CN112811978A - Preparation method of Z-1,3,3, 3-tetrafluoropropene - Google Patents
Preparation method of Z-1,3,3, 3-tetrafluoropropene Download PDFInfo
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Abstract
The invention discloses a preparation method of Z-1,3,3, 3-tetrafluoropropene, which takes 1,3,3, 3-tetrafluoropropene or/and 1,1,3, 3-tetrafluoropropadiene isomer thereof as a raw material and carries out gas-phase selective hydrogenation in the presence of a hydrogenation catalyst to obtain Z-1,3,3, 3-tetrafluoropropene. The invention is mainly used for efficiently and circularly producing the Z-1,3,3, 3-tetrafluoropropene in a gas phase continuous way.
Description
Technical Field
The invention relates to a method for preparing Z-1,3,3, 3-tetrafluoropropene with high conversion rate and high selectivity, in particular to a method for preparing Z-1,3,3, 3-tetrafluoropropene with high conversion rate and high selectivity by using 1-3,3, 3-tetrafluoropropene or/and 1,1,3, 3-tetrafluoropropene isomer as a raw material through gas-phase hydrogenation reaction, and a method for synthesizing 1-3,3, 3-tetrafluoropropene and 1,1,3, 3-tetrafluoropropene isomer.
Background
Since the compound energy of Z-1,3,3, 3-tetrafluoropropene is higher than that of E-1,3,3, 3-tetrafluoropropene, which is less stable than E-1,3,3, 3-tetrafluoropropene and therefore, in the gas-phase fluorination reaction of E-1-chloro-3, 3, 3-trifluoropropene or Z-1-chloro-3, 3, 3-trifluoropropene, the dehydrofluorination reaction of 1,1,1,3, 3-pentafluoropropane, the main product is E-1,3,3, 3-tetrafluoropropene, while the selectivity of the by-product Z-1,3,3, 3-tetrafluoropropene is too low, the content is much less than that of E-1,3,3, 3-tetrafluoropropene, and thus none of the above methods is an ideal route for the synthesis of Z-1,3,3, 3-tetrafluoropropene.
Currently, Z-1,3,3, 3-tetrafluoropropene is generally synthesized by using an isomerization reaction of E-1,3,3, 3-tetrafluoropropene.
U.S. Pat. No. 3, 99907 reports that E-1,3,3, 3-tetrafluoropropene isomerizes under the action of the chlorine radical provided by chlorine, the E-1,3,3, 3-tetrafluoropropene and chlorine species are in the ratio of 177.6/1, the reaction temperature is 650 ℃, the contact time is 4.9s, the conversion of E-1,3,3, 3-tetrafluoropropene is 28.1%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene is 92.2%. The route has the defects of low conversion rate of E-1,3,3, 3-tetrafluoropropene and low selectivity of Z-1,3,3, 3-tetrafluoropropene at high temperature (such as 650 ℃).
U.S. Pat. No. 3, 112103 reports that zirconium oxyfluoride catalyzes the isomerization of E-1,3,3, 3-tetrafluoropropene at 500 ℃ for 30s, resulting in a conversion of E-1,3,3, 3-tetrafluoropropene of 25.3% and a selectivity of Z-1,3,3, 3-tetrafluoropropene of 99.3%. The route has the problem of low conversion rate of E-1,3,3, 3-tetrafluoropropene at high temperature (such as 500 ℃).
CN101535228B reports that when E-1,3,3, 3-tetrafluoropropene is isomerized at 350 ℃ under the catalysis of chromium oxide gel, the contact time is 60s, the conversion rate of E-1,3,3, 3-tetrafluoropropene is 40.1%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene is 77.6%. The route has the defect that the selectivity of Z-1,3,3, 3-tetrafluoropropene is too low.
