明做进一步详细描述，但本发明不仅仅局限于以下实施例。
实施例1
将200ml Al 2O 3/Cr/Mg(按质量百分比，组成为：Al 2O 3：95％；Cr 2O 3：4％；MgO：1％)催化剂装入第一反应器，升温到床层温度330℃，通入HF进行活化，HF流量：100g/h，热点温度＜380℃，当热点温度和床层温度一样却不再升高时，氟化结束。
第一反应器升温到反应温度，通入HFO-1233zd(Z)进行反应，保持反应器空速在设定值，反应1小时后从第一反应器出口取样分析。不同温度和空速下的反应结果如表1-1。
表1-1：实施例1第一反应器出口有机物组成
Figure PCTCN2018000232-appb-000001
Figure PCTCN2018000232-appb-000002
第二反应器装填Cr 2O 3/ZnO/GaO催化剂(按质量百分比，组成为：Cr 2O 3：80％，ZnO：19％，GaO：1％)，升温到床层温度350℃，通入HF进行活化，HF流量：100g/h，热点温度＜370℃，当热点温度和床层温度一样却不再升高时，继续氟化20小时，氟化结束。
将第一反应器出口混合物分离后，得到纯度99.9％的HFO-1233zd(E)产品，将30wt％的HFO-1233zd(E)产品和HF一起进入第二反应器进行反应，反应1小时后从第二反应器出口取样分析，不同温度、空速、氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比下的反应结果如表1-2。
表1-2：实施例1第二反应器出口有机物组成
Figure PCTCN2018000232-appb-000003
实施例2
将200ml Al 2O 3/Cr/Mg(按质量百分比，组成为：Al 2O 3：90％；Cr 2O 3：8％；MgO：2％)催化剂装入第一反应器，升温到床层温度330℃，通入HF进行活化，HF流量：100g/h，热点温度＜380℃，当热点温度和床层温度一样却不再升高时，氟化结束。
第一反应器升温到反应温度，通入HFO-1233zd(Z)进行反应，保持反应器空速在设定值，反应1小时后从第一反应器出口取样分析。不同温度和空速下的反应结果如表2-1。
表2-1：实施例2第一反应器出口有机物组成
Figure PCTCN2018000232-appb-000004
第二反应器装填Cr 2O 3/ZnO/GaO催化剂(按质量百分比，组成为：Cr 2O 3：90％，ZnO：9.5％，GaO：0.5％)，升温到床层温度350℃，通入HF进行活化，HF流量：100g/h，热点温度＜370℃，当热点温度和床层温度一样却不再升高时，继续氟化20小时，氟化结束。
将第一反应器出口混合物分离后，得到纯度99.9％的HFO-1233zd(E)产品，将40wt％的HFO-1233zd(E)产品和HF一起进入第二反应器进行反应，反应1小时后从第二反应器出口取样分析，不同温度、空速、氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比下的反应结果如表2-2。
表2-2：实施例2第二反应器出口有机物组成
Figure PCTCN2018000232-appb-000005
Figure PCTCN2018000232-appb-000006
实施例3
将200ml Al 2O 3/Cr/Mg(按质量百分比，组成为：Al 2O 3：93％；Cr 2O 3：6％；MgO：1％)催化剂装入第一反应器，升温到床层温度330℃，通入HF进行活化，HF流量：100g/h，热点温度＜380℃，当热点温度和床层温度一样却不再升高时，氟化结束。
第一反应器升温到反应温度，通入HFO-1233zd(Z)进行反应，保持反应器空速在设定值，反应1小时后从第一反应器出口取样分析。不同温度和空速下的反应结果如表3-1。
表3-1：实施例3第一反应器出口有机物组成
Figure PCTCN2018000232-appb-000007
第二反应器装填Cr 2O 3/ZnO/GaO催化剂(按质量百分比，组成为：Cr 2O 3：73％，ZnO：25％，GaO：2％)，升温到床层温度350℃，通入HF进行活化，HF流量：100g/h，热点温度＜370℃，当热点温度和床层温度一样却不再升高时，继续氟化20小时，氟化结束。
将第一反应器出口混合物分离后，得到纯度99.9％的HFO-1233zd(E)产品，将50wt％的HFO-1233zd(E)产品和HF一起进入第二反应器进行反应，反应1小时后从第二反应器出口取样分析，不同温度、空速、氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比下的反应结果如表3-2。
表3-2：实施例3第二反应器出口有机物组成
Figure PCTCN2018000232-appb-000008
实施例4
将200ml Al 2O 3/Cr/Mg(按质量百分比，组成为：Al 2O 3：90％；Cr：7％；Mg：3％)催化剂装入第一反应器，升温到床层温度330℃，通入HF进行活化，HF流量：100g/h，热点温度＜380℃，当热点温度和床层温度一样却不再升高时，氟化结束。
第一反应器升温到反应温度，通入HFO-1233zd(Z)进行反应，保持反应器空速在设定值，反应1小时后从第一反应器出口取样分析。不同温度和空速下的反应结果如表4-1。
表4-1：实施例4第一反应器出口有机物组成
Figure PCTCN2018000232-appb-000009
第二反应器装填Cr 2O 3/ZnO/GaO催化剂(按质量百分比，组成为：Cr 2O 3：85％，ZnO：14％，GaO：1％)，升温到床层温度350℃，通入HF进行活化，HF流量：100g/h， 热点温度＜370℃，当热点温度和床层温度一样却不再升高时，继续氟化20小时，氟化结束。
将第一反应器出口混合物分离后，得到纯度99.9％的HFO-1233zd(E)产品，将70wt％的HFO-1233zd(E)产品和HF一起进入第二反应器进行反应，反应1小时后从第二反应器出口取样分析，不同温度、空速、氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比下的反应结果如表4-2。
表4-2：实施例4第二反应器出口有机物组成
Figure PCTCN2018000232-appb-000010

