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WO2017015779A1 - 一种2，3，3，3-四氟丙烯的生产方法 - Google Patents

一种2，3，3，3-四氟丙烯的生产方法 Download PDF

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WO2017015779A1
WO2017015779A1 PCT/CN2015/000655 CN2015000655W WO2017015779A1 WO 2017015779 A1 WO2017015779 A1 WO 2017015779A1 CN 2015000655 W CN2015000655 W CN 2015000655W WO 2017015779 A1 WO2017015779 A1 WO 2017015779A1
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Prior art keywords
reactor
catalyst
hexafluoropropylene
hfo
tetrafluoropropene
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English (en)
French (fr)
Inventor
雷俊
王爱国
杨波
张彦
周华东
赵阳
朱意
夏海利
施浩进
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ZHEJIANG QUZHOU JUXIN FLUORINE CHEMICAL CO Ltd
Zhejiang Quhua Fluor Chemistry Co Ltd
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ZHEJIANG QUZHOU JUXIN FLUORINE CHEMICAL CO Ltd
Zhejiang Quhua Fluor Chemistry Co Ltd
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Priority to PCT/CN2015/000655 priority Critical patent/WO2017015779A1/zh
Priority to EP15899132.3A priority patent/EP3330244B1/en
Priority to JP2016530202A priority patent/JP6371846B2/ja
Priority to PL15899132T priority patent/PL3330244T3/pl
Priority to US15/378,019 priority patent/US9643904B2/en
Publication of WO2017015779A1 publication Critical patent/WO2017015779A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • 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

Definitions

  • the present invention relates to a process for the preparation of a fluorine-containing olefin, and more particularly to a process for producing 2,3,3,3-tetrafluoropropene.
  • fluorine refrigerant substitutes require an ozone depletion potential (ODP) of 0, a low greenhouse effect potential (GWP), and an atmospheric lifetime as short as possible.
  • ODP ozone depletion potential
  • GWP greenhouse effect potential
  • the first generation of refrigerants such as chlorofluorocarbon dichlorodifluoromethane (CCl 2 F 2 , CFC-12) have been eliminated due to ODP of around 1.
  • hydrochlorofluorocarbon-chlorodifluoromethane CHClF 2 , HCFC-22
  • the third generation refrigerant hydrofluorocarbon 1,1,1,2-tetrafluoroethane (CF 3 CH 2 F, HFC-134a) is widely used in automotive air conditioners, home appliances and industrial refrigeration equipment, and can also be used for foaming. , fire fighting, aerosol and cleaning industries.
  • HFO-1234yf is used instead of HFC-134a refrigerant, car manufacturers can continue to use the Mobile Air-Conditioning (MAC) system. Therefore, HFO-1234yf is considered to be a potential new generation of automotive refrigerant substitutes. It has been accepted by automobile manufacturers in Western Europe and has been gradually promoted in 2011.
  • DuPont and Dao Chemical Company reported the preparation of HFO-1234yf as early as the 1950s, when HFO-1234yf was mainly used to polymerize monomers and comonomers. In the early 1980s, Daikin also began the development of HFO-1234yf technology. After entering the 21st century, Honeywell and DuPont have done a lot of work on the development of HFO-1234yf and have applied for a large number of patents.
  • the trifluoropropene method is a four-step synthesis of HFO-1234yf.
  • the synthesis route is long, the requirements for the chlorination reaction equipment are high, the two-step saponification residual liquid is more, the fluorination reactor is severely corroded, the catalyst life is short, the total yield is low, and the synthesis cost is low. high.
  • the tetrachloropropene method can synthesize HFO-1234yf in two steps, the second step The temperature should be high, the conversion rate of the catalyst is low, and the life is short.
  • HFO-1234yf is synthesized from hexafluoropropylene (HFP) and hydrogen (H 2 ) as a raw material, generally through four steps of reaction: two-step hydrogenation and two-step dehydrofluorination. Therefore, the hexafluoropropylene process has many disadvantages such as many process steps, low yield, large equipment investment, and high cost.
  • the preparation method of the invention comprises: (a) contacting 1,1,1,2,3,3-hexafluoropropylene (HFP) with hydrogen (H 2 ) in the presence of a hydrogenation catalyst to produce 1,1,1 , 2,3,3-hexafluoropropane (HFC-236ea); (b) dehydrofluorination of HFC-236ea (HF) to produce 1,1,1,2,3-pentafluoropropene (HFO-1225ye); c) contacting HFO-1225ye with H 2 in the presence of a hydrogenation catalyst to produce 1,1,1,2,3-pentafluoropropane (HFC-245eb); (d) deactivating HFC-245eb to produce HFO -1234yf.
  • the invention is carried out in four steps, the reaction route is long
  • the invention name a method for preparing a fluorinated olefin.
  • the invention relates to a process for the preparation of fluorinated olefins, in particular to the preparation of 1,1,1,2-tetrafluoropropene and/or 1,1,1,2,3-pentafluorocarbon using a single series of four-unit operations.
  • a process for propylene the unit operation being (1) hydrogenation of a feedstock comprising hexafluoropropylene and optionally recycled 1,1,1,2,3-pentafluoropropene; (2) desired intermediate fluoroalkane Separating, the fluoroalkane such as 1,1,1,2,3,3-hexafluoropropane and/or 1,1,1,2,3-pentafluoropropane; (3) defluorination of an intermediate fluoroalkane, To produce the desired 1,1,1,2,3-pentafluoropropene and/or 1,1,1,2-tetrafluoropropene, followed by isolation of the desired product, and optionally 1,1, 1,2,3-pentafluoropropylene cycle.
  • the two-step hydrogenation of the invention is carried out in one reactor, and the two-step dehydrofluorination is carried out in one reactor, which requires relatively high catalysts and many reaction by-products.
  • FIG. 1 Another example is Chinese Patent Publication No. CN101671229A, published on March 17, 2010, the name of the invention: a method for preparing a fluorinated compound.
  • the invention comprises the steps of: (i) hydrogenating hexafluoropropylene to produce 1,1,1,2,3,3-hexafluoropropane; (ii) making 1,1,1,2 obtained in the previous step Dehydrofluorination of 3,3-hexafluoropropane to produce 1,2,3,3,3-pentafluoro-1-propene; (iii) 1, 2, 3, 3, 3 obtained in the previous step Hydrogenation of pentafluoro-1-propene to produce 1,1,1,2,3-pentafluoropropane; and (iv) dehydrofluorination of 1,1,1,2,3-pentafluoropropane obtained in the previous step To produce 2,3,3,3-tetrafluoro-1-propene.