CN107614471A reports that alumina or zirconia catalyzes the isomerization reaction of E-1,3,3, 3-tetrafluoropropene, when the catalyst is alumina and the reaction temperature is 300 ℃, the contact time of E-1,3,3, 3-tetrafluoropropene is 15s, and when the cumulative charge of E-1,3,3, 3-tetrafluoropropene reaches 5133 g, the conversion rate of E-1,3,3, 3-tetrafluoropropene is 18.8 percent and the selectivity of Z-1,3,3, 3-tetrafluoropropene is 99.5 percent. The route has the defect that the conversion rate of E-1,3,3, 3-tetrafluoropropene is too low at a higher temperature (such as 300 ℃).
WO2010050373A2 reports that chromium oxyfluoride (the fluorine-containing content is 12.2 percent by mass) catalyzes E-1,3,3, 3-tetrafluoropropene to carry out isomerization reaction at 380 ℃, the ratio of the mass of the catalyst to the flow rate of the E-1,3,3, 3-tetrafluoropropene is 40 g.s/mL, the conversion rate of the E-1,3,3, 3-tetrafluoropropene is 40.7 percent, and the selectivity of the Z-1,3,3, 3-tetrafluoropropene is 64.4 percent. This route has the disadvantage that the selectivity for Z-1,3,3, 3-tetrafluoropropene is too low.
In summary, the above technical solution has a problem that the yield per pass of Z-1,3,3, 3-tetrafluoropropene is too low to be 31.1% at the maximum (see CN 101535228B). To date, no literature reports a method for synthesizing Z-1,3,3, 3-tetrafluoropropene with high conversion rate and high selectivity.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the background technology and provide the method which has high single-pass yield and high catalyst activity and can prepare the Z-1,3,3, 3-tetrafluoropropene with high selectivity.
In order to achieve the object of the present invention, the present invention provides a process for producing a catalyst for hydrogenation in the presence of a hydrogenation catalyst in a tubular reactor,or/and isomers thereofAnd carrying out gas phase selective hydrogenation reaction with hydrogen to obtain Z-1,3,3, 3-tetrafluoropropene. The reaction equation is as follows:
the hydrogenation catalyst consists of noble metal, auxiliary metal and carrier, wherein the noble metal is any one or more of elementary substances of palladium and platinum, the auxiliary is any one or more of elementary substances of bismuth, copper and iron, and the carrier is any one or more of metal fluorides of aluminum, iron, magnesium, calcium, barium, zinc and copper; the mass percentages of the noble metal, the auxiliary metal and the carrier are respectively 1-5%: 0.1-5%: 98.9-90 percent, and the sum of the mass percentages of the three is 1.
The preparation method of the hydrogenation catalyst comprises the following steps: dissolving soluble salts of precious metals and soluble salts of auxiliaries in water together, and adjusting the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain an impregnation solution, wherein the soluble salts of the precious metals are any one or more of palladium nitrate, palladium acetate, palladium chloride, platinum nitrate, platinum acetate, platinum chloride and chloroplatinic acid, and the soluble salts of the auxiliaries are any one or more of nitrates, chlorides and acetates of bismuth, copper and iron; dropwise adding the impregnation liquid to the carrier under the conditions of normal pressure and room temperature, maintaining the impregnation for 1-5 hours after the dropwise adding is finished, and filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 5-10 hours at 100-200 ℃ under the protection of nitrogen, then heating to 250-350 ℃ for roasting for 5-10 hours, and then activating for 8-20 hours at 200-300 ℃ by using a mixed gas with the molar ratio of nitrogen to hydrogen being 4: 1 to prepare the hydrogenation catalyst.
The reaction conditions of the gas phase selective hydrogenation reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 50-300 ℃, or/and isomers thereofThe mass ratio of hydrogen to substance is 1: 1 to 15, and the contact time is 1 to 100 s.
The reaction conditions of the gas phase selective hydrogenation reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-200 ℃,or/and isomers thereofThe mass ratio of hydrogen to substance is 1: 5 to 10, and the contact time is 10 to 100 s.
The above-mentionedThe synthesis method comprises the following steps: in the presence of an isomerization catalyst, the catalyst,isomerization reaction is carried out to obtainWherein the isomerization catalyst is any one of metal fluorine chloride or metal fluorine chloride oxide of Al, Mg, Ca, Ba, Cr, Fe, Co, Ni, Mo, W, Zn or Cu.
