Processes for the co-production of hfc-236ea, z-hfo-1225ye, e-hfo-1225ye, and hfo-1234yf

Abstract

This application provides a process for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye, and HFO-1234yf, comprising: under a first catalyst, reacting hydrogen and HFO-1225ye to obtain a first reaction product stream; mixing the first reaction product stream with HFP and reacting it under a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea; then separating the stream containing HFC-245eb and the stream containing HFC-236ea; under a third catalyst, reacting the stream containing HFC-236ea, washing with water, and extracting to obtain Z-HFO-1225ye and E-HFO-1225ye streams; under a fourth catalyst, reacting the stream containing HFC-245eb, washing with water, and separating to obtain the HFO-1234yf stream.

Description

Technical Field

[0001] This application relates to the field of fluorochemical technology, and in particular to a process and apparatus for the co-production of HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye and HFO-1234yf. Background Technology

[0002] HFO-1234yf (2,3,3,3-tetrafluoropropylene) is a novel environmentally friendly refrigerant with a low global warming potential (GWP) and is widely used to replace the traditional hydrofluorocarbon HFC-134a. HFC-236ea (1,1,1,2,3,3-hexafluoropropane) and HFO-1225ye (1,2,3,3,3-pentafluoropropylene) are also important fluorochemical products, widely used in refrigeration, foaming, and fire extinguishing agents, and are increasingly being applied in the etching field. Traditional preparation methods typically require multi-step reactions and complex separation processes, resulting in low production efficiency and high costs. Therefore, developing an efficient and low-cost co-production process is of great significance.

[0003] Existing technologies report an industrial-scale process for preparing HFO-1234yf from HFP (hexafluoropropylene), which has been scaled up and verified. However, due to the flammability and explosiveness of hydrogen, high-pressure separation and recovery of hydrogen during the entire process is one of the hazardous points. The two isomers of HFO-1225ye (E / Z) are difficult to separate directly by distillation due to their similar boiling points, requiring extremely sophisticated equipment. Therefore, there are few reports on the separation of these two isomers.

[0004] In recent years, with the gradual application of HFC-236ea, E-HFO-1225ye and Z-HFO-1225ye in the etching field, their synthesis and separation have attracted much attention. However, there are no reports on the co-production of HFO-1234yf, HFC-236ea, E-HFO-1225ye and Z-HFO-1225ye in the current technology. Summary of the Invention

[0005] To address the technical problems existing in the prior art, this application provides a process and apparatus for the co-production of HFO-1234yf, HFC-236ea, E-HFO-1225ye and Z-HFO-1225ye. The process achieves the simultaneous production of multiple products through a reverse feeding process, which is simple in process flow, has high production efficiency and low investment cost.

[0006] The specific technical solution of this application is as follows:

[0007] This application provides a process for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye, and HFO-1234yf, comprising:

[0008] Under the action of a first catalyst, hydrogen and recovered HFO-1225ye are reacted to obtain a first reaction product stream; the first reaction product stream is mixed with HFP and reacted under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea.

[0009] The stream containing HFC-245eb and HFC-236ea was separated to obtain a stream containing HFC-245eb and a stream containing HFC-236ea respectively.

[0010] Under the action of a third catalyst, the stream containing HFC-236ea was reacted, and then washed with water and extracted to obtain the streams Z-HFO-1225ye and E-HFO-1225ye, respectively.

[0011] Under the action of a fourth catalyst, the stream containing HFC-245eb was reacted and then separated by water washing to obtain the stream containing HFO-1234yf.

[0012] Preferably, in the process described above, the first catalyst and the second catalyst are supported catalysts comprising one or more of the following: Pd, Pt, Ni and Zn;

[0013] Optionally, the support for the supported catalyst is activated carbon, alumina, metal fluoride, or molecular sieve.

[0014] Preferably, in the process described above, the third and fourth catalysts are Lewis acid catalysts. Optionally, the Lewis acid catalyst is selected from one or more of chromium oxide, aluminum oxide, magnesium oxide, chromium fluoride, aluminum fluoride, magnesium fluoride, and barium fluoride.

[0015] Preferably, in the process described above, the first reaction temperature is 120-250°C in the reaction of hydrogen and recovered HFO-1225ye to obtain the first reaction product stream; and / or

[0016] The initial reaction pressure is 0.01-0.5 MPa; and / or

[0017] The molar ratio of hydrogen to HFO-1225ye is 1.1-1.8:1; and / or

[0018] The first airspeed is 100-500 h / h -1 .

[0019] Preferably, in the process described above, the second reaction temperature is 120-250°C in the process of mixing the first reaction product stream with HFP and reacting under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea; and / or

[0020] The second reaction pressure is 0.01-0.6 MPa; and / or

[0021] The molar ratio of hydrogen to HFP is 0.1-0.99:1; and / or

[0022] The second reaction space velocity is 100-500 h⁻¹ -1 .

[0023] Preferably, in the process described above, the third reaction temperature is 260-380°C during the reaction of the stream containing HFC-236ea; and / or

[0024] The third reaction pressure is 0.01-0.6 MPa; and / or

[0025] The third airspeed is 20-200 h. -1 .

[0026] Preferably, in the process described above, the fourth reaction temperature is 260-380°C during the reaction of the stream containing HFC-245eb; and / or

[0027] The fourth reaction pressure is 0.01-0.7 MPa; and / or

[0028] The fourth airspeed is 40-200 h. -1 .

[0029] Preferably, for any of the above-described processes, the extractant used in the extraction is N,N-dimethylformamide (DMF) and / or ethyl acetate, or selected from one or more of n-heptane, dimethyl carbonate, carbon tetrachloride and heptafluoroisobutyronitrile.

[0030] This application provides an apparatus for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye, and HFO-1234yf, comprising:

[0031] The unit that generates the first reaction product stream is used to react hydrogen and recovered HFO-1225ye under the action of a first catalyst to obtain the first reaction product stream.

[0032] A unit for producing a stream containing HFC-245eb and HFC-236ea is used to mix a first reaction product stream with HFP and react it under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea.

[0033] A unit that generates a stream containing HFC-245eb and a stream containing HFC-236ea, which is used to separate the streams containing HFC-245eb and HFC-236ea to obtain streams containing HFC-245eb and HFC-236ea respectively.