  • Steps (ii) and (iv) are carried out using a mixture of water and potassium hydroxide at a temperature of 110 to 180 ° C.
  • potassium hydroxide accounts for 58 to 86 by weight of the mixture. %.
  • the invention aims at the deficiencies of the prior art, and provides a method for producing 2,3,3,3-tetrafluoropropene with short process route, low equipment investment, high conversion rate and high selectivity.
  • the technical solution adopted by the present invention is: a method for producing 2,3,3,3-tetrafluoropropene, comprising the following steps:
  • hexafluoropropylene and hydrogen are introduced into the reactor I, and the reaction is carried out under the action of a catalyst to obtain 1,1,1,2,3-pentafluoropropene, 1,1,1,2,3,3.
  • a first mixture of hexafluoropropane, hydrogen fluoride and a small amount of hexafluoropropylene the molar ratio of the hexafluoropropylene to hydrogen is 1:0.95 to 0.99, the space velocity is 200 to 1000 h-1, and the reaction temperature is 50 to 400 ° C;
  • step (b) The first mixture obtained in the step (a) is subjected to alkali washing, dried, and then introduced into the first rectification column, and the first rectification column is charged to obtain 1,1,1,2,3,3-hexafluoropropane.
  • 1,1,1,2,3-pentafluoropropene and a small amount of hexafluoropropylene are obtained, and 1,1,1,2,3,3-hexafluoropropane is recycled to the reactor I, and 1,1 1,2,3-pentafluoropropene and a small amount of hexafluoropropylene are introduced into the second rectification column, the second rectification column is topped to obtain hexafluoropropylene, and the column is charged with 1,1,1,2,3-five Fluoropropylene, recycling hexafluoropropylene to reactor I;
  • step (d) The second mixture obtained in the step (c) is subjected to alkali washing, dried, and then passed to a third rectification column, and the column is stirred to obtain 1,1,1,2,3-pentafluoropropane, which is recycled to the reactor. II. The top of the column gives the product 2,3,3,3-tetrafluoropropene.
  • the space velocity described in the step (a) is preferably from 400 to 800 h -1 , and the reaction temperature is preferably from 100 to 300 °C.
  • the space velocity described in the step (c) is preferably 600 to 1500 h -1 , and the temperature is preferably 120 to 400 °C.
  • the catalyst described in the reactor I is preferably divided into upper and lower stages, and the upper stage catalyst is preferably Pd/C, wherein the mass percentage of Pd is preferably 0.1 to 1%.
  • the lower stage catalyst is preferably chromium oxide.
  • reactor II in the catalyst is preferably charged into two sections, the upper section of catalyst is preferably a Pd / Al 2 O 3, wherein the mass percentage of Pd is preferably from 0.2 to 1.5%
  • the composition of the lower stage catalyst is preferably a mass percentage, and the composition thereof is preferably: 80 to 90% of chromium oxide and 10 to 20% of zinc oxide.
  • said reactor I and reactor II are preferably adiabatic reactors.
  • Both reactor I and reactor II of the present invention can be divided into two sections, each section being loaded with a different catalyst.
  • the raw materials hexafluoropropylene and H 2 are preheated by the preheater, they are introduced into the reactor I, and the reaction is carried out under the action of the upper and lower two stages of the catalyst.
  • the hexafluoropropylene is slightly excessively mixed, and the H 2 is completely converted, and the obtained mixture includes the reaction.
  • HFC-236ea undergoes a gas phase de-HF reaction, and the resulting mixture contains a mixture of HFC-236ea, HFO-1225ye, HF and a small amount of hexafluoropropylene, and the unreacted HFC-236ea and a small amount of hexafluoropropylene are separated after separation.
  • HFO-1225ye and fresh H 2 are preheated by preheater and then enter reactor II. The reaction is carried out under the action of the upper and lower two catalysts. H 2 is slightly excessive and HFO-1225ye is completely converted.
  • Reactor I carries out the hexafluoropropylene hydrogenation reaction and HFC-236ea de-HF reaction.
  • the hexafluoropropylene hydrogenation reaction is a strong exothermic reaction.
  • the reaction temperature has a great influence on the activity of the catalyst and the selectivity of the product, and the hot spot is too high. It will cause the hydrogenation catalyst to coke and deactivate.
  • the temperature of the hydrogenation reaction is lower than the temperature of the dehydrogenation reaction.
  • the temperature of the lower part is partly supplied by the heat generated by the upper hydrogenation reaction.
  • the heat of the upper hydrogenation reaction passes through the excess HFC-236ea. take away.
  • the temperature of the upper stage of the reactor I is controlled at 50 to 150 ° C, preferably 80 to 120 ° C, and the temperature of the lower stage is controlled at 250 to 400 ° C.
  • the space velocity increases, the amount of material contacted by the surface of the catalyst is increased, and the reaction load is increased.
  • the space velocity is selected to be 200-1000 h -1 , preferably 400-800 h -1 .
  • the hexafluoropropylene can be continuously returned to the reactor I, and the molar ratio of hexafluoropropylene to hydrogen is selected to be 1:0.95 to 0.99.
  • Reactor II carries out HFO-1225ye hydrogenation reaction and HFC-245eb dehydrogenation reaction, similar to the reaction of reactor I.
  • the heat in the lower part is also supplied by the heat generated by the upper hydrogenation reaction, which completely converts HFO-1225ye and avoids Subsequent to the problem of difficult separation of HFO-1225ye and HFO-1234yf, the temperature of the upper part of reactor II is controlled at 80-200 ° C, preferably 100-150 ° C, the temperature of the lower section is controlled by 300-500 ° C, and the space velocity is controlled by 300-2000 h -1 . Preferably, it is 600 to 1500 h -1 , and the molar ratio of H 2 and HFO-1225ye is 1:0.95 to 0.99.
  • the upper part of the reactor I and the reactor II of the present invention are filled with a noble metal Pd catalyst, the precious metal loading is too low, the catalytic activity is insufficient, and the Pd content and the catalyst activity have an optimum balance point.
  • the choice of carrier is crucial for the catalyst.
  • the hydrogenation of HFP is easier to carry out.