The preparation method of the isomerization catalyst comprises the following steps: placing the metal oxide in a reactor, wherein the reaction temperature is 300-500 ℃, and the mass ratio of the introduced substances is 1: 4, the mixed gas consisting of the fluorochloroalkane and the nitrogen, or the mass ratio of the introduced substances is 1: activating the mixed gas of the halogenated olefin of 4 and nitrogen for 4 to 20 hours, and stopping introducing the mixed gas to prepare the catalyst. Wherein the metal oxide is any one or more of chromium oxide, chromium dioxide, molybdenum trioxide, molybdenum dioxide, molybdenum trioxide, tungsten dioxide, tungsten trioxide, aluminum oxide, magnesium oxide, calcium oxide, barium oxide, ferric oxide, ferrous oxide, ferroferric oxide, cobalt oxide, nickel oxide, zinc oxide and copper oxide; the halogenated hydrocarbon is one or more of difluorodichloromethane, chlorodifluoromethane, dichlorofluoromethane, chloropentafluoroethane, 2, 2-dichloro-1, 1, 1-trifluoroethane, 1-chloro-1, 2,2, 2-tetrafluoroethane, 1-chloro-2, 2, 2-trifluoroethane, 2-chloro-1, 1,1, 2-tetrafluoropropane, 3-chloro-1, 1,1, 3-tetrafluoropropane and 2, 3-dichloro-1, 1, 1-trifluoropropane.
The reaction conditions of the isomerization reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 0-200 ℃, and the contact time of the tetrafluoro propadiene is 1-100 s.
SaidThe synthesis method comprises the following steps: in the presence of an alkali metal oxide or an alkaline earth metal oxide, of the formulaElimination reaction of the dicarboxylic acid halide to obtainThe reaction conditions are as follows: the reaction temperature is 100 to500℃,The amount of the substance to the alkali metal oxide or alkaline earth metal oxide is 1: 4-10, and the reaction time is 2-20 h; wherein R is1、R2Is any one of F, Cl, Br or I, the alkali metal oxide is one or more of lithium oxide, sodium oxide, potassium oxide, rubidium oxide or cesium oxide, and the alkaline earth metal oxide is one or more of magnesium oxide, calcium oxide, barium oxide or strontium oxide.
SaidThe synthesis method comprises the following steps: in the presence of an oxidation catalyst, of the formulaThe halogenated cyclopentene and oxygen or oxygen diluted by inert gas are subjected to oxidation reaction to obtain dicarboxylic halideThe oxidation catalyst is a catalyst in which silver oxide is loaded on one or more carriers of iron oxide, chromium oxide, zinc oxide, magnesium oxide, zirconium oxide, chromium fluoride, iron fluoride, zinc fluoride, magnesium fluoride and aluminum fluoride, wherein the mass percentages of the silver oxide and the carriers are respectively 0.1% -30%: 70 to 99.9 percent.
The preparation method of the oxidation catalyst comprises the following steps: dissolving a proper amount of silver nitrate in a proper amount of water according to the mass percentage composition of the silver oxide and the carrier, adding one or more carriers of iron oxide, chromium oxide, zinc oxide, magnesium oxide, zirconium oxide, chromium fluoride, iron fluoride, zinc fluoride, magnesium fluoride or aluminum fluoride, soaking for 18 hours, filtering, drying in an oven at 80 ℃ for 12-48 hours, and roasting at 500 ℃ for 5-20 hours under the protection of nitrogen to obtain the oxidation catalyst.
The reaction conditions of the oxidation reaction are as follows: the reaction temperature is 100-600 ℃,the molar ratio of the inert gas to the oxygen is 1: 1-10, the molar ratio of the inert gas to the oxygen is 0-5: 1, and the contact time is 0.01-100 s, wherein R1、R2The inert gas can be one or more of nitrogen, helium, argon and neon.
