CN111499489B - Isomerization method of fluorine-containing olefin - Google Patents
Isomerization method of fluorine-containing olefin Download PDFInfo
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- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/56—Platinum group metals
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Abstract
The invention discloses a method for isomerizing fluorine-containing olefin, at least one part of a compound shown in a general formula (I) is converted into a compound shown in a general formula (II) in the presence of a catalyst,
Description
Technical Field
The invention belongs to the field of olefin isomerization, and particularly relates to a method for isomerizing fluorine-containing olefin.
Background
The fluorine-containing olefin compound has a double bond in its molecule, has a short atmospheric lifetime and a small global warming effect, and can be used as a substitute for Hydrochlorofluorocarbons (HCFCs) and Hydrofluorocarbons (HFCs) as a cleaning agent, a solvent, a blowing agent, and the like.
The fluorine-containing olefin compound has two configurations, cis-isomer (cis) and trans-isomer (trans), according to the arrangement mode of substituents around a double bond in a molecule. Fluorine-containing olefins of different configurations, generally having different physical and chemical properties, are used in different fields. Therefore, from the application field, it is required to obtain fluorine-containing olefin with one configuration as much as possible, and therefore, it is required to develop a method for isomerizing fluorine-containing olefin, which can convert fluorine-containing olefin from one configuration to another configuration.
For 1,3,3,3-tetrafluoropropene, also known as "HFO-1234ze," there are both cis-HFO-1234ze and trans-HFO-1234ze configurations. As for the production process of 1, 3-tetrafluoropropene, china CN104603089A reports a process for producing 1-chloro-3, 3-trifluoro-1-propene (HCFC-1233 zd) and 1, 3-tetrafluoropropene (HFO-1234 ze), the reaction temperature needs to be above 400 ℃, and chlorine gas is added as a free radical generator.
With respect to the preparation of compounds of different configurations of other fluoroolefin compounds, the following are reported in the prior art:
PCT patent application WO2008008351 discloses a process for preparing cis-1,2,3,3,3-pentafluoropropene (HFO-1225 ye) by using a supported SbCl w F 5-w 、TiCl x F 4-x ,SnCl y F 4-y 、TaCl z F 5-z (w and z =0 to 4, x and y =0 to 3) of an aluminum fluoride or activated carbon catalyst to convert trans-1, 2, 3-pentafluoropropene to cis-1, 2, 3-pentafluoropropene, thereby increasing the ratio of cis-1, 2, 3-pentafluoropropene to trans-1, 2, 3-pentafluoropropene in the compound;
PCT patent application WO2008125825 discloses a process for isomerizing (hydrohalo) fluoroolefins by converting trans-HFO-1225ye to cis-HFO-1225ye in the presence of a catalyst selected from the group consisting of lewis acids, catalysts containing chromium oxide and at least one metal of Zn, mg, ni, co, ag, cu, al, sn, zr, or alumina.
The above-mentioned isomerization method of fluorine-containing olefin has problems that the reaction temperature is too high without using a catalyst, and that the catalyst activity cycle is short and the selectivity of the target product is low when using a catalyst. Therefore, there is a need for further technical improvements in the process for the isomerization of fluorine-containing olefins.
Disclosure of Invention
The invention aims to provide a method for isomerizing fluorine-containing olefin, which comprises the steps of converting fluorine-containing olefin with one configuration into fluorine-containing olefin with another configuration in the presence of a catalyst, converting at least one part of a compound shown as a general formula (I) in a raw material composition into a compound shown as a general formula (II) under the action of the catalyst, wherein:
X 1 、X 2 independently selected from H or F, Y is selected from F or Cl, and X 1 、X 2 And Y is not simultaneously F.