  • the activated carbon is used as the carrier.
  • the activated carbon has a high specific surface area, which is beneficial to make the supported catalytic active material less and the dispersion is high, and the activity is high. catalyst.
  • the catalyst used in the lower stage of the reactor I and the reactor II of the present invention may be a catalyst having chromium oxide as an active component known in the art, the lower catalyst of the reactor I is pure chromium oxide, and the lower catalyst of the reactor II is composed by mass percentage. It is: 80-90% of chromium oxide and 10-20% of zinc oxide.
  • the preparation method of the catalyst is: mixing the nitrates of chromium and zinc according to a certain ratio, formulating a dilute solution of a certain concentration, adding a precipitating agent to carry out the reaction, and then filtering, washing with water, drying, roasting, granulating and tableting.
  • the precursor, after fluorination, produces a catalyst, and the pretreatment of the catalyst can be carried out in other reactors.
  • the reactor I and the reactor II in the present invention may be of an adiabatic type or an isothermal type, preferably an adiabatic type, and the material of the reactor may be carbon steel or stainless steel.
  • the present invention has the following advantages:
  • the de-HF reaction fully utilizes the heat generated by the hydrogenation reaction, and the comprehensive utilization of heat reduces the energy consumption.
  • Figure 1 is a process flow diagram of the present invention.
  • 1 is reactor I
  • 2 is the first alkali washing tower
  • 3 is the first drying tower
  • 4 is the first rectification column
  • 5 is the second rectification column
  • 6 is the reactor II
  • 7 is The second alkali washing tower
  • 8 is a second drying tower
  • 9 is a third rectification column
  • 10 to 21 are pipelines.
  • the process of the present invention is shown in Figure 1.
  • the raw materials hexafluoropropylene and H 2 enter the reactor I, and the mixture obtained at the outlet of the reactor I after the reaction comprises HFC-236ea, HFO-1225ye, HF and a small amount of HFP, and the mixture is passed through the pipeline.
  • 10 enters the first alkali washing tower 2, and the mixture after removing HF enters the first drying tower 3 via the line 11, is dried, and then enters the first rectification column 4 via the line 12, and the tower is charged with HFC-236ea, and the reaction is circulated through the line 13 to the reaction.
  • the top of the tower gets HFO-1225ye and a small amount of HFP, enters the second rectification column 5 via line 14, the HFP is obtained at the top of the column, and is recycled to the reactor I through the line 15, and the HFA-1225ye is obtained through the line 16 and enters through the line 16 Reactor II, fresh H 2 is additionally added, and the mixture obtained at the outlet of the reactor II after the reaction includes HFC-245eb, HFO-1234yf, HF and a small amount of H 2 , and the mixture enters the second caustic scrubber 7 via line 17 to remove HF.
  • the subsequent mixture enters the second drying column 8 via line 18, is dried and then enters the third rectification column 9 via line 19, and the HFC-245eb obtained in the column is recycled to the reactor II via line 20, and the product HFO-1234yf is obtained at the top of the column.
  • H 2 is vented as non-condensable gas.
  • the molar ratio of hexafluoropropylene to H 2 was 1 :0.95, and the space velocity was 300 h -1 .
  • the outlet of the reactor I was subjected to alkali washing and sampled and analyzed. The results are shown in Table 1-1.
  • the reactor After pretreatment for 15 hours at a temperature of 350 ° C, a H 2 :N 2 molar ratio of 1:19, and a space velocity of 1200 ml g -1 (catal.) h -1 , the reactor is charged into the reactor.
  • the upper part of II the upper part of the reactor II is heated to 100 ° C
  • the lower stage is heated to 320 ° C
  • the HFO-1225ye and H 2 obtained in the reactor I are introduced into the reactor II, and the molar ratio of H 2 and HFO-1225ye is 1:0.96.
  • the space velocity was 500 h -1
  • the reactor II was subjected to alkali washing and sample analysis. The results are shown in Table 1-2.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1. 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of reactor I (adiabatic type, reactor material was carbon steel), and 150 ml of pretreated Pd/C catalyst (Pd content of 0.3% by mass) was charged into the reaction.
  • the upper part of the reactor I In the upper part of the reactor I, the upper part of the reactor I is heated to 80 ° C, the lower stage is heated to 280 ° C, hexafluoropropylene and H 2 are introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 is 1:0.95, and the space velocity is After 200 h -1 , the outlet of the reactor I was subjected to alkali washing and sampled and analyzed. The results are shown in Table 2-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 88% chromium oxide, 12% zinc oxide) was charged into the lower part of reactor II (adiabatic type, reactor material is carbon steel).
  • 180 ml of pretreated Pd/Al 2 O 3 catalyst Pd content of 0.5% by mass was charged into the upper stage, and the upper part of the reactor II was heated to 120 ° C, and the lower stage was heated to 300 ° C to obtain the HFO of the reactor I.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged to the lower stage of reactor I (adiabatic type, reactor material was carbon steel), and 150 ml of pretreated Pd/C catalyst (Pd content of 0.5% by mass) was loaded into the upper stage.
  • the upper part of the reactor I was heated to 100 ° C, the lower stage was heated to 320 ° C, and hexafluoropropylene and H 2 were introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 was 1 :0.97, and the space velocity was 800 h -1 .
  • the reactor I was subjected to alkaline washing and sample analysis. The results are shown in Table 2-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 88% chromium oxide, 12% zinc oxide) was charged into the lower part of reactor II (adiabatic type, reactor material is carbon steel).
  • 180 ml of pretreated Pd/Al 2 O 3 catalyst Pd content of 0.8% by mass was charged into the upper stage, and the upper stage of the reactor II was heated to 150 ° C, and the lower stage was heated to 400 ° C to obtain the HFO of the reactor I.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of the reactor I (adiabatic type, the reactor material was stainless steel), and 150 ml of the pretreated Pd/C catalyst (the mass percentage of Pd was 0.8%) was placed in the upper stage.
  • the upper part of the reactor I was heated to 120 ° C, the lower stage was heated to 310 ° C, and hexafluoropropylene and H 2 were introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 was 1 :0.97, and the space velocity was 600 h -1 .