[0034] The unit that generates Z-HFO-1225ye stream and E-HFO-1225ye stream is used to react the stream containing HFC-236ea under the action of a third catalyst, and then wash and extract it with water to obtain Z-HFO-1225ye stream and E-HFO-1225ye stream respectively.

[0035] The unit that generates the HFO-1234yf stream is used to react the stream containing HFC-245eb under the action of a fourth catalyst and then wash it with water to obtain the HFO-1234yf stream.

[0036] Preferably, in the apparatus described above, the unit generating the first reaction product stream comprises a first reactor; and / or

[0037] The unit for generating a stream containing HFC-245eb and HFC-236ea includes a second reactor, wherein a first reaction product stream obtained from the first reactor and HFP are fed into the second reactor and reacted under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea; and / or

[0038] The unit for generating streams containing HFC-245eb and HFC-236ea includes a first separation tower and a second separation tower. The streams containing HFC-245eb and HFC-236ea collected from the second reactor enter the first separation tower for separation. The stream collected from the bottom of the first separation tower enters the second separation tower. The stream containing HFC-236ea is collected from the top of the second separation tower, and the stream containing HFC-245eb is collected from the bottom of the second separation tower; and / or

[0039] The unit for generating Z-HFO-1225ye and E-HFO-1225ye streams includes a third reactor, a first washing treatment device, a third separation tower, an extraction tower, and a fourth separation tower. The stream containing HFC-236ea, collected from the top of the second separation tower, enters the third reactor and reacts under the action of a third catalyst to obtain a stream containing HFO-1225ye. This HFO-1225ye-containing stream enters the first washing treatment device for washing and drying to obtain a dried HFO-1225ye-containing stream. The dried HFO-1225ye-containing stream enters the third separation tower for separation. The stream containing a mixture of Z-HFO-1225ye and E-HFO-1225ye, collected from the top of the third separation tower, enters the extraction tower for extraction to obtain Z-HFO-1225ye and E-HFO-1225ye streams respectively; and / or

[0040] The unit for generating the HFO-1234yf stream includes a fourth reactor and a second water washing treatment device. The stream containing HFC-245eb is drawn from the bottom of the second separation tower and enters the fourth reactor. Under the action of the fourth catalyst, it reacts to obtain the stream containing HFO-1234yf. The stream containing HFO-1234yf enters the second water washing treatment device for washing and drying to obtain the HFO-1234yf stream.

[0041] Preferably, in the apparatus described above, the extraction tower comprises a first extraction tower, a second extraction tower, and a third extraction tower. The stream containing the mixture of Z-HFO-1225ye and E-HFO-1225ye enters the first extraction tower for extraction. The stream containing Z-1225ye is collected from the top of the first extraction tower and enters the second extraction tower for separation. The Z-1225ye stream is collected from the top of the second extraction tower.

[0042] The stream collected from the bottom of the first extraction tower enters the third extraction tower for separation. The stream containing E-1225ye is collected from the top of the third extraction tower and separated to obtain the E-1225ye stream.

[0043] Preferably, in the apparatus described above, the unit for generating the Z-HFO-1225ye stream and the E-HFO-1225ye stream further includes an absorption tower and a fourth separation tower. The stream containing E-1225ye is drawn from the top of the third extraction tower and enters the absorption tower, and then enters the fourth separation tower for separation to obtain the E-1225ye stream.

[0044] Preferably, in the apparatus described above, the separation pressure of the first extraction tower is 0.4-1.0 MPa; and / or

[0045] The top temperature of the first extraction column is 40-60℃; and / or

[0046] The bottom temperature of the first extraction tower is 50-90℃.

[0047] Preferably, in the apparatus described above, the separation pressure of the second extraction column is 0.1-0.4 MPa, and / or the bottom temperature of the second extraction column is 30-60°C, and / or

[0048] The top temperature of the second extraction column is 10-40℃.

[0049] Preferably, in the apparatus described above, the separation pressure of the third extraction tower is 0.01-0.3 MPa, and / or the...

[0050] The bottom temperature of the third extraction column is 40-80℃, and / or

[0051] The top temperature of the third extraction column is 0-40℃.

[0052] Preferably, in the apparatus described above, the extractant is N,N-dimethylformamide (DMF) and / or ethyl acetate, or selected from one or more of n-heptane, dimethyl carbonate, carbon tetrachloride, and heptafluoroisobutyronitrile.

[0053] The effects of the invention

[0054] The process described in this application enables the simultaneous production of four products: HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye, and HFO-1234yf, thereby improving production efficiency. Furthermore, it reduces the use of compressors and separation towers through a reverse feeding process. Additionally, the process flow is simplified and the operation difficulty is reduced through a reasonable reactor and separation tower design.

[0055] The process described in this application uses an extractant for extraction, which can separate Z-HFO-1225ye and E-HFO-1225ye, which have similar boiling points. Furthermore, the Z-HFO-1225ye and E-HFO-1225ye streams obtained have high contents of Z-HFO-1225ye and E-HFO-1225ye, exceeding 99.9%.

[0056] Furthermore, the process described in this application uses common catalysts and extractants, which reduces equipment investment and operating costs, and reduces waste emissions, thus meeting the requirements of green chemistry.

[0057] The apparatus described in this application uses an extraction tower for extraction, which can separate Z-HFO-1225ye and E-HFO-1225ye, which have similar boiling points. Attached Figure Description

[0058] Figure 1 This is a schematic diagram of the apparatus for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye and HFO-1234yf according to this application. Detailed Implementation

[0059] The present application will now be described in detail with reference to the described embodiments. 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 to the embodiments set forth herein. Rather, these embodiments are provided so that this application will be thorough and complete, and will fully convey the scope of the present application to those skilled in the art.

[0060] It should be noted that certain terms are used in the specification and claims to refer to specific components. Those skilled in the art will understand that different terms may be used to refer to the same component. This specification and claims do not distinguish components based on differences in terminology, but rather on differences in function. The terms "comprising" or "including" used throughout the specification and claims are open-ended and should be interpreted as "comprising but not limited to." The following descriptions in the specification are preferred embodiments for carrying out this application; however, these descriptions are for the purpose of understanding the general principles of the specification and are not intended to limit the scope of this application. The scope of protection of this application shall be determined by the appended claims.