The selective hydrogenation reaction process of the invention belongs to a gas phase independent circulation continuous process method. Because the boiling point difference between the raw material and the reaction product is large, the raw material and the reaction product can be effectively separated by adopting a distillation mode of a distillation tower, the unreacted raw material is continuously recycled to the reactor to continuously participate in the reaction, and the main product Z-1,3,3, 3-tetrafluoropropene or the by-product E-1,3,3, 3-tetrafluoropropene and the 1,1,1, 3-tetrafluoropropane are respectively extracted out of the system. Wherein the boiling point of Z-1,3,3, 3-tetrafluoropropene is 9.8 ℃ (760 mmHg); the boiling point of E-1,3,3, 3-tetrafluoropropene is-18.95 ℃ (760 mmHg); boiling point of 1,1,1, 3-tetrafluoropropane is 29-30 deg.C (760 mmHg); the boiling point of 1,3,3, 3-tetrafluoropropene is-50 ℃ (760 mmHg); the boiling point of tetrafluoropropadiene is-37 deg.C (760 mmHg); the boiling point of hydrogen was-258.8 deg.C (760 mmHg).
The type of reactor used for the reaction of the present invention is not critical, and a tubular reactor, a fluidized bed reactor, etc. may be used. Alternatively, adiabatic reactors or isothermal reactors may be used.
The invention has the advantages that:
(1) the method has high single-pass yield of Z-1,3,3, 3-tetrafluoropropene synthesis;
(2) the hydrogenation catalyst has the characteristics of high activity and long service life;
(3) the invention adopts a gas phase method to prepare Z-1,3,3, 3-tetrafluoropropene, and carries out independent circulation on materials which are not completely reacted through a gas phase independent circulation process, so that the initial raw materials can be almost completely converted into the target product, and the target product is finally extracted from a process system, thereby not generating liquid waste and waste gas and realizing green production.
Drawings
FIG. 1 shows a flow chart of a process for producing Z-1,3,3, 3-tetrafluoropropene using 1,3,3, 3-tetrafluoropropene as a raw material.
The reference numerals in fig. 1 have the following meanings. Pipeline: 1. 2,3, 5, 7, 8, 10, 11, 13 and 14; a hydrogenation reactor: 4; a first distillation column: 6; a second distillation column: 9; a third distillation column: 12.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The present invention is described in further detail with reference to fig. 1. But not to limit the invention. Fresh 1,3,3, 3-tetrafluoropropine enters a hydrogenation reactor 4 filled with a hydrogenation catalyst through a pipeline 3 together with fresh hydrogen through a pipeline 2 and a mixture of 1,3,3, 3-tetrafluoropropine and hydrogen recycled through a pipeline 7 to carry out gas phase selective hydrogenation reaction, reaction product streams are Z-1,3,3, 3-tetrafluoropropene, E-1,3,3, 3-tetrafluoropropene, 1,1,1, 3-tetrafluoropropane and unreacted 1,3,3, 3-tetrafluoropropine and hydrogen, and the reaction product flows through a pipeline 5 to enter a first distillation tower 6 for separation; the components at the top of the first distillation tower 6 are 1,3,3, 3-tetrafluoro propine and hydrogen, and the components are continuously circulated to the hydrogenation reactor 4 through the pipeline 7 and the pipeline 3 for continuous reaction; the bottom components of the first distillation tower 6 are Z-1,3,3, 3-tetrafluoropropene, E-1,3,3, 3-tetrafluoropropene and 1,1,1, 3-tetrafluoropropane, and the components enter a second distillation tower 9 through a pipeline 8 for separation; the tower top component of the second distillation tower 9 is E-1,3,3, 3-tetrafluoropropene, and a high-purity byproduct E-1,3,3, 3-tetrafluoropropene can be obtained through subsequent deacidification, dehydration and rectification; the bottom components of the second distillation tower 9 are Z-1,3,3, 3-tetrafluoropropene and 1,1,1, 3-tetrafluoropropane, the Z-1,3, 3-tetrafluoropropene and the 1,1,1, 3-tetrafluoropropane enter a fourth distillation tower 12 through a pipeline 11 for separation, the bottom components of the Z-1,3, 3-tetrafluoropropane are led out through a pipeline 14, and high-purity by-products 1,1,1, 3-tetrafluoropropane can be obtained through subsequent deacidification, dehydration and rectification; the tower top component of the fourth distillation tower 12 is Z-1,3,3, 3-tetrafluoropropene which is led out through a pipeline 13, and the target product Z-1,3,3, 3-tetrafluoropropene can be obtained through deacidification, dehydration and rectification.