  • the outlet of the reactor I was subjected to alkali washing and sampled and analyzed. The results are shown in Table 4-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 85% chromium oxide, 15% zinc oxide) was charged to the lower part of reactor II (adiabatic type, stainless steel reactor material), 180ml
  • the pretreated Pd/Al 2 O 3 catalyst (1.5% by mass of Pd) was charged into the upper stage, the upper stage of the reactor II was heated to 130 ° C, the lower stage was heated to 350 ° C, and the HFO-1225ye obtained in the reactor I was obtained.
  • H 2 was introduced into the reactor II, the molar ratio of H 2 and HFO-1225ye was 1:0.97, the space velocity was 1000 h -1 , and the reactor II was subjected to alkali washing after sampling, and the results are shown in Table 4-2.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of the reactor I (adiabatic type, the reactor material was stainless steel), and 150 ml of the pretreated Pd/C catalyst (Pd content of 1.0% by mass) was placed in the upper stage.
  • the upper part of the reactor I was heated to 150 ° C
  • the lower stage was heated to 330 ° C
  • hexafluoropropylene and H 2 were introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 was 1:0.98, and the space velocity was 1000 h -1 .
  • the outlet of the reactor I was subjected to alkali washing and sampled and analyzed. The results are shown in Table 5-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 90% chromium oxide, 10% zinc oxide) was charged into the lower part of reactor II (adiabatic type, stainless steel reactor material), 180 ml
  • the pretreated Pd/Al 2 O 3 catalyst (the mass percentage of Pd is 0.5%) is charged into the upper stage, the upper part of the reactor II is heated to 100 ° C, the lower stage is heated to 450 ° C, and the HFO-1225ye obtained in the reactor I is obtained.
  • H 2 was introduced into the reactor II, the molar ratio of H 2 and HFO-1225ye was 1:0.98, the space velocity was 1500 h -1 , and the reactor II was subjected to alkali washing after sampling, and the results are shown in Table 5-2.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of reactor I (adiabatic type, reactor material is stainless steel), and 150 ml of pretreated Pd/C catalyst (Pd content of 1.0% by mass) was placed in the upper stage.
  • the upper part of the reactor I was heated to 130 ° C, the lower stage was heated to 400 ° C, and hexafluoropropylene and H 2 were introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 was 1:0.98, and the space velocity was 500 h -1 .
  • the outlet of the reactor I was subjected to alkali washing and sampled and analyzed. The results are shown in Table 6-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 80% chromium oxide, 20% zinc oxide) was charged into the lower section of reactor II (adiabatic type, reactor material is stainless steel), 180 ml
  • the pretreated Pd/Al 2 O 3 catalyst (the mass percentage of Pd is 0.3%) is charged into the upper stage, the upper part of the reactor II is heated to 100 ° C, the lower stage is heated to 500 ° C, and the HFO-1225ye obtained in the reactor I is obtained.
  • H 2 was introduced into the reactor II, the molar ratio of H 2 and HFO-1225ye was 1:0.95, the space velocity was 2000 h -1 , and the reactor II was subjected to alkali washing after sampling, and the results are shown in Table 6-2.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of the reactor I (adiabatic type, the reactor material was stainless steel), and 150 ml of the pretreated Pd/C catalyst (Pd content of 0.3% by mass) was placed in the upper stage.
  • the upper part of the reactor I was heated to 100 ° C
  • the lower stage was heated to 300 ° C
  • hexafluoropropylene and H 2 were introduced into the reactor I.
  • the molar ratio of hexafluoropropylene to H 2 was 1 :0.99, and the space velocity was 300 h -1 .
  • the outlet of the reactor I was subjected to alkali washing and sampled and analyzed. The results are shown in Table 7-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 90% chromium oxide, 10% zinc oxide) was charged into the lower part of reactor II (adiabatic type, stainless steel reactor material), 180 ml
  • the pretreated Pd/Al 2 O 3 catalyst (the mass percentage of Pd is 0.5%) is charged into the upper stage, the upper part of the reactor II is heated to 150 ° C, the lower stage is heated to 300 ° C, and the HFO-1225ye obtained in the reactor I is obtained.
  • H 2 was introduced into the reactor II, the molar ratio of H 2 and HFO-1225ye was 1:0.99, the space velocity was 600 h -1 , and the reactor II was subjected to alkali washing after sampling, and the results are shown in Table 7-2.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of the reactor I (adiabatic type, the reactor material was stainless steel), and 150 ml of the pretreated Pd/C catalyst (Pd content of 0.3% by mass) was placed in the upper stage.
  • the upper part of the reactor I was heated to 120 ° C, the lower stage was heated to 250 ° C, and hexafluoropropylene and H 2 were introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 was 1 :0.99, and the space velocity was 500 h -1 .
  • the reactor I was subjected to alkali washing after sampling, and the results are shown in Table 8-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 90% chromium oxide, 10% zinc oxide) was charged into the lower part of reactor II (adiabatic type, stainless steel reactor material), 180 ml
  • the pretreated Pd/Al 2 O 3 catalyst (the mass percentage of Pd is 0.3%) is charged into the upper stage, the upper part of the reactor II is heated to 150 ° C, the lower stage is heated to 300 ° C, and the HFO-1225ye obtained by the reactor I is obtained.
  • the activation of the Cr 2 O 3 catalyst and the pretreatment of the Pd/C catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 catalyst was charged into the lower stage of the reactor I (adiabatic type, the reactor material was stainless steel), and 150 ml of the pretreated Pd/C catalyst (Pd content of 0.3% by mass) was placed in the upper stage.
  • the upper part of the reactor I was heated to 80 ° C, the lower stage was heated to 320 ° C, and hexafluoropropylene and H 2 were introduced into the reactor I, the molar ratio of hexafluoropropylene to H 2 was 1 :0.99, and the space velocity was 500 h -1 .
  • the reactor I was subjected to alkali washing after sampling, and the results are shown in Table 8-1.
  • the activation of Cr 2 O 3 +ZnO 2 and the pretreatment of the Pd/Al 2 O 3 catalyst were the same as in Example 1.
  • 200 ml of activated Cr 2 O 3 +ZnO 2 catalyst (by mass percentage, catalyst composition: 90% chromium oxide, 10% zinc oxide) was charged into the lower part of reactor II (adiabatic type, stainless steel reactor material), 180 ml
  • the pretreated Pd/Al 2 O 3 catalyst (the mass percentage of Pd is 0.5%) is charged into the upper stage, the upper part of the reactor II is heated to 100 ° C, the lower stage is heated to 350 ° C, and the HFO-1225ye obtained in the reactor I is obtained.