[0061] This application provides a process for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye, and HFO-1234yf, comprising:

[0062] Under the action of a first catalyst, hydrogen and recovered HFO-1225ye are reacted to obtain a first reaction product stream; the first reaction product stream is mixed with HFP and reacted under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea.

[0063] The stream containing HFC-245eb and HFC-236ea was separated to obtain a stream containing HFC-245eb and a stream containing HFC-236ea respectively.

[0064] Under the action of a third catalyst, the stream containing HFC-236ea was reacted, and then washed with water and extracted to obtain Z-HFO-1225ye and E-HFO-1225ye, respectively.

[0065] Under the action of a fourth catalyst, the stream containing HFC-245eb was reacted and separated by water washing to obtain HFO-1234yf.

[0066] The process described in this application achieves the simultaneous production of multiple products through a reverse feeding process. The process flow is simple, the production efficiency is high, the investment cost is low, and the number of compressors and separation towers used is reduced due to the use of the reverse feeding process.

[0067] In some embodiments, the first catalyst and the second catalyst are supported catalysts comprising one or more of the following: Pd, Pt, Ni and Zn;

[0068] Optionally, the support for the supported catalyst is activated carbon, alumina, metal fluoride, or molecular sieve.

[0069] In this application, no restrictions are placed on the preparation methods of the first catalyst and the second catalyst. They can be prepared using conventional methods in the art, such as the method described in Example 1.

[0070] In this application, no restrictions are placed on the shape of the first catalyst and the second catalyst. Any suitable shape can be selected as needed, such as a cylindrical, spherical, or irregular shape.

[0071] Similarly, this application does not impose any restrictions on the amount of the first catalyst and the second catalyst used. Those skilled in the art can select the amount of the first catalyst and the second catalyst used based on actual needs.

[0072] In some embodiments, the third and fourth catalysts are Lewis acid catalysts, optionally selected from one or more of chromium oxide, aluminum oxide, magnesium oxide, chromium fluoride, aluminum fluoride, magnesium fluoride, and barium fluoride.

[0073] In this application, no restrictions are placed on the preparation methods of the third and fourth catalysts. Those skilled in the art can use conventional methods in the field to prepare them, such as the method disclosed in CN109999788B.

[0074] In this application, no restrictions are placed on the shape of the third and fourth catalysts. They can be selected in any suitable shape as needed, such as cylindrical, spherical or irregular shapes.

[0075] Similarly, this application does not impose any restrictions on the amount of the third and fourth catalysts used, and those skilled in the art can choose the amount of the third and fourth catalysts used based on actual needs.

[0076] In some embodiments, the first reaction temperature is 120-250°C in the reaction of hydrogen and recovered HFO-1225ye to obtain a first reaction product stream; and / or

[0077] The initial reaction pressure is 0.01-0.5 MPa; and / or

[0078] The molar ratio of hydrogen to HFO-1225ye is 1.1-1.8:1; and / or

[0079] The first airspeed is 100-500 h / h -1 .

[0080] For example, the first reaction temperature can be 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, 250℃, etc.

[0081] The initial reaction pressure can be 0.01 MPa, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa, 0.06 MPa, 0.07 MPa, 0.08 MPa, 0.09 MPa, 0.10 MPa, 0.11 MPa, 0.12 MPa, 0.13 MPa, 0.14 MPa, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, or 0.19 MPa. 0.20MPa, 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, 0.26MPa, 0.27MPa, 0.28MPa, 0.29MPa, 0.30MPa, 0.31MPa, 0.32MPa, 0.33MPa, 0.34MPa, 0.35MPa, 0.36MPa, 0.40MPa, 0.45MPa, 0.50MPa, etc.

[0082] The molar ratio of hydrogen to HFO-1225ye (n) 氢气 :n HFO-1225ye The ratios can be 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, etc.

[0083] The first airspeed can be 100 h. -1 150h -1 200h -1 250h -1 300h -1 350h -1 400h -1 450h -1 500h -1 wait.

[0084] In some embodiments, in the process of mixing the first reaction product stream with HFP and reacting it under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea, the second reaction temperature is 120-250°C; and / or

[0085] The second reaction pressure is 0.01-0.6 MPa; and / or

[0086] The molar ratio of hydrogen to HFP is 0.1-0.99:1; and / or

[0087] The second reaction space velocity is 100-500 h⁻¹ -1 .

[0088] For example, the second reaction temperature can be 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, 250℃, etc.

[0089] The second reaction pressure can be 0.01 MPa, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa, 0.06 MPa, 0.07 MPa, 0.08 MPa, 0.09 MPa, 0.10 MPa, 0.11 MPa, 0.12 MPa, 0.13 MPa, 0.14 MPa, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa, or 0.20 MPa. 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, 0.26MPa, 0.27MPa, 0.28MPa, 0.29MPa, 0.30MPa, 0.31MPa, 0.32MPa, 0.33MPa, 0.34MPa, 0.35MPa, 0.36MPa, 0.40MPa, 0.45MPa, 0.50MPa, 0.55MPa, 0.60MPa, etc.

[0090] The molar ratio of hydrogen to HFP (n) 氢气 :n HFP The ratios can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 0.99:1, etc.

[0091] The second airspeed can be 100 h. -1 150h -1 200h -1 250h -1 300h -1 350h -1 400h -1 450h -1 500h -1 wait.

[0092] In some embodiments, during the reaction of the stream containing HFC-236ea, the third reaction temperature is 260-380°C; and / or

[0093] The third reaction pressure is 0.01-0.6 MPa; and / or

[0094] The third airspeed is 20-200 h. -1 .

[0095] For example, the third reaction temperature can be 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, etc.

[0096] The third reaction pressure can be 0.01 MPa, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa, 0.06 MPa, 0.07 MPa, 0.08 MPa, 0.09 MPa, 0.10 MPa, 0.11 MPa, 0.12 MPa, 0.13 MPa, 0.14 MPa, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa, or 0.20 MPa. 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, 0.26MPa, 0.27MPa, 0.28MPa, 0.29MPa, 0.30MPa, 0.31MPa, 0.32MPa, 0.33MPa, 0.34MPa, 0.35MPa, 0.36MPa, 0.40MPa, 0.45MPa, 0.50MPa, 0.55MPa, 0.60MPa, etc.

