A method for preparing E-1-chloro-3,3,3-trifluoropropene

Abstract

The present application discloses a method for preparing E-1-chloro-3,3,3-trifluoropropene, which comprises: in the presence of a catalyst, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene and HF undergo a gas phase fluorine-chlorine exchange reaction to obtain E-1-chloro-3,3,3-trifluoropropene. The present application uses E-1-chloro-3,3,3-trifluoropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene as raw materials and synthesizes E-1-chloro-3,3,3-trifluoropropene through a gas-phase fluorine-chlorine exchange reaction. Using the method of the present application, the selectivity of E-1-chloro-3,3,3-trifluoropropene is high, the single-pass conversion rate of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene is also high, and it is also easier to achieve gas-phase continuous production.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a method for preparing E-1-chloro-3,3,3-trifluoropropene. Background Art

[0002] Among the many synthetic routes for E-1-chloro-3,3,3-trifluoropropene, the fluorine-chlorine exchange reaction of halogenated organic raw materials is one of the important routes. To date, there are few reports on fluorine-chlorine exchange reactions using E-1-chloro-3,3,3-trifluoropropene or Z-1,3,3,3-tetrachloropropene as raw materials. Only Patent Document 1 discloses a process for a liquid-phase fluorine-chlorine exchange reaction, which includes a liquid-phase fluorine-chlorine exchange reaction between hydrogen fluoride and 1,3,3,3-tetrachloropropene in a molar ratio of 3-4:1, catalyzed by antimony pentafluoride (the mass ratio of antimony pentafluoride to 1,3,3,3-tetrachloropropene is 1-1.2:1), at a reaction temperature of 120-125° C., a reaction time of 4-6 hours, and a reaction pressure of less than 6.5 MPa. The reaction results in a 1,3,3,3-tetrachloropropene conversion rate of 99.8%, and a combined selectivity of 99.8% for both E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene.

[0003] The above-mentioned existing technologies are all intermittent processes, using liquid-phase fluorination catalyst antimony pentafluoride, which requires strict anhydrous operation and is difficult to recycle and reuse. The reaction pressure is too high, which easily generates industrial waste and is difficult to achieve continuous large-scale production.

[0004] Prior art literature

[0005] Patent document 1CN105152850A public text Summary of the Invention

[0006] In order to overcome the deficiencies in the prior art, the present application provides a method for preparing E-1-chloro-3,3,3-trifluoropropene by utilizing a gas-phase fluorine-chlorine exchange reaction. The method of the present application has the characteristics of high selectivity and high conversion rate, and can realize continuous large-scale production.

[0007] The specific technical solutions of this application are as follows:

[0008] 1. A method for preparing E-1-chloro-3,3,3-trifluoropropene, characterized in that it comprises:

[0009] In the presence of a catalyst, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene undergoes a gas phase fluorine-chlorine exchange reaction with HF to obtain E-1-chloro-3,3,3-trifluoropropene.

[0010] 2. The method according to item 1, characterized in that the reaction temperature is 100 to 400°C.

[0011] 3. The method according to item 1, characterized in that the reaction temperature is 150 to 350°C.

[0012] 4. The method according to item 1, characterized in that the reaction temperature is 200-300°C.

[0013] 5. The method according to any one of items 1 to 4, characterized in that the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4 to 30.

[0014] 6. The method according to any one of items 1 to 4, characterized in that the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4 to 15.

[0015] 7. The method according to any one of items 1 to 4, characterized in that the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:6 to 10.

[0016] 8. The method according to any one of items 1 to 4, characterized in that the reaction time is 1 to 200 s.

[0017] 9. The method according to any one of items 1 to 4, characterized in that the reaction time is 1 to 150 seconds.

[0018] 10. The method according to any one of items 1 to 4, characterized in that the reaction time is 1 to 10 seconds.

[0019] 11. The method according to any one of items 1 to 4, wherein the reaction pressure is 0.1 to 0.5 MPa.