An analytical instrument: shimadzu GC-2010, column model InterCap1 (i.d. 0.25 mm; length 60 m; J & W Scientific Inc.).
Gas chromatographic analysis method: high purity helium and hydrogen were used as carrier gases. The temperature of the detector is 240 ℃, the temperature of the vaporization chamber is 150 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is raised to 240 ℃ at the rate of 20 ℃/min, and the temperature is kept for 10 minutes.
EXAMPLE 1 preparation of tetrafluoropropadiene
Step (1): according to the mass percentage composition of the silver oxide and the carrier, a proper amount of silver nitrate is dissolved in a proper amount of water, an aluminum fluoride carrier is added, the mixture is soaked for 18 hours, then filtered, dried in an oven at 80 ℃ for 24 hours, and then roasted at 400 ℃ for 10 hours under the protection of nitrogen, so that the oxidation catalyst is obtained. A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10ml of the oxidation catalyst 10% Ag prepared by the above method2O/AlF3. The reaction conditions are as follows: the reaction temperature is 260 ℃, and the molar ratio of the inert gases helium, oxygen and octafluorocyclopentene is 1: 1: 1, the contact time is 0.1s, and the reaction pressure is 0.1 MPa. Collecting reaction products by a sampling bag made of polytetrafluoroethylene materials, sampling from the sampling bag after 10 hours, and carrying out GC analysis, wherein the reaction result is as follows: the conversion of octafluorocyclopentene was 98.6% and the selectivity of hexafluoroglutaryl fluoride was 98.8%.
Step (2): adding 0.5mol of potassium oxide into a 1 liter high-pressure autoclave made of 316 materials, vacuumizing, rapidly adding 0.1mol of hexafluoroglutaryl fluoride at room temperature under stirring, heating to 200 ℃ after the materials are completely introduced, reacting for 10 hours, and collecting a gas-phase product tetrafluoropropadiene in the reaction system by using a 200mL small steel bottle made of 316 materials after the reaction is finished, wherein the yield is 99.1% and the purity is 99.6% (GC analysis).
Example 21 preparation of 3,3,3, 3-Tetrafluoropropyne
Preparation of isomerization catalyst: placing alumina in a reactor, and introducing the alumina into the reactor at the temperature of 400 ℃ in a mass ratio of 1: 4, activating the mixed gas consisting of monochlorodifluoromethane and nitrogen for 12 hours, and stopping introducing the mixed gas to prepare the catalyst.
A tubular reactor having an inner diameter of 1/2 inches and a length of 30cm and made of Incar was charged with 10mL of the catalyst prepared above. The reaction conditions are as follows: the reaction temperature is 20 ℃, the contact time of the tetrafluoro propadiene is 60s, and the reaction pressure is 0.1 MPa. After 10h of operation, the reaction product was collected and heated, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of tetrafluoropropadiene was 100%, and the selectivity of 1,3,3, 3-tetrafluoropropyne was 99.5%.
Example 3
Preparation of hydrogenation catalyst: according to Pd, Bi, AlF3The mass percentages of the three components are respectively 2%: 0.2%: dissolving palladium chloride and bismuth chloride together in water at 97.8%, and adjusting the pH value of the solution to 4-6 by using dilute hydrochloric acid to obtain an impregnation solution; adding the impregnation liquid to the AlF carrier under the conditions of normal pressure and room temperature3Dropwise adding, maintaining the impregnation for 4 hours after the dropwise adding is finished, and filtering and drying to obtain a catalyst precursor; drying the catalyst precursor for 8 hours at 120 ℃ under the protection of nitrogen, then heating to 300 ℃ for roasting for 8 hours, activating for 14 hours at 250 ℃ by using a mixed gas with the molar ratio of nitrogen to hydrogen being 4: 1 to prepare the hydrogenation catalyst, and confirming by XRD that the existence form of Pd and Bi in the hydrogenation catalyst is simple substance.