[0097] The third airspeed can be 20 h.-1 30 h -1 40 h -1 50 h -1 60 h -1 70 h -1 80 h -1 90 h -1 100h -1 110 h -1 120 h -1 130 h -1 140 h -1 150 h -1 160 h -1 170 h -1 180 h -1 190 h -1 200 h -1 wait.

[0098] In some embodiments, during the reaction of the stream containing HFC-245eb, the fourth reaction temperature is 260-380°C; and / or

[0099] The fourth reaction pressure is 0.01-0.7 MPa; and / or

[0100] The fourth airspeed is 40-200 h. -1 .

[0101] For example, the fourth reaction temperature can be 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, etc.

[0102] The fourth reaction pressure can be 0.01 MPa, 0.02 MPa, 0.03 MPa, 0.04 MPa, 0.05 MPa, 0.06 MPa, 0.07 MPa, 0.08 MPa, 0.09 MPa, 0.10 MPa, 0.11 MPa, 0.12 MPa, 0.13 MPa, 0.14 MPa, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa, 0.20 MPa, or 0.21 MPa. 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, 0.26MPa, 0.27MPa, 0.28MPa, 0.29MPa, 0.30MPa, 0.31MPa, 0.32MPa, 0.33MPa, 0.34MPa, 0.35MPa, 0.36MPa, 0.40MPa, 0.45MPa, 0.50MPa, 0.55MPa, 0.60MPa, 0.65MPa, 0.70MPa, etc.

[0103] The fourth airspeed can be 40 h -1 50 h -1 60 h -1 70 h -1 80 h -1 90 h -1 100 h -1 110 h -1 120 h -1 130 h -1 140 h -1 150 h -1 160 h -1 170 h -1 180 h -1 190 h -1 200 h -1 wait.

[0104] In some embodiments, the extractant used for extraction is N,N-dimethylformamide (DMF) and / or ethyl acetate, or selected from one or more of n-heptane, dimethyl carbonate, carbon tetrachloride, and heptafluoroisobutyronitrile; preferably, when the extractant is N,N-dimethylformamide (DMF) and ethyl acetate, their mass ratio is 5-1:1. For example, the mass ratio of DMF to ethyl acetate (m...) DMF :m 乙酸乙酯 The ratios can be 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, etc.

[0105] The process described in this application can simultaneously produce HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye and HFO-1234yf, improving production efficiency, and using conventional catalysts and extractants in the art, reducing equipment investment and operating costs.

[0106] The process described in this application uses reverse feeding, which uses hydrogen and the recovered intermediate HFO-1225ye(E / Z) to react, eliminating the need for hydrogen recovery. The hydrogen is then reacted with HFP, thus reducing the number of compressors and separation towers used.

[0107] This application provides an apparatus for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye, and HFO-1234yf, comprising:

[0108] The unit that generates the first reaction product stream is used to react hydrogen and recovered HFO-1225ye under the action of a first catalyst to obtain the first reaction product stream.

[0109] A unit for producing a stream containing HFC-245eb and HFC-236ea is used to mix a first reaction product stream with HFP and react it under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea.

[0110] A unit that generates a stream containing HFC-245eb and a stream containing HFC-236ea, which is used to separate the streams containing HFC-245eb and HFC-236ea to obtain streams containing HFC-245eb and HFC-236ea respectively.

[0111] The unit that generates Z-HFO-1225ye stream and E-HFO-1225ye stream is used to react the stream containing HFC-236ea under the action of a third catalyst, and then wash and extract it with water to obtain Z-HFO-1225ye stream and E-HFO-1225ye stream respectively.

[0112] The unit that generates the HFO-1234yf stream is used to react the stream containing HFC-245eb under the action of a fourth catalyst and then wash it with water to obtain the HFO-1234yf stream.

[0113] Figure 1 An apparatus according to one specific embodiment of this application is shown, comprising:

[0114] The unit for generating the first reaction product stream includes a first reactor 2, which is used to react hydrogen and the recovered HFO-1225ye stream 23 under the action of a first catalyst to obtain the first reaction product stream 1; and / or

[0115] The unit for generating stream 4 containing HFC-245eb and HFC-236ea includes a second reactor 3. A first reaction product stream 1 obtained from the first reactor 2 and HFP enter the second reactor 3 and react under the action of a second catalyst to obtain stream 4 containing HFC-245eb and HFC-236ea; and / or

[0116] The unit for generating stream 11 containing HFC-245eb and stream 9 containing HFC-236ea includes a first separation tower 6 and a second separation tower 8. Stream 4 containing HFC-245eb and HFC-236ea, collected from the second reactor 3, enters the first separation tower 6 for separation. Stream 7, mainly containing HFC-245eb, collected from the bottom of the first separation tower 6, enters the second separation tower 8. Stream 11 containing HFC-236ea is collected from the top of the second separation tower 8, and stream 9 containing HFC-245eb is collected from the bottom of the second separation tower 8; and / or

[0117] The unit that generates Z-HFO-1225ye stream 30 and E-HFO-1225ye stream 35 includes a third reactor 12, a first water washing treatment device, a third separation tower 19, an extraction tower (not shown), and a fourth separation tower 34. Stream 11 containing HFC-236ea is collected from the top of the second separation tower 8 and enters the third reactor 12; alternatively, HFC-236ea can be collected as a product. The reaction, under the action of a third catalyst, yields stream 13 containing a mixture of HFC-236ea, HFO-1225ye, and hydrogen fluoride. Stream 13 contains HFC-236ea and HFO... The stream 13, a mixture of HFO-1225ye and hydrogen fluoride, enters a first washing treatment unit for washing and drying to obtain a dried stream 18 containing HFO-1225ye; the dried stream 18 containing HFO-1225ye (E / Z) and HFC-236ea enters a third separation tower 19 for separation; the stream 21, containing a mixture of Z-HFO-1225ye and E-HFO-1225ye, collected from the top of the third separation tower 19, enters an extraction tower for extraction to obtain streams 30 of Z-HFO-1225ye and 35 of E-HFO-1225ye; and / or

[0118] The unit that generates HFO-1234yf stream 44 includes a fourth reactor 36 and a second water washing treatment device. Stream 9 containing HFC-245eb is taken from the bottom of the second separation tower 8 and enters the fourth reactor 36. Under the action of a fourth catalyst, it reacts to obtain stream 37 containing a mixture of HFC-245eb and HFO-1234yf. Stream 37 containing the mixture of HFC-245eb and HFO-1234yf enters the second water washing treatment device for washing and drying to obtain stream 44 of HFO-1234yf.