[0020] 12. The method according to any one of items 1 to 4, characterized in that the catalyst is selected from any one or more of aluminum fluoride, magnesium fluoride, iron fluoride, calcium fluoride, chromium fluoride, tungsten oxyfluoride, molybdenum oxyfluoride, and activated carbon.

[0021] 13. The method according to any one of items 1 to 4, characterized in that the catalyst is any one of tungsten oxyfluoride, molybdenum oxyfluoride, chromium fluoride, and activated carbon.

[0022] 14. The method according to any one of items 1 to 4, characterized in that the method is a method for continuously preparing E-1-chloro-3,3,3-trifluoropropene in the gas phase.

[0023] Effects of the Invention

[0024] The present application uses E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene as raw materials, and carries out a gas-phase fluorine-chlorine exchange reaction under catalyst conditions. The selectivity of E-1-chloro-3,3,3-trifluoropropene is high, and the single-pass conversion rate of the reaction raw materials is also high, which makes it easier to achieve gas-phase continuous production. The present application further uses a gas-phase independent circulation continuous process to independently circulate the incompletely reacted materials, so that the initial raw materials can be almost completely converted into the target product, and the target product and by-products are finally extracted from the process system, thereby not generating liquid waste and waste gas, and realizing green production. The method of the present application has the characteristics of high conversion rate and high selectivity, and is easy to achieve continuous large-scale production, and can co-produce Z-1-chloro-3,3,3-trifluoropropene and E-1-chloro-3,3,3-trifluoropropene. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a process flow chart for preparing E-1-chloro-3,3,3-trifluoropropene in this application.

[0026] Explanation of symbols

[0027] 1 Pipeline LA 2 Pipeline LG 3 Reactor

[0028] 4 Pipeline LB 5 First distillation column 6 Pipeline LI

[0029] 7-line LC 8-phase splitter 9-line LF

[0030] 10 Pipeline LD 11 Second distillation column 12 Pipeline LH

[0031] 13 Pipeline LE 14 Third distillation column 15 Pipeline LJ

[0032] 16 pipeline LK DETAILED DESCRIPTION

[0033] The present application is described in detail below. Although specific embodiments of the present application are shown, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0034] It should be noted that the terms "including" and "comprising" used throughout the specification and claims are open-ended and should be interpreted as "including but not limited to." The specification subsequently describes preferred embodiments of the present application. However, such descriptions are intended to provide a general understanding of the specification and are not intended to limit the scope of the present application. The scope of protection of the present application shall be determined by the appended claims.

[0035] The present application provides a method for preparing E-1-chloro-3,3,3-trifluoropropene, which comprises:

[0036] In the presence of a catalyst, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene undergoes a gas phase fluorine-chlorine exchange reaction with HF to obtain E-1-chloro-3,3,3-trifluoropropene.

[0037] The reaction route of the preparation method of this application is as follows:

[0038]

[0039] The present application uses E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene and HF as reaction raw materials, and promotes the fluorination of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene in the presence of a catalyst to obtain E-1-chloro-3,3,3-trifluoropropene.

[0040] In one embodiment, the reaction temperature is 100-400°C, for example, 100°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 25 0℃, 255℃, 260℃, 265℃, 270℃, 275℃, 280℃, 285℃, 290℃, 295℃, 300℃, 305℃, 310℃, 315℃, 320℃, 325℃, 330℃, 335℃, 340℃, 345℃, 350℃, 355℃, 360℃, 365℃, 370℃, 375℃, 380℃, 385℃, 390℃, 395℃, 400℃, etc., preferably 150-350℃, more preferably 200-300℃.

[0041] In a specific embodiment, the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, for example, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, etc., preferably 1:4-15, and more preferably 1:6-10. In the present application, the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF refers to the ratio of the total molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to the molar ratio of HF.