  • H 2 was introduced into the reactor II, the molar ratio of H 2 and HFO-1225ye was 1:0.95, the space velocity was 400 h -1 , and the reactor II was subjected to alkali washing after sampling, and the results are shown in Table 9-2.

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Abstract

本发明公开了一种2，3，3，3-四氟丙烯的生产方法，将六氟丙烯、氢气通入反应器I，在催化剂的作用下进行反应，得到含1，1，1，2，3-五氟丙烯、1，1，1，2，3，3-六氟丙烷、氟化氢和少量六氟丙烯的混合物，经碱洗、干燥、精馏，分别得到1，1，1，2，3，3-六氟丙烷、六氟丙烯和1，1，1，2，3-五氟丙烯，将1，1，1，2，3，3-六氟丙烷和六氟丙烯循环到反应器I，将1，1，1，2，3-五氟丙烯通入反应器II，同时通入氢气，在催化剂的作用下进行反应，得到含1，1，1，2，3-五氟丙烷、2，3，3，3-四氟丙烯、HF和少量H2的混合物，经碱洗、干燥、精馏，得到产品2，3，3，3-四氟丙烯。本发明具有工艺简单，三废少，产品收率和选择性高的优点。

Description

一种2，3，3，3-四氟丙烯的生产方法 技术领域
本发明涉及含氟烯烃的制备方法，尤其涉及一种2，3，3，3-四氟丙烯的生产方法。
背景技术
氟制冷剂替代品作为全球热门话题，要求其臭氧消耗潜值(ODP)为O，温室效应潜值(GWP)要低，大气寿命尽可能短。第一代制冷剂氟氯烃二氯二氟甲烷(CCl2F2，CFC-12)等由于ODP在1左右已被淘汰。作为第一代、第二代过渡性制冷剂替代品氢氟氯烃一氯二氟甲烷(CHClF2，HCFC-22)等，其ODP＞0，也在逐步被淘汰。第三代制冷剂氢氟烃1，1，1，2-四氟乙烷(CF3CH2F，HFC-134a)，广泛应用于汽车空调、家电及工商制冷设备，还可应用于发泡、灭火、气溶胶和清洗等行业。但是HFC-134a温室效应比较高(GWP＝1300)、大气寿命长，大量使用会引起全球气候变暖，也已经进入了倒计时阶段。
2，3，3，3-四氟丙烯(HFO-1234yf)作为单一工质制冷剂，具有优异的环境参数，GWP＝4，ODP＝0，寿命期气候性能(LCCP)低于HFC-134a，大气分解物与HFC-134a相同。而且其系统性能优于HFC-134a。若选用HFO-1234yf替代HFC-134a制冷剂，则汽车生产商就可以继续沿用原车载空调(Mobile Air-Conditioning，MAC)系统。所以HFO-1234yf被认为是较具潜力的新一代汽车制冷剂替代品，目前在西欧已被汽车生产商所接受，在2011年开始逐步推广。
HFO-1234yf优良的性能和广泛的用途，使其合成技术越来越引起了人们的关注。早在20世纪50年代杜邦和道化学公司就报道了HFO-1234yf的制备，当时HFO-1234yf主要用于聚合单体和共聚单体。20世纪80年代初，大金公司也开始进行了HFO-1234yf的技术开发。进入21世纪后，霍尼韦尔公司、杜邦公司对HFO-1234yf的研发进行了大量的工作，并申报了大量的专利。
HFO-1234yf的制备方法主要有三条路线：三氟丙烯法、六氟丙烯法和四氯丙烯法，其它方法都是这三条路线的分支路线。三氟丙烯法路线四步合成HFO-1234yf，合成路线长，对氯化反应设备要求高，两步皂化残液较多，氟化反应器腐蚀严重，催化剂寿命短，总收率低，合成成本高。四氯丙烯法路线可通过两步合成HFO-1234yf，第二步反 应温度高，催化剂的转化率低，寿命短。
以六氟丙烯(HFP)和氢气(H2)为原料合成HFO-1234yf，一般经过四步反应：两步加氢，两步脱氟化氢。因此六氟丙烯法存在工艺步骤多，收率低，设备投资大，成本高的缺点。
如中国专利公开号CN102026947A，公开日2011年4月20日，发明名称：制备2，3，3，3-四氟丙烯的方法。该发明的制备方法包括：(a)在氢化催化剂的存在下使1，1，1，2，3，3-六氟丙烯(HFP)与氢气(H2)接触，以产生1，1，1，2，3，3-六氟丙烷(HFC-236ea)；(b)使HFC-236ea脱氟化氢(HF)以产生1，1，1，2，3-五氟丙烯(HFO-1225ye)；(c)在氢化催化剂的存在下使HFO-1225ye与H2接触，以产生1，1，1，2，3-五氟丙烷(HFC-245eb)；(d)使HFC-245eb脱HF以产生HFO-1234yf。该发明分四步进行，反应路线长，总的收率不高，设备投资大。
又如中国专利公开号CN101544536A，公开日2009年9月30日，发明名称：制备氟化烯烃的方法。该发明涉及制备氟化烯烃的方法，具体而言，提供了利用单一系列的四单元操作制备1，1，1，2-四氟丙烯和/或1，1，1，2，3-五氟丙烯的方法，所述单元操作是(1)包含六氟丙烯和任选循环的1，1，1，2，3-五氟丙烯的原料的加氢；(2)期望的中间氟代烷烃的分离，所述氟代烷烃例如1，1，1，2，3，3-六氟丙烷和/或1，1，1，2，3-五氟丙烷；(3)中间氟代烷烃脱氟化氢，以制备得到期望的1，1，1，2，3-五氟丙烯和/或1，1，1，2-四氟丙烯，接着再分离出期望的产物，以及任选地将1，1，1，2，3-五氟丙烯循环。该发明两步加氢在一个反应器进行，两步脱氟化氢在一个反应器进行，对催化剂的要求比较高，反应副产物多。
又如中国专利公开号CN101671229A，公开日2010年3月17日，发明名称：氟化化合物的制备方法。该发明包括如下步骤：(i)使六氟丙烯氢化以产生1，1，1，2，3，3-六氟丙烷；(ii)使在前一步骤中得到的1，1，1，2，3，3-六氟丙烷脱氟化氢以产生1，2，3，3，3-五氟-1-丙烯；(iii)使在前一步骤中得到的1，2，3，3，3-五氟-1-丙烯氢化以产生1，1，1，2，3-五氟丙烷；和(iv)使在前一步骤中得到的1，1，1，2，3-五氟丙烷脱氟化氢以产生2，3，3，3-四氟-1-丙烯。在110～180℃的温度下，使用水和氢氧化钾的混合物进行步骤(ii)和(iv)，在该水和氢氧化钾的混合物中，氢氧化钾占所述混合物的58～86重量％。不足之处是工艺路线长，液相脱氟化氢，三废较多，收率低，反应器内部腐蚀严重。
发明内容
本发明针对现有技术的不足之处，提供一种工艺路线短、设备投资小、转化率和选择性高的2，3，3，3-四氟丙烯的生产方法。
为了解决上述技术问题，本发明采用的技术方案为：一种2，3，3，3-四氟丙烯的生产方法，包括以下步骤：
(a)将六氟丙烯和氢气通入反应器I，在催化剂的作用下进行反应，得到含1，1，1，2，3-五氟丙烯、1，1，1，2，3，3-六氟丙烷、氟化氢和少量六氟丙烯的第一混合物，所述六氟丙烯和氢气的摩尔比为1∶0.95～0.99，空速为200～1000h-1，反应温度为50～400℃；
(b)将步骤(a)得到的第一混合物经碱洗、干燥后通入第一精馏塔，第一精馏塔塔釜得到1，1，1，2，3，3-六氟丙烷，塔顶得到1，1，1，2，3-五氟丙烯和少量的六氟丙烯，将1，1，1，2，3，3-六氟丙烷循环到反应器I，将1，1，1，2，3-五氟丙烯和少量的六氟丙烯通入第二精馏塔，第二精馏塔塔顶得到六氟丙烯，塔釜得到1，1，1，2，3-五氟丙烯，将六氟丙烯循环到反应器I；
(c)将步骤(b)得到的1，1，1，2，3-五氟丙烯通入反应器II，同时通入氢气，在催化剂的作用下进行反应，得到含1，1，1，2，3-五氟丙烷、2，3，3，3-四氟丙烯、HF和少量H2的第二混合物，所述氢气和1，1，1，2，3-五氟丙烯的摩尔比为1∶0.95～0.99，空速为300～2000h-1，反应温度为80～500℃；