[0119] In some embodiments, the extraction tower includes a first extraction tower 22, a second extraction tower 29, and a third extraction tower 26. The stream 21 containing a mixture of Z-HFO-1225ye and E-HFO-1225ye enters the first extraction tower 22 for extraction. The stream 24 containing Z-HFO-1225ye and trace extractant is collected from the top of the first extraction tower 22 and enters the second extraction tower 29 for separation. The Z-HFO-1225ye stream 30 is collected from the top of the second extraction tower.

[0120] The stream 25 containing E-1225ye and extractant, collected from the bottom of the first extraction tower 22, enters the third extraction tower 26 for separation. The stream 31 containing E-HFO-1225ye and a small amount of extractant is collected from the top of the third extraction tower 26, and the stream 35 containing E-HFO-1225ye is separated.

[0121] In some embodiments, the unit that generates Z-HFO-1225ye stream 30 and E-HFO-1225ye stream 35 further includes an absorption tower 32 and a fourth separation tower 34. Stream 31 containing E-HFO-1225ye and a small amount of extractant is drawn from the top of the third extraction tower 26 and enters the absorption tower 32, and then enters the fourth separation tower 34 for separation to obtain E-HFO-1225ye stream 35.

[0122] In this application, the first extraction tower 22 is filled with an extractant for extraction, while the second extraction tower 29 and the third extraction tower 26 are not filled with an extractant and are only used for separation.

[0123] In some embodiments, the first water washing treatment apparatus includes a first water alkali tower 14 and a first drying system 17. The stream 13 containing a mixture of HFC-236ea, HFO-1225ye and hydrogen fluoride enters the first water alkali tower 14 for water washing, and then enters the first drying system 17 for drying to obtain a dried stream 18 containing HFO-1225ye (E / Z) and HFC-236ea.

[0124] In some embodiments, the second water washing treatment device includes a second water alkali tower 38 and a second drying system 41. The stream 37 containing hydrogen fluoride, HFC-245eb and HFO-1234yf enters the second water alkali tower 38 for water washing, and then enters the second drying system 41 for drying and separation to obtain the HFO-1234yf stream 44.

[0125] The device described in this application solves the problem of hydrogen recovery by reverse feeding, reduces the use of compressors, and lowers the difficulty of operation.

[0126] In some embodiments, the separation pressure of the first extraction column is 0.4-1.0 MPa; and / or

[0127] The top temperature of the first extraction column is 40-60℃; and / or

[0128] The bottom temperature of the first extraction tower is 50-90℃.

[0129] For example, the separation pressure of the first extraction tower can be 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, etc.

[0130] The top temperature of the first extraction tower is 40℃, 41℃, 42℃, 43℃, 44℃, 45℃, 46℃, 47℃, 48℃, 49℃, 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, etc.

[0131] The bottom temperature of the first extraction tower is 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, etc.

[0132] In some embodiments, the separation pressure of the second extraction column is 0.1-0.4 MPa, and / or

[0133] The bottom temperature of the second extraction column is 30-60℃, and / or

[0134] The top temperature of the second extraction column is 10-40℃.

[0135] For example, the separation pressure of the second extraction tower can be 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, etc.

[0136] The bottom temperature of the second extraction tower can be 30℃, 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃, 39℃, 40℃, 41℃, 42℃, 43℃, 44℃, 45℃, 46℃, 47℃, 48℃, 49℃, 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, etc.

[0137] The top temperature of the second extraction tower can be 10℃, 11℃, 12℃, 13℃, 14℃, 15℃, 16℃, 17℃, 18℃, 19℃, 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, 28℃, 29℃, 30℃, 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃, 39℃, 40℃, etc.

[0138] In some embodiments, the separation pressure of the third extraction column is 0.01-0.3 MPa, and / or

[0139] The bottom temperature of the third extraction column is 40-80℃, and / or

[0140] The top temperature of the third extraction column is 0-40℃.

[0141] For example, the separation pressure of the third extraction tower can be 0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa, 0.10MPa, 0.11MPa, 0.12MPa, 0.13MPa, 0.14MPa, 0.15MPa, 0.16MPa, 0.17MPa, 0.18MPa, 0.19MPa, 0.20MPa, 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, 0.26MPa, 0.27MPa, 0.28MPa, 0.29MPa, 0.30MPa, etc.

[0142] The bottom temperature of the third extraction tower can be 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, etc.

[0143] The top temperature of the third extraction tower can be 0, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, etc.

[0144] In some embodiments, the extractant is N,N-dimethylformamide (DMF) and / or ethyl acetate, or selected from one or more of n-heptane, dimethyl carbonate, carbon tetrachloride and heptafluoroisobutyronitrile.

[0145] In some embodiments, the apparatus further includes an adsorption tower 32 for adsorbing the stream 31 containing E-HFO-1225ye and a small amount of extractant to remove the extractant before it enters a fourth separation tower 34 for separation.

[0146] In some implementations, the stream 5 collected from the top of the first separation tower is returned to the first reactor 2.

[0147] In some embodiments, the stream 21 containing a mixture of Z-HFO-1225ye and E-HFO-1225ye drawn from the top of the third separation tower 19 can be returned to the first reactor 2 for reaction.

[0148] In some embodiments, the stream 28 containing a small amount of extractant and Z-HFO-1225ye drawn from the bottom of the second extraction tower 29 and the stream 27 containing a mixture of extractant and a small amount of E-HFO-1225ye drawn from the bottom of the third extraction tower 26 can be returned to the first extraction tower 22 for extraction.

[0149] In this application, the reactors, separation towers, and their associated raw material conveying pipes, discharge pipes, and related units should be made of corrosion-resistant materials. Commonly used corrosion-resistant materials include nickel-containing alloys, stainless steel, and copper-plated steel.

[0150] In this application, the reactors, separation towers, extraction towers, water washing devices, drying systems, and adsorption towers used are all conventional devices in the art.