[0042] In a specific embodiment, the reaction time is 1 to 200 s, for example, 1 s, 2 s, 4 s, 5 s, 6 s, 8 s, 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, 180 s, 190 s, 200 s, etc., preferably 1 to 150 s, more preferably 1 to 10 s. The reaction time of the present application, also referred to as the contact time, refers to the single-pass reaction time of the raw materials and the catalyst.

[0043] In one embodiment, the reaction pressure is 0.1-0.5 MPa, for example, 0.1 MPa, 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, normal pressure, etc.

[0044] Any catalyst known in the art that can promote the fluorination of E-1,3,3,3-tetrachloropropene and / or Z-1,3,3,3-tetrachloropropene and / or 1,1,3,3-tetrachloropropene can be used in this method. In one embodiment, the suitable catalyst is selected from any one or more of aluminum fluoride, magnesium fluoride, iron fluoride, calcium fluoride, chromium fluoride, tungsten oxyfluoride, molybdenum oxyfluoride, and activated carbon, preferably any one of tungsten oxyfluoride, molybdenum oxyfluoride, chromium fluoride, and activated carbon.

[0045] In one embodiment, the preparation method of the metal fluoride or metal oxyfluoride in the catalyst is as follows:

[0046] (1) dissolving a soluble salt of a metal in water, then adding a precipitant dropwise to completely precipitate the metal ions, adjusting the pH value to 7.0-9.0, allowing the metal ions to fully precipitate under stirring conditions, aging for 12-36 hours, filtering the formed slurry, and then drying at 100-250° C. for 6-24 hours, crushing the obtained solid, and pressing it into a shape to obtain a catalyst precursor; wherein the soluble salt of the metal is any one or more of molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride, and chlorides, nitrates, or acetates of Al, Mg, Fe, Ca, and Cr, and the precipitant is at least one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide, and rubidium hydroxide.

[0047] (2) The obtained catalyst precursor is calcined at 300-500°C under a nitrogen atmosphere for 6-24 hours, and then activated at 200-400°C with a mixture of hydrogen fluoride and nitrogen at a molar ratio of 1:2 for 12-24 hours to obtain a catalyst. Aluminum fluoride, magnesium fluoride, iron fluoride, calcium fluoride, chromium fluoride, tungsten oxyfluoride, and molybdenum oxyfluoride can be prepared according to the above method.

[0048] In a specific embodiment, the activated carbon in the catalyst can be commercially available, such as coconut shell charcoal, wood charcoal, coal charcoal, etc.

[0049] In one specific embodiment, the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-400° C., the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, and the contact time is 1-200 s.

[0050] In one specific embodiment, the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 150-350° C., the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-15, and the contact time is 1-150 s.

[0051] In one specific embodiment, the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 200-300° C., the molar ratio of E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:6-10, and the contact time is 1-10 seconds.

[0052] In a specific embodiment, the reaction temperature is 100-400° C., preferably 150-350° C., more preferably 200-300° C., the molar ratio of the E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, preferably 1:4-15, more preferably 1:6-10, and the reaction time is 1-200 s, preferably 1-150 s, more preferably 1-10 s.

[0053] In a specific embodiment, the reaction temperature is 100-400° C., preferably 150-350° C., more preferably 200-300° C., the molar ratio of the E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, preferably 1:4-15, more preferably 1:6-10, and the reaction pressure is 0.1-0.5 MPa.

[0054] In a specific embodiment, the reaction temperature is 100-400° C., preferably 150-350° C., more preferably 200-300° C., the molar ratio of the E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, preferably 1:4-15, more preferably 1:6-10, the reaction pressure is 0.1-0.5 MPa, and the catalyst is selected from any one or more of aluminum fluoride, magnesium fluoride, iron fluoride, calcium fluoride, chromium fluoride, tungsten oxyfluoride, molybdenum oxyfluoride, and activated carbon, preferably any one of tungsten oxyfluoride, molybdenum oxyfluoride, chromium fluoride, and activated carbon.

