WO2016197280A1 - 一种联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法 - Google Patents
一种联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法 Download PDFInfo
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- WO2016197280A1 WO2016197280A1 PCT/CN2015/000654 CN2015000654W WO2016197280A1 WO 2016197280 A1 WO2016197280 A1 WO 2016197280A1 CN 2015000654 W CN2015000654 W CN 2015000654W WO 2016197280 A1 WO2016197280 A1 WO 2016197280A1
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
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- 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
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- 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
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- This invention relates to a process for the preparation of fluoroolefins, and more particularly to a process for the co-production of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene.
- Hydrofluoroolefin such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3-tetrafluoropropene (HFO-1234ze), HFO-1234yf boiling point - 29.5 ° C, GWP value of 4, atmospheric life of 10 days, can be used as refrigerant, fire extinguishing agent, propellant, foaming agent, foaming agent, carrier fluid, polishing abrasive, power cycle working fluid.
- HFO-1234yf is in the field of refrigerants, as a fourth-generation refrigerant to replace 1,1,1,2-tetrafluoroethane (HFC-134a).
- HFO-1234ze has two types, Z type and E type.
- Z type has a boiling point of 9 ° C
- E type has a boiling point of -19 ° C
- GWP value is 6.
- Z type can be used as a foaming agent, and type E can be mixed with other substances. Refrigerant use.
- HFO-1234ze has many preparation routes, mainly 1,1,1,3,3-pentafluoropropane (HFC-245fa) gas phase de-HF method, 1,1,1,2,3-pentafluoropropane (HFC-245eb
- the gas phase de-HF method, etc., HFC-245eb raw materials are not easy to obtain, so the current use of HFC-245fa gas phase de-HF method to produce HFO-1234ze.
- the preparation methods of HFO-1234yf with industrial production prospects mainly include 3,3,3-trifluoropropene method, hexafluoropropylene method and 1,1,2,3-tetrachloropropene method.
- 3,3,3-trifluoropropene raw material 3,3,3-trifluoropropene is not easy to obtain, and the process route is long, three wastes are high, and the product cost is high; 1,1,2,3-tetrachloropropene method
- the preparation of 1,1,2,3-tetrachloropropene raw materials is complicated, and there are more three wastes in the process;
- hexafluoropropylene can be prepared by difluorochloromethane (HCFC-22), so HFO is synthesized from hexafluoropropylene.
- -1234yf is an ideal process route from the perspective of the industrial chain.
- HFO-1234yf from hexafluoropropylene (HFP) and hydrogen (H 2 ) is generally carried out in four steps: two-step hydrogenation, two-step dehydrofluorination, and the first reaction of hexafluoropropylene and hydrogen to form 1,1 1,2,3,3-hexafluoropropane (HFC-236ea), the second step of HFC-236ea gas phase or liquid phase saponification dehydrofluorination to obtain 1,1,1,2,3-pentafluoropropene (HFO-1225ye) In the third step, HFO-1225ye and hydrogen are reacted to form 1,1,1,2,3-pentafluoropropane (HFC-245eb).
- HFC-245eb is subjected to gas phase or liquid phase saponification dehydrofluorination to obtain HFO-1234yf. Therefore, the hexafluoropropylene process has many disadvantages such as many process steps, low yield, large equipment investment, and high cost.
- Chinese Patent Publication No. CN102267869A published on December 7, 2011, the invention name: 2,3,3,3-tetrafluoropropene synthesis method.
- the invention uses hexafluoropropylene as a starting material to prepare 1,1,1,2,3,3-hexafluoropropane by hydrogenation of a) 1,1,1,2,3,3-hexafluoropropylene; Preparation of 1,1,1,2,3-pentafluoropropene by dehydration of 1,1,1,2,3,3-hexafluoropropane; c) 1,1,1,2,3-pentafluoropropene catalytic addition Preparation of 1,1,1,2,3-pentafluoropropane by hydrogen; d) Preparation of 2,3,3,3-tetrafluoropropene by dehydrogenation of 1,1,1,2,3-pentafluoropropane.