(d)将步骤(c)得到的第二混合物经碱洗、干燥后通入第三精馏塔，塔釜得到1，1，1，2，3-五氟丙烷，将其循环到反应器II，塔顶得到产品2，3，3，3-四氟丙烯。
作为本发明的优选实施方式，步骤(a)中所述的空速优选为400～800h-1，反应温度优选为100～300℃。
作为本发明的优选实施方式，步骤(c)中所述的空速优选为600～1500h-1，温度优选为120～400℃。
作为本发明的优选实施方式，反应器I中所述的催化剂优选分为上下两段装填，所述上段催化剂优选为Pd/C，其中Pd的质量百分含量优选为0.1～1％，所述下段催化剂优选为氧化铬。
作为本发明的优选实施方式，反应器II中所述的催化剂优选分为上下两段装填，所述上段催化剂优选为Pd/Al2O3，其中Pd的质量百分含量优选为0.2～1.5％，所述下段催化剂按质量百分比，其组成优选为：氧化铬80～90％，氧化锌10～20％。
作为本发明的优选实施方式，所述的反应器I和反应器II优选为绝热反应器。
本发明反应器I和反应器II都可分为两段，每段装填不同的催化剂。原料六氟丙烯和H2经预热器预热后，进入反应器I中，在上、下两段催化剂的作用下进行反应，六氟丙烯稍微过量，H2完全转化，得到的混合物包括反应生成的HFC-236ea及少量未反应的六氟丙烯。该混合物进入下段，HFC-236ea进行气相脱HF反应，得到的混合物含HFC-236ea、HFO-1225ye、HF和少量六氟丙烯的混合物，分离后未反应的HFC-236ea和少量六氟丙烯返回到反应器I中，HFO-1225ye和新鲜的H2经预热器预热后进入反应器II，在上、下两段催化剂的作用下进行反应，H2稍微过量，HFO-1225ye完全转化，得到的混合物包括HFO-1234yf、HFC-245eb、HF和少量H2，分离后得到产品HFO-1234yf，未反应的HFC-245eb返回到反应器II中，少量H2放空处理。
反应器I进行六氟丙烯加氢反应和HFC-236ea脱HF反应，六氟丙烯加氢反应是强放热反应，反应温度对催化剂的活性和产物的选择性有较大的影响，热点过高会导致加氢催化剂结焦而失活，加氢反应的温度比脱HF反应的温度低，下段的温度一部分要靠上段加氢反应产生的热量供给，上段加氢反应的热量通过过量的HFC-236ea带走。反应器I上段的温度控制在50～150℃，优选80～120℃，下段的温度控制250～400℃。空速增加，单位催化剂表面接触的物料多，反应的负荷提高，综合考虑选择空速为200～1000h-1，优选为400～800h-1。本发明为了让H2完全转化，避免后续的H2分离问题，让六氟丙烯适当过量，可以继续返回到反应器I，选择六氟丙烯和氢气的摩尔比为1∶0.95～0.99。
反应器II进行HFO-1225ye加氢反应和HFC-245eb脱HF反应，和反应器I的反应类似，下段的部分热量也是靠上段加氢反应产生的热量供给，让HFO-1225ye完全转化，避免了后续HFO-1225ye和HFO-1234yf分离难的问题，反应器II上段的温度控制在80～200℃，优选100～150℃，下段的温度控制300～500℃，空速控制300～2000h-1，优选为600～1500h-1，H2和HFO-1225ye的摩尔比为1∶0.95～0.99。
本发明反应器I和反应器II上段装填贵金属Pd催化剂，贵金属负载量过低，催化活性不够，Pd的含量和催化剂的活性有一个最佳的平衡点。载体的选择对催化剂是至关重要的，HFP的加氢较易进行，选择活性炭做载体，活性炭具有很高的比表面积，有利于使负载的催化活性物质少而分散度高，制得高活性催化剂。HFO-1225ye的加氢较为困难，Al2O3载体具有较强的酸性，活性组分Pd在载体上的分散度更好，Al2O3载体的机械强度高，催化剂寿命长。通过试验发现，反应器I上段装填Pd/C催化剂，Pd的 质量百分含量为0.1～1％，反应器II上段装填Pd/Al2O3，Pd的质量百分含量为0.2～1.5％，催化剂的预处理可以在其它反应器进行。
本发明反应器I和反应器II下段所用催化剂可采用本领域已知的氧化铬为活性组分的催化剂，反应器I下段催化剂为纯的氧化铬，反应器II下段催化剂按质量百分比，其组成为：氧化铬80～90％，氧化锌10～20％。催化剂的制备方法为：将铬和锌的硝酸盐按一定的配比混合，配成一定浓度的稀溶液，加入沉淀剂进行反应，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，催化剂的预处理可以在其它反应器进行。
本发明中的反应器I和反应器II可采用绝热型式或等温型式，优选绝热型式，反应器的材质可以选用碳钢或者不锈钢。
与现有技术相比，本发明具有以下优点：
1、两步气相法路线，工艺流程简单，三废少；
2、转化率和选择性高，六氟丙烯的转化率＞99％，HFO-1225ye的转化率100％；HFC-236ea和HFC-245eb的选择性100％。
3、反应器I H2完全转化，反应器IIHFO-1225ye完全转化，解决了未反应的H2和HFO-1225ye的分离问题；
4、脱HF反应充分利用加氢反应产生的热量，热量综合利用，降低了能耗。
附图说明
图1为本发明的工艺流程图。
如图所示：1为反应器I，2为第一碱洗塔，3为第一干燥塔，4为第一精馏塔，5为第二精馏塔，6为反应器II，7为第二碱洗塔，8为第二干燥塔，9为第三精馏塔，10～21为管线。
具体实施方式
本发明流程如图1所示，原料六氟丙烯、H2进入反应器I，反应后在反应器I出口 得到的混合物包括HFC-236ea、HFO-1225ye、HF和少量的HFP，该混合物经管线10进入第一碱洗塔2，去除HF后的混合物经管线11进入第一干燥塔3，干燥后经管线12进入第一精馏塔4，塔釜得到HFC-236ea，经管线13循环到反应器I，塔顶得到HFO-1225ye和少量的HFP，经管线14进入第二精馏塔5，塔顶得到HFP，通过管线15循环到反应器I，塔釜得到HFO-1225ye，通过管线16进入反应器II，新鲜H2另外加入，反应后在反应器II出口得到的混合物包括HFC-245eb、HFO-1234yf、HF和少量H2，该混合物经管线17进入第二碱洗塔7，去除HF后的混合物经管线18进入第二干燥塔8，干燥后经管线19进入第三精馏塔9，塔釜得到的HFC-245eb经管线20循环到反应器II，塔顶得到产品HFO-1234yf，H2作为不凝气放空。
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 Cr2O3催化剂在温度350℃条件下，通入HF氟化30小时，得到活化后的Cr2O3催化剂，然后将活化后的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为碳钢)的下段，将150m1Pd/C催化剂(Pd的质量百分含量为0.1％)在温度350℃，H2∶N2摩尔比1∶19，空速1200ml g-1(catal.)h-1条件下预处理15小时，然后装入反应器I上段，将反应器I上段升温到50℃，下段升温到300℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.95，空速为300h-1，反应器I出口碱洗后取样分析，结果如表1-1。
表1-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 36.2 63.5 0.3