[0055] In one embodiment, the reaction temperature is 100-400° C., preferably 150-350° C., more preferably 200-300° C., the reaction time is 1-200 s, preferably 1-150 s, more preferably 1-10 s, and the reaction pressure is 0.1-0.5 MPa.

[0056] In a specific embodiment, the reaction temperature is 100-400°C, preferably 150-350°C, more preferably 200-300°C, the reaction time is 1-200s, preferably 1-150s, more preferably 1-10s, and the reaction pressure is 0.1-0.5MPa. The catalyst is selected from any one or more of aluminum fluoride, magnesium fluoride, iron fluoride, calcium fluoride, chromium fluoride, tungsten oxyfluoride, molybdenum oxyfluoride, and activated carbon, preferably any one of tungsten oxyfluoride, molybdenum oxyfluoride, chromium fluoride, and activated carbon.

[0057] In one specific embodiment, the reaction temperature is 100-400° C., preferably 150-350° C., more preferably 200-300° C., the molar ratio of the E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, preferably 1:4-15, more preferably 1:6-10, the reaction time is 1-200 s, preferably 1-150 s, more preferably 1-10 s, and the reaction pressure is 0.1-0.5 MPa.

[0058] In a specific embodiment, the reaction temperature is 100-400° C., preferably 150-350° C., more preferably 200-300° C., the molar ratio of the E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene to HF is 1:4-30, preferably 1:4-15, more preferably 1:6-10, the reaction time is 1-200 s, preferably 1-150 s, more preferably 1-10 s, and the reaction pressure is 0.1-0.5 MPa. The catalyst is selected from any one or more of aluminum fluoride, magnesium fluoride, iron fluoride, calcium fluoride, chromium fluoride, tungsten oxyfluoride, molybdenum oxyfluoride, and activated carbon, preferably any one of tungsten oxyfluoride, molybdenum oxyfluoride, chromium fluoride, and activated carbon.

[0059] The present application also provides a device for preparing E-1-chloro-3,3,3-trifluoropropene, such as Figure 1 As shown, it includes: a reactor 3, a first distillation column 5, a phase separator 8, a second distillation column 11, a pipeline LA1, a pipeline LB 4, a pipeline LC 7, a pipeline LD 10, a pipeline LE 13, a pipeline LF 9 and a pipeline LG 2; wherein,

[0060] The reactor 3 is filled with a catalyst and has a feed inlet and a product outlet. HF, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene flow into the reactor 3 from the feed inlet and undergo a gas-phase fluorine-chlorine exchange reaction in the presence of the catalyst. After the reaction, a product stream containing E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, hydrogen chloride, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene, and HF flows out from the product outlet.

[0061] The first distillation tower 5 has: an inlet 1, a bottom outlet 1 and a top outlet 1, and the product stream enters the first distillation tower 5 from the inlet 1 through the pipeline LB 4 for separation to remove hydrogen chloride;

[0062] The phase separator 8 has: a phase separator 8 inlet, an inorganic phase outlet, and an organic phase outlet. The material flow out of the bottom outlet of the first distillation tower 5 enters the phase separator 8 from the phase separator 8 inlet through the pipeline LC 7 and continues to separate to obtain an inorganic phase and an organic phase. The inorganic phase flows out from the inorganic phase outlet, and the organic phase flows out from the organic phase outlet.

[0063] The second distillation tower 11 has: an inlet 2, a bottom outlet 2 and a top outlet 2. The organic phase enters the second distillation tower 11 from the inlet 2 through the pipeline LD 10 for further separation, and a stream containing E-1-chloro-3,3,3-trifluoropropene flows out of the top outlet 2.

[0064] The pipeline LA1 is connected to the raw material supply end, the pipeline LE 13 is connected to the second bottom outlet of the second distillation tower 11, the pipeline LF 9 is connected to the inorganic phase outlet of the phase separator 8, and the pipeline LA1, pipeline LE 13 and pipeline LF 9 are connected to the raw material inlet of the reactor 3 through pipeline LG 2, so that the raw material from the raw material supply end, the inorganic phase and the material flow out of the second bottom outlet flow into the reactor 3 together.