- the invention is carried out in four steps, the reaction route is long, the total yield is not high,
- 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 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.
- the invention aims at the deficiencies of the prior art, and provides a co-production of 2,3,3,3-tetrafluoropropene and 1,3,3,3- with simple process, low investment, low energy consumption and high conversion rate.
- the technical solution adopted by the present invention is: a method for co-producing 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene, comprising the following steps:
- the C stage is reacted at the temperature of the B stage material to obtain a mixture containing 1,1,1,2,3-pentafluoropropane, 1,1,1,2,3,3-hexafluoropropane and hydrogen fluoride. ;
- step (b) The mixture obtained in the step (a) is introduced into the first rectification column, and 1,1,1,2,3,3-hexafluoropropane is obtained at the top of the column, and is recycled to the lower portion of the first stage of the first reactor.
- the 1,1,1,2,3-pentafluoropropane and hydrogen fluoride obtained in the column reactor are introduced into the second reactor, and the reaction is carried out under the action of a catalyst.
- the second reactor has a reaction temperature of 200 to 450 ° C, and the obtained 2 is obtained. a mixture of 3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, hydrogen fluoride and unreacted 1,1,1,2,3-pentafluoropropane;
- step (c) The mixture obtained in the step (b) is washed with water, washed with alkali, and dried to obtain 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene and 1,1,1.
- a mixture of 2,3-pentafluoropropane the mixture is passed to a second rectification column, and 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene are obtained at the top of the column.
- 1,1,1,2,3-pentafluoropropane recycling 1,1,1,2,3-pentafluoropropane to the second reactor;
- the molar ratio of hydrogen to hexafluoropropylene described in the step (a) is preferably 2 to 2.5:1, the space velocity is preferably 200 to 800 h -1 , and the reaction temperature of the A stage is preferably 55 to The reaction temperature in the B-stage is preferably from 180 to 250 ° C at 150 °C.
- the second reactor reaction temperature described in the step (b) is preferably from 250 to 400 °C.
- the stage A catalyst described in the step (a) is preferably Pd/Al 2 O 3 , wherein the mass percentage of Pd is preferably from 0.3 to 3%.
- the composition of the B-stage catalyst described in the step (a) is preferably a mass percentage, and the composition thereof is preferably 5 to 10% of chromium oxide, 80 to 90% of alumina, and 3 to 10% of zinc oxide.
- the C-stage catalyst described in the step (a) is preferably Pd/AlF 3 or Pd/C, wherein the mass percentage of Pd is preferably from 0.3 to 3%.
- the first reactor of the invention is divided into three sections A, B and C, each section is filled with different catalysts, and the raw materials hexafluoropropylene and H 2 are preheated by the preheater, and then enter the first reactor, in turn, in A, B.
- the reaction is carried out in the third stage of C, and the hexafluoropropylene is completely converted in the A stage, and the obtained mixture includes HFC-236ea formed by the reaction and an excessive amount of H 2 .
- the mixture enters the B stage, and the HFC-236ea undergoes a gas phase dehydrogenation reaction in the B stage, and the resulting mixture enters the C stage to continue the reaction, thereby obtaining a mixture containing HFC-236ea, HFC-245eb and a small amount of HF.
- the first reactor A is a hydrogenation reaction of hexafluoropropylene.
- the 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.
- the reaction temperature is increased, which contributes to the improvement of the activity of the catalyst.
- the hydrogenation of hexafluoropropylene is easier, the conversion of hexafluoropropylene and the selectivity of FC-236ea can reach 100% at a lower temperature.
- the reaction temperature should be lowered as much as possible to reduce the energy consumption.
- the reaction temperature in the A stage is 50 to 200 ° C, and the reaction temperature is preferably 55 to 150 ° C.