将200ml Cr2O3+ZnO2(按质量百分比，催化剂组成为：氧化铬90％，氧化锌10％)催化剂在温度350℃条件下，通入HF氟化30小时，得到活化后的Cr2O3+ZnO2催化剂，然后将活化后的Cr2O3+ZnO2催化剂装入反应器II(绝热型式，反应器材质为碳钢)的下段，将180ml Pd/Al2O3催化剂(Pd的质量百分含量为0.3％)在温度350℃，H2∶N2摩尔比1∶19，空速1200ml g-1(catal.)h-1条件下预处理15小时后，装入反应器II上段，将反应器II上段升温到100℃，下段升温到320℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.96，空速为500h-1，反应器II出口碱 洗后取样分析，结果如表1-2。
表1-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 28.3 71.7
实施例2
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为碳钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为0.3％)装入反应器I上段，将反应器I上段升温到80℃，下段升温到280℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.95，空速为200h-1，反应器I出口碱洗后取样分析，结果如表2-1。
表2-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 42.5 57.3 0.2
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬88％，氧化锌12％)装入反应器II(绝热型式，反应器材质为碳钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为0.5％)装入上段，将反应器II上段升温到120℃，下段升温到300℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.95，空速为800h-1，反应器II出口碱洗后取样分析，结果如表2-2。
表2-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 31.7 68.3
实施例3
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为碳钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为0.5％)装入上段，将反应器I上段升温到100℃，下段升 温到320℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.97，空速为800h-1，反应器I出口碱洗后取样分析，结果如表2-1。
表3-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 54.3 45.6 0.1
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬88％，氧化锌12％)装入反应器II(绝热型式，反应器材质为碳钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为0.8％)装入上段，将反应器II上段升温到150℃，下段升温到400℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.97，空速为800h-1，反应器II出口碱洗后取样分析，结果如表3-2。
表3-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 56.8 43.2
实施例4
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为不锈钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为0.8％)装入上段，将反应器I上段升温到120℃，下段升温到310℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.97，空速为600h-1，反应器I出口碱洗后取样分析，结果如表4-1。
表4-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 57 42.8 0.2
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬85％，氧化锌15％)装入反应器II(绝热型式，反应器材质为不锈钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为1.5％)装入上段，将反应器II上段升温到130℃，下段升温到 350℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.97，空速为1000h-1，反应器II出口碱洗后取样分析，结果如表4-2。
表4-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 61.5 38.5
实施例5
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为不锈钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为1.0％)装入上段，将反应器I上段升温到150℃，下段升温到330℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.98，空速为1000h-1，反应器I出口碱洗后取样分析，结果如表5-1。
表5-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 68.4 31.5 0.1
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬90％，氧化锌10％)装入反应器II(绝热型式，反应器材质为不锈钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为0.5％)装入上段，将反应器II上段升温到100℃，下段升温到450℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.98，空速为1500h-1，反应器II出口碱洗后取样分析，结果如表5-2。
表5-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 79.7 20.3
实施例6
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为不锈钢)的下段，150ml预处理的Pd/C 催化剂(Pd的质量百分含量为1.0％)装入上段，将反应器I上段升温到130℃，下段升温到400℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.98，空速为500h-1，反应器I出口碱洗后取样分析，结果如表6-1。
表5-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 74.4 25.4 0.2