A tubular reactor having an inner diameter of 1/2 inches and a length of 30cm and made of Incar was charged with 10mL of the catalyst prepared above. The reaction conditions are as follows: the reaction temperature is 100 ℃, and the mass ratio of 1,3,3, 3-tetrafluoropropyne to hydrogen is 1: 10, the contact time is 30s and the reaction pressure is 0.1 MPa. After 10h operation, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,3,3, 3-tetrafluoro-propyne was 98.4%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.3%.
Example 4
The same operation as in example 3 was carried out, except that the reaction temperature was changed to 200 ℃, and the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.2%.
Example 5
The same operation as in example 3 was carried out, except that the reaction temperature was changed to 300 ℃, and the reaction results were: the conversion of 1,3,3, 3-tetrafluoropropyne was 100%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 85.8%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 10.3%, and the selectivity for 1,1,1, 3-tetrafluoropropane was 3.9%.
Example 6
The same operation as in example 3 was conducted, except that the reaction temperature was changed to 200 ℃, and the ratio of the amounts of 1,3,3, 3-tetrafluoropropene and hydrogen was changed to 1: 1, the reaction result is: the conversion of 1,3,3, 3-tetrafluoro-propyne was 72.3%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.7%.
Example 7
The same operation as in example 3 was conducted, except that the reaction temperature was changed to 200 ℃, and the ratio of the amounts of 1,3,3, 3-tetrafluoropropene and hydrogen was changed to 1: 5, the reaction result is: the conversion of 1,3,3, 3-tetrafluoro-propyne was 98.4%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.4%.
Example 8
The same operation as in example 3 was conducted, except that the reaction temperature was changed to 200 ℃, and the ratio of the amounts of 1,3,3, 3-tetrafluoropropene and hydrogen was changed to 1: 15, the reaction result is: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 97.5%.
Example 9
The same operation as in example 3, except that the reaction temperature was changed to 200 ℃ and the contact time was changed to 1s, the reaction result was: the conversion of 1,3,3, 3-tetrafluoro-propyne was 38.4% and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.6%.
Example 10
The same operation as in example 3, except that the reaction temperature was changed to 200 ℃ and the contact time was changed to 10s, the reaction result was: the conversion of 1,3,3, 3-tetrafluoro-propyne was 87.9%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.5%.
Example 11
The same operation as in example 3 was carried out, except that the reaction temperature was changed to 200 ℃ and the contact time was changed to 60s, and the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 98.5%.
Example 12
The same operation as in example 3, except that the reaction temperature was changed to 200 ℃ and the contact time was changed to 100 seconds, the reaction result was: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 95.1%.
Example 13
The same operation as in example 3, except that the reaction temperature was changed to 200 ℃ and the reaction pressure was changed to 0.3MPa, the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 88.5%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.0%.
Example 14
The same operation as in example 3, except that the reaction temperature was changed to 200 ℃ and the reaction pressure was changed to 0.5MPa, the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 71.3%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 98.3%.
Example 15
The same operation as in example 3 was carried out, except that the supported AlF of the hydrogenation catalyst was used3To MgF2The reaction temperature was changed to 200 ℃, and the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.4%.
Example 16
The same operation as in example 3 was carried out, except that the supported AlF of the hydrogenation catalyst was used3Changed to BaF2The reaction temperature was changed to 200 ℃, and the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.0%.
Example 17
The same operation as in example 3 was carried out, except that the supported AlF of the hydrogenation catalyst was used3Modified to FeF3The reaction temperature was changed to 200 ℃, and the reaction results were: the conversion of 1,3,3, 3-tetrafluoro-propyne was 100%, and the selectivity of Z-1,3,3, 3-tetrafluoropropene was 99.5%.
Example 18
The same operation as in example 3 was carried out, except that the supported AlF of the hydrogenation catalyst was used3Modified to FeF3The reaction temperature was changed to 200 ℃, the starting material 1,3,3, 3-tetrafluoropropene was changed to the same amount of tetrafluoropropadiene, and the reaction results were: the conversion of tetrafluoropropadiene was 100%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 93.8%, and the selectivity for 1,1,3, 3-tetrafluoropropene was 4.5%.