- the space velocity increases, the contact time between the reactant and the catalyst bed decreases, the activity of the catalyst decreases, and the complete conversion of hexafluoropropylene is ensured, and the space velocity is selected to be 100 to 1000 h -1 , preferably 200 to 800 h -1 .
- the molar ratio of H 2 and hexafluoropropylene has a great influence on the reaction, the molar ratio is low, the concentration of H 2 in the reaction system is low, the catalyst activity is low, and the molar ratio of H 2 and hexafluoropropylene is increased, which is effectively prevented.
- Catalyst coke formation occurs, the selectivity and stability of the catalyst are improved, and the activity of the catalyst is gradually increased. Considering that excess hydrogen can carry away the heat of reaction and provide hydrogenation feedstock for the C-stage reaction, hydrogen and hexafluoropropylene are selected.
- the molar ratio is from 2 to 5:1, preferably from 2 to 2.5:1.
- Part B is a gas phase dehydrofluorination reaction with high temperature and high conversion of HFC-236ea, but the selectivity of the target product is low.
- the reaction temperature is selected from 150 to 300 ° C, preferably 180 °. 250 ° C.
- the first reactor C section does not require external heating. By directly entering the material of the B section into the C section, the reaction temperature required for the C section is provided, thereby achieving comprehensive utilization of heat and reducing energy consumption.
- the reaction temperature of the second reactor is too low, the single-pass conversion of HFC-245eb is low, and the reaction moves in the direction of generating HFO-1234ze; the temperature is high, and the reaction moves in the direction of generating HFO-1234yf, which can be adjusted according to the needs of the product.
- the reaction temperature of the reactor Considering the conversion ratio and the composition of the finished product, the reaction temperature of the second reactor in the present invention is 200 to 450 ° C, and the reaction temperature is preferably 250 to 400 ° C.
- Pd loss Pd loss
- Pd sintering coking carbon deposits
- catalyst poisoning the main reasons for the deactivation of Pd catalysts.
- the moisture content in the raw material gas is too high, the loss of the active component Pd in the catalyst is caused.
- the temperature is high, the specific surface area of the catalyst and the micropores decrease, the active component Pd is supported in the pores of the carrier, the micropores are partially filled so that the number and the pore volume are reduced, and the high temperature also causes the sintering of the Pd particles.
- Impurities such as arsenic, sulfur, and carbon monoxide in the raw materials may also cause catalyst poisoning.
- the catalyst used in the first reactor B section and the second reactor of the present invention may employ a catalyst known in the art as chromium oxide as an active component, and the catalyst described in the first reactor section B is preferably a mass percentage, and its composition is preferably : Chromium oxide 5-10%, alumina 80-90%, zinc oxide 3-10%.
- the catalyst is prepared by impregnating a chloride salt of chromium and zinc on an alumina carrier, followed by drying, roasting, and chromium. And the chloride of zinc turns into an oxide, and after fluorination, a catalyst is obtained.
- the catalyst described in the second reactor preferably has a composition of: chromium oxide 60-80%, indium oxide 4-10%, nickel oxide 10-35%, and the catalyst is prepared by: chromium, indium and nickel.
- the chloride salt reacts with the precipitating agent to form a suspended solid of hydroxide, which is filtered, washed, dried and calcined to obtain chromium, aluminum and zinc oxide, and then granulated and tableted to obtain a catalyst precursor, which is prepared by fluorination. Get a catalyst. Activation of the catalyst can be carried out in other reactors.
- the first reactor and the second reactor in the present invention may be of an isothermal or adiabatic type, and the material of the reactor may be selected from acid corrosion resistant materials such as Inconel.
- a perforated baffle may be disposed between each section of the first reactor, and the catalyst is loaded in the order of C, B, and A from bottom to top.
- the shape of the catalyst is preferably spherical or columnar, and the reaction gas velocity is kept smooth to ensure uniform void ratio. Prevent the gas mixture from being dispersed in the axial and radial directions.