The inventor of the present application found in the course of research that fluorine-containing olefin compounds are easily coked on the catalyst surface due to the presence of double bonds in the molecule, resulting in the covering of the active sites of the catalyst, thereby losing reactivity. According to the catalyst provided by the invention, through the synergistic action among the main catalyst, the cocatalyst and the cocatalyst can form a metal active center and an acid center on the main catalyst, and can synergistically complete a fluorine-containing olefin cis-trans isomerization process, so that the activity of the catalyst is effectively improved, side reactions are reduced, the problems are well solved, the compound shown in the general formula (I) is converted into the compound shown in the general formula (II), and the target product has high selectivity, high stability and long service life.
The invention provides a catalyst, which comprises a main catalyst, a cocatalyst and a promoter, wherein the main catalyst comprises zirconium, the cocatalyst comprises at least one selected from copper, cobalt, vanadium, nickel, tin, ruthenium, rubidium and platinum, and the promoter is at least one selected from yttrium, lanthanum, cerium, praseodymium, neodymium, calcium and magnesium.
As for the catalyst, as a preferred embodiment, the catalyst includes a main catalyst including zirconium, a co-catalyst including at least one selected from copper, cobalt, nickel, tin and platinum, and a co-catalyst selected from at least one selected from yttrium, lanthanum and magnesium.
As for the catalyst, the proportion among the main catalyst, the cocatalyst and the cocatalyst is such that when the catalyst is applied to the fluorine-containing olefin isomerization reaction, the compound represented by the general formula (I) is favorably converted into the compound represented by the general formula (II). In a preferred embodiment, the catalyst comprises a main catalyst, a cocatalyst and a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 65-98.99. As another preferred embodiment, the catalyst comprises a main catalyst, a cocatalyst and a cocatalyst, and the molar ratio of the main catalyst to the cocatalyst is 80-96.9.
The catalyst provided by the invention can be prepared according to the methods commonly used in the field, such as an impregnation method, a precipitation method and a mechanical mixing method, so as to realize the combination of the main catalyst, the cocatalyst and the cocatalyst.
In the preparation process of the catalyst, the raw materials of the main catalyst, the cocatalyst and the cocatalyst are preferably fluorides, oxides, hydroxides, chlorides, oxychlorides, carbonates, nitrates, acetates and sulfates corresponding to the metals of the main catalyst, the cocatalyst and the cocatalyst.
As a preferred embodiment, the procatalyst is selected from the group consisting of zirconium containing compounds. As a further preferred embodiment, the zirconium-containing compound is at least one selected from the group consisting of zirconium oxychloride, zirconium carbonate, and zirconium nitrate.
As a preferred embodiment, the feedstock of the co-catalyst comprises a co-catalyst compound, preferably at least one selected from the group consisting of chlorides, carbonates, nitrates and sulfates of the co-catalyst.
As a preferred embodiment, the raw material of the promoter includes a promoter compound, preferably at least one selected from the group consisting of a chloride, a carbonate, a nitrate and a sulfate of the promoter.
As a preferred embodiment, the preparation method of the catalyst of the present invention is a precipitation-impregnation method, comprising the steps of:
(1) Preparing a main catalyst compound and an auxiliary catalyst compound into a mixed solution, adding a dispersing agent and ammonia water into the mixed solution, filtering the solution to obtain a filter cake, putting the filter cake into an alcohol organic solvent, and heating for azeotropic distillation and dehydration to obtain primary powder;
(2) Calcining the primary powder at the temperature of 400-800 ℃ to obtain calcined primary powder, namely the zirconia containing the cocatalyst;
(3) Preparing an aqueous solution containing a co-catalyst compound, putting the calcined primary powder into the aqueous solution containing the co-catalyst compound for dipping, and after dipping, molding, drying and roasting to obtain the catalyst.
In the preparation method of the catalyst provided by the invention, the used dispersing agent can be a dispersing agent commonly used in the field. As a preferred embodiment, the dispersant is at least one selected from the group consisting of polyethylene glycol, polyvinyl alcohol, phenol resin, carboxymethyl cellulose and sorbitan oleate.