Claims (10)
1. A preparation method of Z-1,3,3, 3-tetrafluoropropene is characterized by comprising the following steps:
in the presence of a hydrogenation catalyst, in a tubular reactor,or/and isomers thereofCarrying out gas phase selective hydrogenation reaction with hydrogen to obtain Z-1,3,3, 3-tetrafluoropropene; the hydrogenation catalyst consists of noble metal, auxiliary metal and carrier, wherein the noble metal is any one or more of elementary substances of palladium and platinum, the auxiliary is any one or more of elementary substances of bismuth, copper and iron, and the carrier is any one or more of metal fluorides of aluminum, iron, magnesium, calcium, barium, zinc and copper; the mass percentages of the noble metal, the auxiliary metal and the carrier are respectively 1-5%: 0.1-5%: 98.9-90 percent, and the sum of the mass percentages of the three is 1.
2. The method of claim 1, wherein: wherein the noble metal is any one or more of palladium and platinum simple substances, the auxiliary agent is any one or more of bismuth, copper and iron simple substances, and the carrier is any one or more of metal fluorides of aluminum, iron, magnesium and barium; the mass percentages of the noble metal, the auxiliary agent and the carrier are respectively 1-3%: 0.1-1%: 96 to 98.9 percent.
3. The method of claim 1, wherein: the reaction conditions of the gas phase selective hydrogenation reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 50-300 ℃,or/and isomers thereofThe mass ratio of hydrogen to substance is 1: 1 to 15, and the contact time is 1 to 100 s.
4. The method of claim 3, wherein: the reaction conditions of the gas phase selective hydrogenation reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-200 ℃,or/and isomers thereofThe mass ratio of hydrogen to substance is 1: 5 to 10, and the contact time is 10 to 100 s.
5. The method of claim 1, wherein: saidThe synthesis method comprises the following steps: in the presence of an isomerization catalyst, the catalyst,a gas phase isomerization reaction occurs to obtainWherein the isomerization catalyst is any one of metal fluorine chloride or metal fluorine chloride oxide of Al, Mg, Ca, Ba, Cr, Fe, Co, Ni, Mo, W, Zn or Cu.
6. The method of claim 5, wherein: the reaction conditions of the isomerization reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 0-200 ℃, and the contact time of the tetrafluoro propadiene is 1-100 s.
8. The method of claim 7, wherein: the reaction conditions of the elimination reaction are as follows: the reaction temperature is 100-500 ℃,the amount of the substance to the alkali metal oxide or alkaline earth metal oxide is 1: 4-10, and the reaction time is 2-20 h; wherein R is1、R2Is any one of F, Cl, Br or I, the alkali metal oxide is one or more of lithium oxide, sodium oxide, potassium oxide, rubidium oxide or cesium oxide, and the alkaline earth metal oxide is one or more of magnesium oxide, calcium oxide, barium oxide or strontium oxide.
9. The method of claim 7, wherein: saidThe synthesis method comprises the following steps: halogenated cyclopentenes in the presence of an oxidation catalystCarrying out gas phase contact oxidation reaction with oxygen or oxygen diluted by inert gas to obtain the dicarboxylic acid halideThe oxidation catalyst is silver oxide loaded on iron oxide, chromium oxide, zinc oxide, magnesium oxide, zirconium oxide, chromium fluoride, iron fluoride, zinc fluoride and magnesium fluorideAnd one or more supported catalysts in aluminum fluoride, wherein the mass percentages of the silver oxide and the carrier are respectively 0.1-30%: 70 to 99.9 percent.
10. The method of claim 9, wherein: the reaction conditions of the oxidation reaction are as follows: the reaction temperature is 100-600 ℃,the molar ratio of the inert gas to the oxygen is 1: 1-10, the molar ratio of the inert gas to the oxygen is 0-5: 1, and the contact time is 0.01-100 s, wherein R1、R2Is any one of F, Cl and Br, and the inert gas is one or more of nitrogen, helium, argon and neon.
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