- the present invention has the following advantages:
- the process is simple, the first reactor is filled with three different catalysts, and three reactions can be performed, which simplifies the process flow;
- the conversion rate is high. By adjusting the molar ratio of H 2 to hexafluoropropylene in the reactor, and optimizing parameters such as catalyst, reaction temperature and space velocity, the conversion rate of hexafluoropropylene reaches 100%;
- the first reactor C section does not need external heating, by directly entering the B section of the material into the C section, providing the reaction temperature required for the C section, achieving comprehensive utilization of heat, reducing energy consumption;
- Figure 1 is a process flow diagram of the present invention.
- 1 is a preheater
- 2 is a first reactor
- 3 is a first rectification column
- 4 is a second reactor
- 5 is a water washing tower
- 6 is an alkali washing tower
- 7 is a drying tower
- 8 For the second rectification column
- 9 is the third rectification column
- 10 to 23 are pipelines.
- the process of the present invention is shown in FIG. 1.
- the first reactor 2 is divided into three sections A, B and C. Each section is filled with different catalysts.
- the first reactor 2 is passed through line 11, and the reaction is carried out in three stages A, B, and C.
- the hexafluoropropylene is completely converted in the A stage, and the resulting mixture includes HFC-236ea formed by the reaction and an excess of H 2 .
- the mixture enters the B stage, and the HFC-236ea undergoes a gas phase dehydrogenation reaction in the B stage, and the obtained mixture enters the C stage for hydrogenation reaction to obtain a mixture containing HFC-245eb, HFC-236ea, HF and H 2 , and the mixture is subjected to a mixture.
- the line 13 enters the first rectification column 3, and the HFC-236ea separated from the top of the first rectification column 3 is returned to the lower portion of the first reactor section A via the line 12, and the first rectification column 3 tower is HFC-245eb and HF via line 14 into the second reactor 4, a small amount of noncondensable gas vent H 2.
- the second reactor 4 outlet contains a mixture of HFO-1234yf, HFO-1234ze, HF and unreacted HFC-245eb which enters the water wash column 5 via line 15 and removes most of the HF mixture via line 16 into the caustic wash column 6, further The residual small amount of HF is removed, and the alkali-washed mixture is passed through line 17 to the drying tower 7 to remove a small amount of water in the mixture. After drying, the mixture containing HFO-1234yf, HFO-1234ze and HFC-245eb is passed through line 18 to the second fine.
- the temperature of the first stage of the first reactor was raised to 55 ° C
- the temperature of the B stage was raised to 200 ° C
- the temperature of the second reactor was raised to 300 ° C.
- the temperature was raised to 150 ° C at a normal temperature of 1 ° C / min
- the temperature was raised at 150 ° C or higher by 0.5 ° C / min.
- the feed reaction is started, and the hexafluoropropylene and H 2 are mixed and passed to a preheater.
- the molar ratio of H 2 to hexafluoropropylene is 2:1
- the space velocity is 300 h -1
- the first reactor outlet contains HFC-245eb.
- the reaction mixture of HFC-236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the A section of the first reactor, and the mixture of the column reactor enters the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled, and the composition of the organic matter was analyzed by gas chromatography as follows:
- the temperature of the first stage of the first reactor was raised to 70 ° C
- the temperature of the B stage was raised to 240 ° C
- the temperature of the second reactor was raised to 330 ° C.
- the temperature was raised to 150 ° C at a normal temperature of 1 ° C / min
- the temperature was raised at 150 ° C or higher by 0.5 ° C / min.
- the feed reaction is started, and hexafluoropropylene and H 2 are mixed and passed to a vaporizer.
- the molar ratio of H 2 to hexafluoropropylene is 2.5:1, the space velocity is 500 h -1 , and the first reactor outlet contains HFC-245eb, HFC.
- the reaction mixture of -236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the A stage of the first reactor, and the mixture of the column reactor enters the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled and analyzed by gas chromatography, and the organic composition thereof was as follows:
- the first reactor A is heated to 65 ° C
- the B section is heated to 250 ° C
- the second reactor is heated to 350 ° C
- the first reactor and the second reactor are heated, the normal temperature is 150 ° C, the heating rate is 1 ° C / Min, the heating rate above 150 ° C is 0.5 ° C / min.