The alcohol organic solvent used in the preparation method of the catalyst provided by the invention can be an alcohol organic solvent commonly used in the field. As a preferred embodiment, the alcoholic organic solvent is selected from at least one of methanol, ethanol, propanol, butanol, isopropanol, isobutanol, and t-amyl alcohol.
According to the preparation method of the catalyst provided by the invention, the dosage of the main catalyst compound, the cocatalyst compound and the cocatalyst compound can be determined according to the molar ratio among the main catalyst, the cocatalyst and the cocatalyst in the prepared catalyst.
The catalyst provided by the invention is preferably subjected to activation treatment before use. The method of activating the catalyst may be carried out according to a method of activating a catalyst commonly used in the art. By way of example, the catalyst prepared may be loaded into a reaction zone and subjected to hydrogen reduction and/or fluorination pretreatment.
The isomerization reaction of the fluorine-containing olefin provided by the invention can be carried out in a gas phase.
The isomerization reaction is carried out in the presence of a catalyst. The catalyst is the catalyst.
The isomerization method of the fluorine-containing olefin provided by the invention has the advantages that when the isomerization reaction is carried out in a gas phase, the space velocity is preferably 100-1800 h -1 And further preferably 150 to 900 hours -1 。
When the isomerization reaction is carried out in a gas phase, the reaction temperature is preferably 200-500 ℃, more preferably 200-400 ℃, even more preferably 200-350 ℃, and most preferably 250-350 ℃.
As an embodiment of the present invention, X in the compound represented by the general formula (I) and the compound represented by the general formula (II) 1 Is H, X 2 In the case where H and Y are Cl, the temperature of the isomerization reaction is preferably 200 to 500 ℃ and more preferably 250 to 350 ℃.
As an embodiment of the present invention, X in the compound represented by the general formula (I) and the compound represented by the general formula (II) 1 Is H, X 2 In the case where H and Y are F, the temperature of the isomerization reaction is preferably 200 to 500 ℃ and more preferably 250 to 350 ℃.
As an embodiment of the present invention, X in the compound represented by the general formula (I) and the compound represented by the general formula (II) 1 Is F, X 2 In the case where H and Y are Cl, the temperature of the isomerization reaction is preferably 200 to 500 ℃ and more preferably 250 to 350 ℃.
The invention provides a method for isomerizing fluorine-containing olefin, which comprises an isomerization reaction, wherein at least one part of a compound shown in a general formula (I) in a raw material composition is converted into a compound shown in a general formula (II) under the action of a catalyst, wherein:
X 1 、X 2 is H, Y is F or Cl;
the catalyst comprises a main catalyst, a cocatalyst and an auxiliary catalyst, wherein the main catalyst comprises zirconium, the auxiliary catalyst comprises at least one selected from copper, cobalt, vanadium, nickel, tin, ruthenium, rubidium and platinum, and the auxiliary catalyst is at least one selected from yttrium, lanthanum, cerium, praseodymium, neodymium, calcium and magnesium;
the isomerization reaction is carried out at the temperature of 200-00 ℃ and the airspeed of 100-1800 h -1 。
The invention provides a method for isomerizing fluorine-containing olefin, which comprises an isomerization reaction, wherein at least one part of a compound shown in a general formula (I) in a raw material composition is converted into a compound shown in a general formula (II) under the action of a catalyst, wherein:
X 1 、X 2 is H, Y is F or Cl;
the catalyst comprises a main catalyst, a cocatalyst and a promoter, wherein the main catalyst comprises zirconium, the cocatalyst comprises at least one selected from copper, cobalt, nickel, tin and platinum, and the promoter is at least one selected from yttrium, lanthanum and magnesium;
the isomerization reaction is carried out at the temperature of 250-350 ℃, and the space velocity is 150-00 h -1 。
The invention provides a method for isomerizing fluorine-containing olefin, which is a preferred implementation method, wherein the isomerization reaction is carried out in the presence of inert gas.