[0065] In one embodiment, Figure 1 As shown, the device of the present application further includes a third distillation column 14 and a pipeline LH12; wherein,

[0066] The third distillation tower 14 has an inlet three, a bottom outlet three, and a top outlet three. The stream flowing out of the top outlet two enters the third distillation tower 14 from the inlet three through the pipeline LH12 for further separation. The top outlet three flows out E-1-chloro-3,3,3-trifluoropropene, and the bottom outlet three flows out Z-1-chloro-3,3,3-trifluoropropene.

[0067] In a specific embodiment, in the device of the present application, hydrogen chloride flows out from the top outlet of the first distillation tower 5, and E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, HF, E-1,3,3,3-tetrachloropropene and / or Z-1,3,3,3-tetrachloropropene and / or 1,1,3,3-tetrachloropropene flows out from the bottom outlet of the first distillation tower 5;

[0068] The inorganic phase contains HF, the organic phase contains E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene, the inorganic phase flows out through the inorganic phase outlet, and the organic phase flows out through the organic phase outlet;

[0069] The second top outlet of the second distillation tower 11 flows out E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene, and the second bottom outlet of the second distillation tower 11 flows out E-1,3,3,3-tetrachloropropene and / or Z-1,3,3,3-tetrachloropropene and / or 1,1,3,3-tetrachloropropene.

[0070] The present application also provides a method for preparing E-1-chloro-3,3,3-trifluoropropene using any of the aforementioned devices.

[0071] In a specific embodiment, the E-1-chloro-3,3,3-trifluoropropene product prepared by the method of the present application can be further subjected to deacidification, dehydration, and distillation to obtain a high-purity E-1-chloro-3,3,3-trifluoropropene product.

[0072] In a specific embodiment, the method of the present application comprises the following steps: E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene and HF are passed through pipeline LA1, together with E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene recycled through pipeline LE13, and HF recycled through pipeline LF9, and passed through pipeline LG2 into reactor 3 filled with catalyst for gas-phase fluorine-chlorine exchange reaction, and the reaction product stream is E-1-chloro-3,3,3-trifluoropropene. , Z-1-chloro-3,3,3-trifluoropropene, hydrogen chloride and unreacted E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene and HF, the reaction product flows through pipeline LB4 into the first distillation tower 5 for separation; the top component of the first distillation tower 5 is hydrogen chloride, and the bottom component is E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene and HF, the top component is passed through pipeline LB4. The LI6 extraction system can be further separated, purified, and dehydrated to obtain high-purity HCl, or it can be configured into hydrochloric acid of different concentrations for sale; the bottom component of the first distillation tower 5 enters the phase separator 8 through the pipeline LC7 for further separation; the upper layer of the phase separator 8 is an inorganic phase rich in HF, and the lower layer is an organic phase rich in E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene or / and 1,1,3,3-tetrachloropropene. The inorganic phase is circulated to the reactor 3 through the pipeline LF9 and the pipeline LG2 to continue the reaction, and the organic phase is The product enters the second distillation tower 11 through the pipeline LD10 for further separation; the top component of the second distillation tower 11 is E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene, and the bottom component is E-1,3,3,3-tetrachloropropene and / or Z-1,3,3,3-tetrachloropropene and / or 1,1,3,3-tetrachloropropene. The bottom component is circulated into the reactor 3 through the pipeline LE13 and the pipeline LG2 for further reaction, and the top component is entered into the third distillation tower 14 through the pipeline LH12 for further separation; the top component of the third distillation tower 14 is E-1-chloro-3,3,3-trifluoropropene, which is recycled through the pipeline LJ 15 is extracted, and the bottom component is Z-1-chloro-3,3,3-trifluoropropene, which is extracted through pipeline LK16. The top component can obtain high-purity E-1-chloro-3,3,3-trifluoropropene product through subsequent deacidification, dehydration and distillation. The bottom component can obtain high-purity Z-1-chloro-3,3,3-trifluoropropene product through subsequent deacidification, dehydration and distillation.