[0151] Example

[0152] This application provides a general and / or specific description of the materials and test methods used in the experiments. In the following examples, unless otherwise specified, % represents wt%, i.e., weight percentage. Reagents or instruments used, unless otherwise specified, are all commercially available conventional reagent products.

[0153] Example 1: Preparation of the first and second catalysts

[0154] Weigh the required amount of PdCl2•2H2O and dissolve it in a certain amount of water. Add a small amount of hydrochloric acid to accelerate the dissolution. Adsorb the solution in activated carbon at 60℃ for 18 h and dry it at 105℃ for 6 h to obtain a 3% PdCl2 / AC supported catalyst precursor. Place it in a reactor and purge it with hydrogen gas for reduction until there is no acidity in the tail gas. The catalyst activation is considered complete. Place it in the reactor and keep it under nitrogen protection for later use.

[0155] Example 2: Preparation of the third and fourth catalysts

[0156] Weigh out the required amounts of chromium trichloride and barium trichloride, dissolve them in water at a mass ratio of 6:4, add concentrated ammonia dropwise to precipitate, adjust the pH to 7.5, then wash with water, filter, and dry in an oven at 80℃ for 36 hours. Crush the resulting solid, press it into tablets, and prepare the catalyst precursor. Add the catalyst precursor to a reactor, calcine it at 450℃ for 8 hours under nitrogen gas, with a nitrogen space velocity of 200 h⁻¹. -1 Then the temperature was lowered to 300°C, and a mixture of hydrogen fluoride and nitrogen in a molar ratio of 1:2 was introduced, with a total gas space velocity of 220 h⁻¹. -1 Activation was performed for 24 hours; then the temperature was raised to 375°C, and a mixture of nitrogen and nitrogen trifluoride in a molar ratio of 10:1 was introduced, with a total gas space velocity of 660 h⁻¹. -1 After oxidizing for 24 hours, the above mixed gas was stopped, and nitrogen was used for blowing to obtain the third and fourth catalysts for HF removal.

[0157] Example 3: Process and apparatus for the co-production of HFO-1234yf, Z-HFO-1225ye, HFO-1225ye and HFC-236ea

[0158] The first catalyst prepared in Example 1 was added to the first reactor 2, which has a tube-side volume of 500 L. The recovered HFO-1225ye stream 23 and the newly added hydrogen were mixed and then fed into the first reactor 2. The molar ratio of H2 to HFO-1225ye was 1.9:1. The first reaction temperature was controlled at 200 °C, the first reaction pressure was 0.3 MPa, and the first space velocity was 300 h⁻¹. -1 The first reaction product stream 1 was collected from the first reactor 2 and analyzed according to conventional methods in the art. The organic phase contained 99.05% HFC-245eb, 0.87% HFO-1225ye (E / Z), and 0.07% HFO-1234yf. The first reaction product stream 1 was not separated and was directly mixed with newly added HFP before entering the second reactor 3. In the second reactor 3, the H2:HFP molar ratio was 0.9:1, the second reaction temperature was controlled at 250°C, the second reaction pressure was 0.2 MPa, and the second space velocity was 300 h⁻¹. -1In the second reactor 3, a stream containing HFC-245eb and HFC-236ea was collected. The stream was analyzed according to conventional methods in the art, revealing that the content of HFC-245eb was 49.91%, HFC-236ea was 44.97%, HFP was 5.0%, and other components were 0.12%. The stream containing HFC-245eb and HFC-236ea was pressurized by the first compressor 45 and then entered the first separation tower 6 for separation. The top temperature of the first separation tower 6 was controlled at -30 to -25°C, the top pressure at 0.7 to 0.8 MPa, and the bottom temperature at 30 to 35°C. The top stream 5 of the first separation tower 6 is determined by conventional methods in the art to have an HFP content greater than 99% and contain a small amount of hydrogen. It is returned to the first reactor 2 for further reaction. The stream 7, mainly containing HFC-245eb, is collected from the bottom of the first separation tower 6 and enters the second separation tower 8 for separation. The top temperature of the second separation tower 8 is controlled at 15-20°C, the top pressure at 0.35-0.40 MPa, and the bottom temperature at 30-40°C. The top stream 11 containing HFC-236ea is collected from the top of the second separation tower 8. The HFC-236ea content of stream 11 is determined by conventional methods in the art to be greater than 99.9%. It can be directly collected as the first product. The bottom stream 9 containing HFC-245eb is collected from the bottom of the second separation tower 8.

[0159] The stream 11 containing HFC-236ea was introduced into the third reactor 12, which contained the third catalyst prepared in Example 2. The reaction was carried out in the third reactor 12 at a third reaction temperature of 380°C, a third reaction pressure of 0.2 MPa, and a third space velocity of 200 h⁻¹. -1Under the action of a third catalyst, a stream 13 containing a mixture of HFC-236ea, HFO-1225ye, and hydrogen fluoride was obtained. Measured according to conventional methods in the art, the product conversion at the outlet of the third reactor 12 was 90%, and the selectivity for HFO-1225ye was 99.7%. The stream 13 containing the mixture of HFC-236ea, HFO-1225ye, and hydrogen fluoride was washed by a first water washing treatment unit 14, and a sample containing HFO-1225ye was collected from the top of the first water washing treatment unit 14. The stream 16 containing (E / Z) and HFC-236ea is drawn from the bottom of the first water washing treatment unit 14. After being pressurized by the third compressor 47, it enters the first drying system 17 for drying and dehydration. The dried stream 18 containing HFO-1225ye (E / Z) and HFC-236ea enters the third separation tower 19 for separation. The top temperature of the third separation tower 19 is controlled at -15 to -10℃, the top pressure is 0.30 to 0.35 MPa, and the bottom temperature is 30 to 40℃. A stream 21 containing a mixture of Z-HFO-1225ye and E-HFO-1225ye is collected from the top of the third separation tower 19. This stream 21 can be returned to the first reactor 2 for further reaction or enter the first extraction tower 22. An unreacted stream 20 containing HFC-236ea is collected from the bottom of the third separation tower 19 and can be returned to the third reactor 12.