- the first reactor and the second reactor were warmed up, they were dried by nitrogen gas for 2 hours.
- the feed reaction is started, and the hexafluoropropylene and H 2 are mixed and passed to a vaporizer.
- the molar ratio of H 2 to hexafluoropropylene is 3:1, the space velocity is 800 h -1 , and the first reactor outlet contains HFC-245eb, HFC.
- the reaction mixture of -236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the A stage of the first reactor, and the mixture of the column reactor enters the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled, and the composition of the organic matter was analyzed by gas chromatography as follows:
- the first reactor A was heated to 100 ° C
- the B section was heated to 210 ° C
- the second reactor was heated to 280. °C
- the temperature rise rate of 150 ° C or more is 0.5 ° C / min.
- the feed reaction is started, and the hexafluoropropylene and H 2 are mixed and passed to a vaporizer.
- the molar ratio of H 2 to hexafluoropropylene is 2.5:1, the space velocity is 200 h -1 , and the first reactor outlet contains HFC-245eb, HFC.
- the reaction mixture of -236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the A stage of the first reactor, and the mixture of the column reactor enters the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled, and the composition of the organic matter was analyzed by gas chromatography as follows:
- the first reactor A is heated to 80 ° C
- the B section is heated to 180 ° C
- the second reactor is heated to 250 ° C.
- the normal temperature is 150 ° C and the heating rate is 1 ° C / Min
- the heating rate above 150 ° C is 0.5 ° C / min.
- the first reactor A is heated to 150 ° C
- the B section is heated to 250 ° C
- the second reactor is heated to 400 ° C
- the first reactor and the second reactor are heated, the normal temperature is 150 ° C, the heating rate is 1 ° C / Min, the heating rate above 150 ° C is 0.5 ° C / min.
- the first reactor and the second reactor were warmed up, they were dried by nitrogen gas for 2 hours.
- the feed reaction is started, and the hexafluoropropylene and H 2 are mixed and passed to a vaporizer.
- the molar ratio of H 2 to hexafluoropropylene is 2.1:1, the space velocity is 300 h -1 , and the first reactor outlet contains HFC-245eb, HFC.
- the reaction mixture of -236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the A stage of the first reactor, and the mixture of the column reactor enters the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled, and the composition of the organic matter was analyzed by gas chromatography as follows:
- the feed reaction is started, and the hexafluoropropylene and H 2 are mixed and passed to a vaporizer.
- the molar ratio of H 2 to hexafluoropropylene is 2:1, the space velocity is 500 h -1 , and the first reactor outlet contains HFC-245eb, HFC.
- the reaction mixture of -236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the A stage of the first reactor, and the mixture of the column reactor enters the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled, and the composition of the organic matter was analyzed by gas chromatography as follows:
- the feed reaction is started, and the hexafluoropropylene and H2 are mixed and passed to a vaporizer.
- the molar ratio of H 2 to hexafluoropropylene is 2.2:1, the space velocity is 600 h -1 , and the first reactor outlet contains HFC-245eb, HFC-.
- the reaction mixture of 236ea and HF enters the first rectification column, and the HFC-236ea at the top of the column is recycled back to the lower portion of the first stage of the first reactor, and the mixture of the column is passed to the second reactor.