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬80％，氧化锌20％)装入反应器II(绝热型式，反应器材质为不锈钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为0.3％)装入上段，将反应器II上段升温到100℃，下段升温到500℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.95，空速为2000h-1，反应器II出口碱洗后取样分析，结果如表6-2。
表6-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 84.6 15.4
实施例7
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为不锈钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为0.3％)装入上段，将反应器I上段升温到100℃，下段升温到300℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.99，空速为300h-1，反应器I出口碱洗后取样分析，结果如表7-1。
表7-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 61.4 38.5 0.1
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬90％，氧化锌10％)装入反应器II(绝热型式，反应器材质为不锈钢)的下段，180ml预处理的Pd/Al2O3催化剂 (Pd的质量百分含量为0.5％)装入上段，将反应器II上段升温到150℃，下段升温到300℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.99，空速为600h-1，反应器II出口碱洗后取样分析，结果如表7-2。
表7-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 62.4 37.6
实施例8
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催化剂装入反应器I(绝热型式，反应器材质为不锈钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为0.3％)装入上段，将反应器I上段升温到120℃，下段升温到250℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.99，空速为500h-1，反应器I出口碱洗后取样分析，结果如表8-1。
表8-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 52.7 47.2 0.1
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬90％，氧化锌10％)装入反应器II(绝热型式，反应器材质为不锈钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为0.3％)装入上段，将反应器II上段升温到150℃，下段升温到300℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.95，空速为600h-1，反应器II出口碱洗后取样分析，结果如表8-2。
表8-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 56.7 43.3
实施例9
Cr2O3催化剂的活化和Pd/C催化剂的预处理同实施例1。将200ml活化的Cr2O3催 化剂装入反应器I(绝热型式，反应器材质为不锈钢)的下段，150ml预处理的Pd/C催化剂(Pd的质量百分含量为0.3％)装入上段，将反应器I上段升温到80℃，下段升温到320℃，将六氟丙烯和H2通入反应器I，六氟丙烯和H2的摩尔比为1∶0.99，空速为500h-1，反应器I出口碱洗后取样分析，结果如表8-1。
表9-1反应器I出口有机物分析数据
组分 HFO-1225ye HFC-236ea HFP
含量(％) 64.1 35.8 0.1
Cr2O3+ZnO2的活化和Pd/Al2O3催化剂的预处理同实施例1。将200ml活化的Cr2O3+ZnO2催化剂(按质量百分比，催化剂组成为：氧化铬90％，氧化锌10％)装入反应器II(绝热型式，反应器材质为不锈钢)的下段，180ml预处理的Pd/Al2O3催化剂(Pd的质量百分含量为0.5％)装入上段，将反应器II上段升温到100℃，下段升温到350℃，将反应器I得到的HFO-1225ye和H2通入反应器II，H2和HFO-1225ye的摩尔比为1∶0.95，空速为400h-1，反应器II出口碱洗后取样分析，结果如表9-2。
表9-2反应器II出口有机物分析数据
组分 HFO-1234yf HFC-245eb
含量(％) 58.4 41.6

Claims (6)

  1. 一种2，3，3，3-四氟丙烯的生产方法，其特征在于包括以下步骤：
    (a)将六氟丙烯和氢气通入反应器I，在催化剂的作用下进行反应，得到含1，1，1，2，3-五氟丙烯、1，1，1，2，3，3-六氟丙烷、氟化氢和少量六氟丙烯的第一混合物，所述六氟丙烯和氢气的摩尔比为1∶0.95～0.99，空速为200～1000h-1，反应温度为50～400℃；
    (b)将步骤(a)得到的第一混合物经碱洗、干燥后通入第一精馏塔，第一精馏塔塔釜得到1，1，1，2，3，3-六氟丙烷，塔顶得到1，1，1，2，3-五氟丙烯和少量的六氟丙烯，将1，1，1，2，3，3-六氟丙烷循环到反应器I，将1，1，1，2，3-五氟丙烯和少量的六氟丙烯通入第二精馏塔，第二精馏塔塔顶得到六氟丙烯，塔釜得到1，1，1，2，3-五氟丙烯，将六氟丙烯循环到反应器I；
    (c)将步骤(b)得到的1，1，1，2，3-五氟丙烯通入反应器II，同时通入氢气，在催化剂的作用下进行反应，得到含1，1，1，2，3-五氟丙烷、2，3，3，3-四氟丙烯、HF和少量H2的第二混合物，所述氢气和1，1，1，2，3-五氟丙烯的摩尔比为1∶0.95～0.99，空速为300～2000h-1，反应温度为80～500℃；
    (d)将步骤(c)得到的第二混合物经碱洗、干燥后通入第三精馏塔，塔釜得到1，1，1，2，3-五氟丙烷，将其循环到反应器II，塔顶得到产品2，3，3，3-四氟丙烯。
  2. 根据权利要求1所述的2，3，3，3-四氟丙烯的生产方法，其特征在于步骤(a)中所述的空速为400～800h-1，反应温度为100～300℃。
  3. 根据权利要求1所述的2，3，3，3-四氟丙烯的生产方法，其特征在于步骤(c)中所述的空速为600～1500h-1，温度为120～400℃。
  4. 根据权利要求1所述的2，3，3，3-四氟丙烯的生产方法，其特征在于反应器I中所述的催化剂分为上下两段装填，所述上段催化剂为Pd/C，其中Pd的质量百分含量为0.1～1％，所述下段催化剂为氧化铬。
  5. 根据权利要求1所述的2，3，3，3-四氟丙烯的生产方法，其特征在于反应器II中所述的催化剂分为上下两段装填，所述上段催化剂为Pd/Al2O3，其中Pd的质量百分含量为0.2～1.5％，所述下段催化剂按质量百分比，其组成为：氧化铬80～90％，氧化锌10～20％。
  6. 根据权利要求1所述的2，3，3，3-四氟丙烯的生产方法，其特征在于所述的反应器 I和反应器II为绝热反应器。
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CN105130743A (zh) 2015-12-09
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