[0160] Stream 21, containing a mixture of Z-HFO-1225ye and E-HFO-1225ye, enters a first extraction column 22. An extractant (a mixture of DMF and ethyl acetate in a mass ratio of 3:2) is added to the first extraction column 22, and extraction takes place. The bottom temperature of the first extraction column 22 is 50°C, the top temperature is 35°C, and the pressure is 0.4 MPa. Stream 24, containing Z-HFO-1225ye and trace amounts of extractant, is collected from the top of the first extraction column 22. Stream 24 then enters a second extraction column 29 for separation. The bottom temperature of the second extraction column is 38°C, the top temperature is 15°C, and the pressure is 0.10-0.15 MPa. Stream 30, containing Z-HFO-1225ye, is collected from the top of the second extraction column and, when determined according to conventional methods in the art, its content is greater than 99.9%. The stream 28, containing a small amount of extractant and Z-HFO-1225ye, collected from the bottom of the second extraction column 29, is returned to the first extraction column 22 for further extraction. The stream 25, containing E-HFO-1225ye and extractant, is collected from the bottom of the first extraction column 22 and enters the third extraction column 26 for separation. The bottom temperature of the third extraction column 26 is 30°C, the top temperature is 5°C, and the pressure is 0.05 MPa. Through pressure swing distillation, the stream 31, containing E-HFO-1225ye and a small amount of extractant, is collected from the top of the third extraction column 26, and the stream 27, containing extractant and a small amount of E-HFO-1225ye, is collected from the bottom and returned to the first extraction column 22 for further extraction. The stream 31 containing E-HFO-1225ye and a small amount of extractant enters the adsorption tower 32 for treatment to remove the small amount of extractant, resulting in stream 33. Then, it enters the fourth separation tower 34 for separation. Stream 35, with an E-HFO-1225ye content greater than 99.0%, is collected from the top of the fourth separation tower.

[0161] The stream 9 containing HFC-245eb (HFC-245eb content greater than 99%), collected from the bottom of the second separation tower 8, enters the fourth reactor 36. The fourth reactor 36 is loaded with the fourth catalyst prepared in Example 2, and the reaction takes place in the fourth reactor 36 at a reaction temperature of 370°C, a reaction pressure of 0.3 MPa, and a space velocity of 150 h⁻¹. -1Under the action of the fourth catalyst, a stream 37 containing hydrogen fluoride, HFC-245eb, and HFO-1234yf is obtained. According to conventional methods in the art, the product conversion rate at the outlet of the fourth reactor 36 is 90%, and the selectivity of HFO-1225ye is 99.7%. Then, the stream 37 containing hydrogen fluoride, HFC-245eb, and HFO-1234yf enters the second water washing treatment device 38. A stream 39 containing a mixture of HFC-245eb and HFO-1234yf is collected from the top of the second water washing treatment device 38, and a stream 40 is collected from the bottom of the second water washing treatment device 38. After being pressurized by the second compressor 46, it enters the second drying system 41 for drying. The dried stream 42 enters the separation system 43 for separation. A stream 44 containing HFO-1234yf with a content greater than 99.9% is collected from the top of the separation system 43. The unreacted stream 10 can be returned from the bottom of the separation system 43 to the fourth reactor 36 to continue the reaction.

[0162] Example 4

[0163] Example 4 compares with Example 3. Stream 21, containing a mixture of Z-HFO-1225ye and E-HFO-1225ye, enters the first extraction column 22. An extractant (a mixture of DMF and ethyl acetate, with a mass ratio of 1:1) is added to the first extraction column 22. Extraction is carried out in the first extraction column 22. The bottom temperature of the first extraction column 22 is 50°C, the top temperature is 35°C, and the pressure is 0.3 MPa. Stream 24, containing Z-HFO-1225ye and trace amounts of extractant, is collected from the top of the first extraction column 22. The Z-HFO-1225ye stream 24 and the trace extractant stream 29 are separated in the second extraction column 29, where the bottom temperature of the second extraction column is 38°C, the top temperature is 15°C, and the pressure is 0.10-0.15 MPa. The Z-HFO-1225ye stream 30 is collected from the top of the second extraction column. According to conventional methods in the art, the Z-HFO-1225ye content is 98.2%, the E-HFO-1225ye content is 1.3%, and the DMF + ethyl acetate content is 0.5%. The E-HFO-1225ye stream 35 with a content of 99.3% is collected from the top of the fourth separation column.

[0164] Example 5

[0165] Example 5 was compared with Example 3. The extractant was DMF. Z-HFO-1225ye stream 30 was collected from the top of the second extraction column. The Z-HFO-1225ye content was determined to be 96.5%, the E-HFO-1225ye content was 3.2%, and the DMF content was 0.3% according to conventional methods in the art. Stream 35, with an E-HFO-1225ye content of 98.3%, was collected from the top of the fourth separation column.

[0166] Comparative Example 1

[0167] The difference between Comparative Example 1 and Example 3 is that a conventional separation column was used instead of the first, second, and third extraction columns. The column had 30 trays, a bottom temperature of 30-35°C, a top temperature of 0-5°C, an operating pressure of 0.30-0.35 MPa, and a split ratio of 2:1. The content of Z-HFO-1225ye obtained from the top of the separation column was 95.50%, the content of E-HFO-1225ye was 4.37%, and the content of other components was 0.13%.

[0168] Comparative Example 2

[0169] Comparing Comparative Example 2 and Example 3, without using the first, second, and third extraction towers, distillation was performed directly. Since the boiling points of Z-HFO-1225ye and E-HFO-1225ye are only slightly different, Z-HFO-1225ye and E-HFO-1225ye were separated, and their contents were 95.3% and 4.7%, respectively.

[0170] The above description is merely a preferred embodiment of this application and is not intended to limit the application in any other way. Any person skilled in the art may make changes or modifications to the disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this application without departing from the scope of the technical solution of this application shall still fall within the protection scope of this application.