- the mixture of the first reactor and the second reactor outlet was sampled, and the composition of the organic matter was analyzed by gas chromatography as follows:
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Abstract
Description
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.1 | 0.05 | 53.4 | 46.25 | 0.2 |
第二反应器(%) | 60.3 | 39.2 | 0 | 0.3 | 0.2 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.2 | 0.2 | 48.5 | 50.8 | 0.3 |
第二反应器(%) | 65.1 | 34.6 | 0 | 0.2 | 0.1 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.1 | 0 | 66.8 | 32.6 | 0.5 |
第二反应器(%) | 69.2 | 30.3 | 0 | 0.1 | 0.4 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.1 | 0 | 45 | 54.8 | 0.1 |
第二反应器(%) | 62.8 | 36.6 | 0.1 | 0.2 | 0.3 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.1 | 0 | 37.8 | 62.0 | 0.2 |
第二反应器(%) | 71.1 | 28.5 | 0.1 | 0.2 | 0.1 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.1 | 0.1 | 28.5 | 71.2 | 0.1 |
第二反应器(%) | 58.5 | 41.0 | 0.1 | 0.2 | 0.2 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.1 | 0 | 44.8 | 55 | 0.1 |
第二反应器(%) | 68.9 | 30.8 | 0.1 | 0.2 | 0 |
组分 | HFO-1234yf | HFO-1234ze | HFC-236ea | HFC-245eb | 其它 |
第一反应器(%) | 0.2 | 0 | 39.5 | 60.2 | 0.1 |
第二反应器(%) | 56.8 | 43.1 | 0 | 0 | 0.1 |
Claims (7)
- 一种联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征在于包括以下步骤:(a)将六氟丙烯和氢气按摩尔比为2~5∶1预热后通入第一反应器,所述第一反应器分为A、B、C三段,每段装填不同的催化剂,六氟丙烯和氢气在空速为100~1000h-1的条件下依次在A、B、C三段中进行反应,所述A段反应温度为50~200℃,B段反应温度为150~300℃,C段在B段物料的温度下进行反应,得到含1,1,1,2,3-五氟丙烷、1,1,1,2,3,3-六氟丙烷和氟化氢的混合物;(b)将步骤(a)得到的混合物进入第一精馏塔,塔顶得到1,1,1,2,3,3-六氟丙烷,将其循环返回到第一反应器的A段下部,塔釜得到的1,1,1,2,3-五氟丙烷和氟化氢进入第二反应器,在催化剂的作用下进行反应,第二反应器反应温度为200~450℃,得到含2,3,3,3-四氟丙烯、1,3,3,3-四氟丙烯、氟化氢和未反应的1,1,1,2,3-五氟丙烷的混合物;(c)将步骤(b)得到的混合物经水洗、碱洗、干燥后得到含2,3,3,3-四氟丙烯、1,3,3,3-四氟丙烯和1,1,1,2,3-五氟丙烷的混合物,将该混合物进入第二精馏塔,塔顶得到2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯,塔釜得到1,1,1,2,3-五氟丙烷,将1,1,1,2,3-五氟丙烷循环到第二反应器;(d)将步骤(c)得到的2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯进入第三精馏塔,塔顶得到2,3,3,3-四氟丙烯产品,塔釜得到1,3,3,3-四氟丙烯产品。
- 根据权利要求1所述的联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征在于步骤(a)中所述的氢气和六氟丙烯的摩尔比为2~2.5∶1,空速为200~800h-1,A段反应温度为55~150℃,B段反应温度为180~250℃。
- 根据权利要求1所述的联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征在于步骤(b)中所述的第二反应器反应温度为250~400℃。
- 根据权利要求1所述的联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征在于步骤(a)中所述的A段催化剂为Pd/Al2O3,其中Pd的质量百分含量为0.3~3%。
- 根据权利要求1所述的联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征在于步骤(a)中所述的B段催化剂按质量百分比,其组成为:氧化铬5~10%,氧化铝80~90%,氧化锌3~10%。
- 根据权利要求1所述的联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征 在于步骤(a)中所述的C段催化剂为Pd/AlF3或Pd/C,其中Pd的质量百分含量为0.3~3%。
- 根据权利要求1所述的联产2,3,3,3-四氟丙烯和1,3,3,3-四氟丙烯的方法,其特征在于步骤(b)中所述的催化剂按质量百分比,其组成为:氧化铬60~80%,氧化铟4~10%,氧化镍10~35%。
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