[0073] The type of reactor used for the reaction in this application is not critical, and a tubular reactor, a fluidized bed reactor, etc. can be used. In addition, an adiabatic reactor or an isothermal reactor can also be used.

[0074] The gas-phase reaction process of the present application is a gas-phase independent circulation continuous process. Due to the significant difference in boiling points between the raw materials and the reaction products, distillation in a distillation tower can effectively separate the raw materials and products. The unreacted raw materials E-1,3,3,3-tetrachloropropene and / or Z-1,3,3,3-tetrachloropropene and / or 1,1,3,3-tetrachloropropene, as well as HF, are continuously circulated to the reactor to continue the reaction, while the product E-1-chloro-3,3,3-trifluoropropene and the byproduct Z-1-chloro-3,3,3-trifluoropropene and hydrogen chloride are extracted from the system. Among them, the boiling point of E-1,3,3,3-tetrachloropropene is 140℃ (760mmHg); the boiling point of Z-1,3,3,3-tetrachloropropene is 160℃ (760mmHg); the boiling point of 1,1,3,3-tetrachloropropene is 151.4℃ (760mmHg); the boiling point of Z-1-chloro-3,3,3-trifluoropropene is 38℃ (760mmHg); the boiling point of E-1-chloro-3,3,3-trifluoropropene is 19.4℃ (760mmHg); the boiling point of HF is 19.5℃ (760mmHg); and the boiling point of HCl is -85℃ (760mmHg).

[0075] The present application adopts the above method, and the selectivity of E-1-chloro-3,3,3-trifluoropropene is above 89%, and can even reach up to 100% (see Example 14); at the same time, the single-pass conversion rate of E-1,3,3,3-tetrachloropropene and / or Z-1,3,3,3-tetrachloropropene and / or 1,1,3,3-tetrachloropropene can reach up to 100%.

[0076] Example

[0077] This application provides general and / or specific descriptions of the materials and experimental methods used in the experiments. In the following examples, unless otherwise specified, % represents wt%, i.e., percentage by weight. All reagents or instruments used without manufacturer indication are commercially available conventional reagents.

[0078] The prepared product was analyzed by GC using Agilent 8890, and the chromatographic column model was InterCap1 (id 0.25 mm; length 60 m; J&W Scientific Inc.).

[0079] The gas chromatography analysis method used in this application is as follows: high-purity helium and hydrogen are used as carrier gases. The detector temperature is 240°C, the vaporization chamber temperature is 150°C, the column initial temperature is 40°C, maintained for 10 minutes, and then the temperature is increased at 20°C / min to 240°C and maintained for 10 minutes.

[0080] Example 1

[0081] A 1 / 2-inch inner diameter, 30 cm long, Inconel tubular reactor was charged with 10 ml of the tungsten oxyfluoride prepared above. The reactor was heated to 300°C, and E-1,3,3,3-tetrachloropropene and HF were introduced to react. The molar ratio of E-1,3,3,3-tetrachloropropene to HF was controlled at 1:8, the contact time was 60 seconds, and the reaction pressure was atmospheric pressure. After 20 hours of reaction, the reaction product was washed with water and then with alkali to separate the organic matter. After drying to remove water, the composition of the organic matter was analyzed by gas chromatography. The experimental results are shown in Table 1.

[0082] Example 2

[0083] The only difference between this embodiment and embodiment 1 is that Z-1,3,3,3-tetrachloropropene is used to replace E-1,3,3,3-tetrachloropropene in equal amounts. The experimental results are shown in Table 1.

[0084] Example 3

[0085] The only difference between this example and Example 1 is that an equal amount of E-1,3,3,3-tetrachloropropene is replaced by a mixture of E-1,3,3,3-tetrachloropropene and Z-1,3,3,3-tetrachloropropene in a molar ratio of 1:1. The experimental results are shown in Table 1.