Claims

1. A process for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye and HFO-1234yf, comprising: Under the action of the first catalyst, hydrogen and recovered HFO-1225ye are reacted to obtain the first reaction product stream; The first reaction product stream is mixed with HFP and reacted under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea; The stream containing HFC-245eb and HFC-236ea was separated to obtain a stream containing HFC-245eb and a stream containing HFC-236ea respectively. Under the action of a third catalyst, the stream containing HFC-236ea was reacted, and then washed with water and extracted to obtain the streams Z-HFO-1225ye and E-HFO-1225ye, respectively. Under the action of a fourth catalyst, the stream containing HFC-245eb was reacted and then separated by water washing to obtain the stream containing HFO-1234yf. The extraction solvent used is N,N-dimethylformamide (DMF) and ethyl acetate, and the mass ratio of N,N-dimethylformamide (DMF) to ethyl acetate is 5-1:

1. The first catalyst and the second catalyst are supported catalysts containing one or more of the following: Pd, Pt, Ni and Zn; The support for the catalyst is activated carbon, alumina, metal fluoride, or molecular sieve. The third and fourth catalysts are Lewis acid catalysts, which are selected from one or more of chromium oxide, aluminum oxide, magnesium oxide, chromium fluoride, aluminum fluoride, magnesium fluoride and barium fluoride. In the reaction of hydrogen and recovered HFO-1225ye to obtain the first reaction product stream, the first reaction temperature is 120-250℃. The initial reaction pressure is 0.01-0.5 MPa; The molar ratio of hydrogen to HFO-1225ye is 1.9:1; The first airspeed is 100-500 h / h -1 ; In the process of mixing the first reaction product stream with HFP and reacting it under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea, the second reaction temperature is 120-250℃. The second reaction pressure is 0.01-0.6 MPa; The molar ratio of hydrogen to HFP is 0.1-0.99:1; The second reaction space velocity is 100-500 h⁻¹ -1 ; In the reaction of the stream containing HFC-236ea, the third reaction temperature is 260-380℃; The third reaction pressure is 0.01-0.6 MPa; The third airspeed is 20-200 h. -1 ; In the reaction of the stream containing HFC-245eb, the fourth reaction temperature is 260-380°C; and / or The fourth reaction pressure is 0.01-0.7 MPa; and / or The fourth airspeed is 40-200 h. -1 .

2. An apparatus for co-producing HFC-236ea, Z-HFO-1225ye, E-HFO-1225ye and HFO-1234yf, comprising: The unit that generates the first reaction product stream is used to react hydrogen and recovered HFO-1225ye under the action of a first catalyst to obtain the first reaction product stream. A unit for producing a stream containing HFC-245eb and HFC-236ea is used to mix a first reaction product stream with HFP and react it under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea. A unit that generates a stream containing HFC-245eb and a stream containing HFC-236ea, which is used to separate the streams containing HFC-245eb and HFC-236ea to obtain streams containing HFC-245eb and HFC-236ea respectively. The unit that generates Z-HFO-1225ye stream and E-HFO-1225ye stream is used to react the stream containing HFC-236ea under the action of a third catalyst, and then wash and extract it with water to obtain Z-HFO-1225ye stream and E-HFO-1225ye stream respectively. The unit that generates the HFO-1234yf stream is used to react the stream containing HFC-245eb under the action of a fourth catalyst and then wash it with water to obtain the HFO-1234yf stream. The unit that generates the first reaction product stream includes a first reactor; and / or The unit for generating a stream containing HFC-245eb and HFC-236ea includes a second reactor, wherein a first reaction product stream obtained from the first reactor and HFP enter the second reactor and react under the action of a second catalyst to obtain a stream containing HFC-245eb and HFC-236ea. and / or The unit for generating streams containing HFC-245eb and HFC-236ea includes a first separation tower and a second separation tower. The streams containing HFC-245eb and HFC-236ea collected from the second reactor enter the first separation tower for separation. The stream collected from the bottom of the first separation tower enters the second separation tower. The stream containing HFC-236ea is collected from the top of the second separation tower, and the stream containing HFC-245eb is collected from the bottom of the second separation tower; and / or The unit for generating Z-HFO-1225ye and E-HFO-1225ye streams includes a third reactor, a first washing treatment device, a third separation tower, an extraction tower, and a fourth separation tower. The stream containing HFC-236ea, collected from the top of the second separation tower, enters the third reactor and reacts under the action of a third catalyst to obtain a stream containing HFO-1225ye. This HFO-1225ye-containing stream enters the first washing treatment device for washing and drying to obtain a dried HFO-1225ye-containing stream. The dried HFO-1225ye-containing stream enters the third separation tower for separation. The stream containing a mixture of Z-HFO-1225ye and E-HFO-1225ye, collected from the top of the third separation tower, enters the extraction tower for extraction to obtain Z-HFO-1225ye and E-HFO-1225ye streams respectively; and / or The unit that generates the HFO-1234yf stream includes a fourth reactor and a second water washing treatment device. The stream containing HFC-245eb is taken from the bottom of the second separation tower and enters the fourth reactor. Under the action of the fourth catalyst, it reacts to obtain the stream containing HFO-1234yf. The stream containing HFO-1234yf enters the second water washing treatment device for washing and drying to obtain the HFO-1234yf stream. The extraction tower includes a first extraction tower, a second extraction tower, and a third extraction tower. The stream containing a mixture of Z-HFO-1225ye and E-HFO-1225ye enters the first extraction tower for extraction. The stream containing Z-1225ye is collected from the top of the first extraction tower and enters the second extraction tower for separation. The Z-1225ye stream is collected from the top of the second extraction tower. The stream collected from the bottom of the first extraction tower enters the third extraction tower for separation. The stream containing E-1225ye is collected from the top of the third extraction tower and separated to obtain the E-1225ye stream. The extraction solvent used is N,N-dimethylformamide (DMF) and ethyl acetate, and the mass ratio of N,N-dimethylformamide (DMF) to ethyl acetate is 5-1:1; The separation pressure of the first extraction tower is 0.4-1.0 MPa; The temperature at the top of the first extraction column is 40-60℃; The bottom temperature of the first extraction column is 50-90℃; The separation pressure of the second extraction tower is 0.1-0.4 MPa. The bottom temperature of the second extraction column is 30-60℃. The top temperature of the second extraction column is 10-40℃; The separation pressure of the third extraction tower is 0.01-0.3 MPa. The bottom temperature of the third extraction column is 40-80℃. The top temperature of the third extraction column is 0-40℃.

3. The apparatus according to claim 2, wherein, The unit that generates Z-HFO-1225ye and E-HFO-1225ye streams also includes an absorption tower and a fourth separation tower. The stream containing E-1225ye is drawn from the top of the third extraction tower and enters the absorption tower, and then enters the fourth separation tower for separation to obtain the E-1225ye stream.

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