Claims (8)

  1. 一种联产多种卤代烯烃和氟代烷烃的方法，其特征在于包括以下步骤：
    (a)将顺式-1-氯-3，3，3-三氟丙烯通入第一反应器，在第一催化剂的作用下发生异构化反应，反应温度为200～400℃，空速为300～1000h -1，得到第一反应器反应产物；
    (b)将步骤(a)得到的第一反应器反应产物进入第一精馏塔，得到产品反式-1-氯-3，3，3-三氟丙烯和第一精馏塔塔釜液；
    (c)将步骤(b)得到的30～70wt％的反式-1-氯-3，3，3-三氟丙烯与氟化氢混合后进入第二反应器，在第二催化剂的作用下进行反应，所述氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比为8～20∶1，反应温度为180～400℃，空速为300～1000h -1，得到第二反应器反应产物；
    (d)将步骤(c)得到的第二反应器反应产物进入相分离器进行分离，得到无机相和有机相；
    (e)将步骤(d)得到的有机相进入第二精馏塔，得到反式-1，3，3，3-四氟丙烯产品和第二精馏塔塔釜液；
    (f)将步骤(e)得到的第二精馏塔塔釜液进入第三精馏塔，得到顺式-1，3，3，3-四氟丙烯产品和第三精馏塔塔釜液；
    (g)将步骤(f)得到的第三精馏塔塔釜液进入第四精馏塔，得到1，1，1，3，3-五氟丙烷产品和第四精馏塔塔釜液。
  2. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于将步骤(b)中所述的第一精馏塔塔釜液循环回第一反应器。
  3. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于将步骤(d)中所述的无机相循环回第二反应器。
  4. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于将步骤(g)中所述的第四精馏塔塔釜液循环回第二反应器。
  5. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于步骤(a)中所述的反应温度为250～320℃，空速为500～800h -1。
  6. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于步骤(c)中所述的氟化氢与反式-1-氯-3，3，3-三氟丙烯的摩尔比为10～15∶1，反应温度为200～350 ℃，空速为500～700h -1。
  7. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于步骤(a)中所述的第一催化剂为氧化铝负载铬和镁，其中铬的负载量为3～8wt％，镁的负载量为1～3wt％。
  8. 根据权利要求1所述的联产多种卤代烯烃和氟代烷烃的方法，其特征在于步骤(c)中所述的第二催化剂按质量百分比，其组成为：氧化铬73～90％，氧化锌9.5～25％，氧化镓0.5～2％。
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JP2019530639A (ja) 2019-10-24
CN107522592B (zh) 2020-06-02
EP3680225A4 (en) 2021-06-09
KR102115770B1 (ko) 2020-05-27
JP6778812B2 (ja) 2020-11-04
KR20190040181A (ko) 2019-04-17
US20200031742A1 (en) 2020-01-30
US10590050B2 (en) 2020-03-17
CN107522592A (zh) 2017-12-29

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