[0086] Example 4

[0087] The only difference between this embodiment and embodiment 1 is that 1,1,3,3-tetrachloropropene is used to replace E-1,3,3,3-tetrachloropropene in equal amounts. The experimental results are shown in Table 1.

[0088] Example 5

[0089] The only difference between this embodiment and embodiment 1 is that the reaction temperature is 170° C. The experimental results are shown in Table 1.

[0090] Example 6

[0091] The only difference between this embodiment and embodiment 1 is that the reaction temperature is 200° C. The experimental results are shown in Table 1.

[0092] Example 7

[0093] The only difference between this embodiment and embodiment 1 is that the reaction temperature is 250° C. The experimental results are shown in Table 1.

[0094] Example 8

[0095] The only difference between this embodiment and embodiment 1 is that the reaction temperature is 350° C. The experimental results are shown in Table 1.

[0096] Example 9

[0097] The only difference between this embodiment and embodiment 1 is that the reaction temperature is 400° C. The experimental results are shown in Table 1.

[0098] Example 10

[0099] The only difference between this embodiment and embodiment 1 is that the molar ratio of E-1,3,3,3-tetrachloropropene to HF is 1:5. The experimental results are shown in Table 1.

[0100] Example 11

[0101] The only difference between this embodiment and embodiment 1 is that the molar ratio of E-1,3,3,3-tetrachloropropene to HF is 1:15. The experimental results are shown in Table 1.

[0102] Example 12

[0103] The only difference between this embodiment and embodiment 1 is that the molar ratio of E-1,3,3,3-tetrachloropropene to HF is 1:4. The experimental results are shown in Table 1.

[0104] Example 13

[0105] The only difference between this embodiment and embodiment 1 is that the molar ratio of E-1,3,3,3-tetrachloropropene to HF is 1:30. The experimental results are shown in Table 1.

[0106] Example 14

[0107] The only difference between this embodiment and embodiment 1 is that the catalyst is aluminum fluoride. The experimental results are shown in Table 1.

[0108] Example 15

[0109] The only difference between this embodiment and embodiment 1 is that the catalyst is molybdenum oxyfluoride. The experimental results are shown in Table 1.

[0110] Example 16

[0111] The only difference between this embodiment and embodiment 1 is that the catalyst is chromium fluoride. The experimental results are shown in Table 1.

[0112] Example 17

[0113] The only difference between this embodiment and embodiment 1 is that the catalyst is coconut shell charcoal. The experimental results are shown in Table 1.

[0114] Table 1 Reaction conditions and experimental results of the embodiment

[0115]

[0116]

[0117] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application in any other manner. Any person skilled in the art may utilize the above disclosed technical content to modify or modify the present application into equivalent embodiments with equivalent variations. However, any simple modifications, equivalent variations, and modifications to the above embodiments that do not depart from the technical content of the present application and are based on the technical essence of the present application shall still fall within the scope of protection of the present application.

Claims

1. A method for preparing E-1-chloro-3,3,3-trifluoropropene, characterized in that: It includes: In the presence of a catalyst, E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene undergoes a gas phase fluorine-chlorine exchange reaction with HF to obtain E-1-chloro-3,3,3-trifluoropropene; Wherein, the reaction temperature is 280~300℃; The molar ratio of the E-1,3,3,3-tetrachloropropene or / and Z-1,3,3,3-tetrachloropropene to HF is 1:7-9; Reaction time is 1 to 60 seconds; The reaction pressure is 0.1~0.45MPa; The catalyst is selected from any one of tungsten oxyfluoride, molybdenum oxyfluoride and chromium fluoride.

2. The method according to claim 1, characterized in that The reaction time is 1 to 10 seconds.

3. The method according to claim 1, characterized in that The method is a method for continuously preparing E-1-chloro-3,3,3-trifluoropropene in a gas phase.

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