The invention provides a method for isomerizing fluorine-containing olefin, which is a preferred implementation method, wherein the isomerization reaction is carried out in the presence of a gas containing oxygen. The oxygen-containing gas may be oxygen, air or a mixture of oxygen and an inert gas.
The invention provides a method for isomerizing fluoroolefin, wherein X is shown in general formulas (I) and (II) 1 Is H, X 2 When H and Y are F, the method further comprises the following steps before the isomerization reaction:
(1) In the presence of a chromium-based catalyst at a temperature of 200 to 400 ℃, CF 3 CH = CHCl with HF in gas phase to obtain a gas phase comprising CF 3 CH = CHF and CF 3 CH 2 CHF 2 The material (2);
(2) In the presence of an aluminum-based catalyst, at a temperature of 300 to 450 ℃, CF 3 CH 2 CHF 2 Gas phase dehydrofluorination to CF 3 CH＝CHF。
Compared with the prior art, the method for isomerizing the fluorine-containing olefin has the following advantages that:
(1) Introducing a certain amount of low-valence cations into the position of zirconium oxide to replace zirconium ions by introducing a cocatalyst to cause great distortion of a coordination layer so as to form a structure with anion defects, wherein Zr on the surface of the structure 4+ Has higher activity, can lead pi bonds in double bonds of fluorine-containing olefin to generate heterolysis, thereby carrying out cis-trans isomerization reaction;
(2) By introducing the co-catalyst, the co-catalyst interacts with the main catalyst to form a metal active center and an acid center in the catalyst to cooperate to complete the cis-trans isomerization process of the fluorine-containing olefin, so that the activity of the catalyst is effectively improved, the occurrence of side reactions is reduced, and the fluorine-containing olefin isomerization catalyst has better low-temperature activity and higher selectivity;
(3) When the catalyst is applied to the reaction of isomerizing trans-HFO-1234ze to generate cis-HFO-1234ze, the single-pass selectivity of the cis-HFO-1234ze can reach more than 99.2 percent, the conversion rate of the trans-HFO-1234ze in the circulating reaction can reach 100 percent, and the catalyst has no obvious deactivation phenomenon after 1000 hours of reaction.
Some of the compounds of the invention are abbreviated as follows:
HFO-1234 (E): trans-1, 3-tetrafluoropropene (trans-HFO-1234 ze)
HFO-1234 (Z): cis-1, 3-tetrafluoropropene (cis-HFO-1234 ze).
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
280.4g ZrOCl 2 ·8H 2 O and 30.6g Y (NO) 3 ) 3 ·6H 2 And O is respectively prepared into 1mol/L solution, the solution is evenly mixed, and polyethylene glycol is added while stirring, so that the mass percentage of the polyethylene glycol in the solution is 10 percent. Dropwise adding 5% ammonia water solution, adjusting pH to 8.5, precipitating, aging for 3 hr, washing with deionized water, and vacuum filtering until AgNO is used 3 No Cl is detected by inspection - . Adding isobutanol into the filtered filter cake, stirring for 0.5 hour, and carrying out dynamic azeotropic distillation when the volume ratio of the filter cake to the alcohol solution is 1. Heating the primary powder to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and calcining for 2 hours to obtain Y/ZrO 2 And (3) powder. 9.4g of Cu (NO) 3 ) 2 ·3H 2 Preparing solution of O, soaking Y/ZrO in the solution in equal volume 2 Drying the powder under vacuum condition at 50 deg.C for 24 hr, tabletting, and adding N 2 Firing at 450 ℃ for 4 hours under an atmosphere to obtain a Cu-Y/ZrO of 87 metal atom mole percentages Cu: Y: zr =5 2 A catalyst.
A tubular reactor made of Incan alloy having an inner diameter of 1/2 inch and a length of 40cm was charged with 5mL of the above catalyst, and N was introduced thereinto at 200 ℃ 2 HF =10, flow rate of 1 mixed gas 25mL/min, hold for 2 hours, then gradually raise temperature to 350 ℃ at 2.5 ℃/min, hold for 1 hour at 350 ℃, N 2 And (5) purging and cooling. HFO-1234 (E) was introduced at a flow rate of 75mL/min,the reaction temperature is 200-500 ℃, the pressure is 0.1MPa, the reaction product is washed by water and alkali, the organic matter is obtained by separation, and the composition of the organic matter is analyzed by gas chromatography after drying and dewatering, and the result is shown in Table 1.
Example 2
The same operation as in example 1 was conducted, except that the fluorine-containing olefin isomerization catalyst was made of Zr (NO) 3 ) 4 ·5H 2 O、La(NO 3 ) 3 ·6H 2 O、Co(NO 3 ) 3 ·6H 2 O was prepared in terms of metal atomic mole percent Co La Zr = 15.
Example 3
The same procedure as in example 1, except that the catalyst for isomerization of fluorinated olefin was prepared from ZrOCl 2 ·8H 2 O、MgCl 2 、RuCl 3 Prepared according to the metal atom mole percentage of Ru: mg: zr = 0.1.
Example 4
The same procedure as in example 1, except that the catalyst for isomerization of fluorinated olefin was prepared from ZrOCl 2 ·8H 2 O、Ce(NO 3 ) 3 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O was prepared according to the metal atom mole percent Ni: ce: zr =1.
Example 5
The same procedure as in example 1, except that the catalyst for isomerization of fluorinated olefin was prepared from ZrOCl 2 ·8H 2 O、CaCl 2 、Cu(NO 3 ) 2 ·3H 2 O was prepared in terms of metal atom mole percent Cu: ca: zr = 20.
Example 6
The same operation as in example 1 was conducted, except that the fluorine-containing olefin isomerization catalyst was composed of Zr (CH) 3 COO) 4 、Mg(CH 3 COO) 2 ·4H 2 O、RbNO 3 、Co(NO 3 ) 3 ·6H 2 O was prepared according to metal atom mole percent Co: rb: mg: zr = 1.5.
Example 7
The same procedure as in example 1, except that the catalyst for isomerization of fluorinated olefin was prepared from ZrOCl 2 ·8H 2 O、La(NO 3 ) 3 ·6H 2 O、SnCl 2 、H 2 PtCl 6 Prepared according to the metal atom mole percentage of Pt: sn: la: zr =0.5 2 :H 2 Reduction treatment was performed with a mixed gas of =10 2 And (5) purging for standby. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 ℃ and a pressure of 0.1MPa, and the results are shown in Table 1.
Example 8
The same operation as in example 7, except that the fluorine-containing olefin isomerization catalyst was prepared from Zr (OH) 4 、PrCl 3 、H 2 PtCl 6 Prepared according to the metal atom mole percentage Pt: pr: zr =2.5 2 :H 2 1, reduction time 1 hour. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 ℃ and a pressure of 0.1MPa, the results being shown in Table 1.
Example 9
The same operation as in example 7 was conducted, except that the fluorine-containing olefin isomerization catalyst was composed of Zr (CH) 3 COO) 4 、Mg(CH 3 COO) 2 ·4H 2 O、PtCl 2 、VCl 3 The alloy is prepared according to the following metal atom mole percentage of V to Pd to Mg to Zr =1 2 :H 2 =4, flow rate 25mL/min, reduction time 4 hours. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 ℃ and a pressure of 0.1MPa, and the results are shown in Table 1.
Example 10
The same operation as in example 1 was conducted, except that 1L of the Cu-Y/ZrO was charged 2 The catalyst and the reaction conditions are changed into that the reaction temperature is 300 ℃ and the space velocity is 200h -1 And the pressure is 0.3MPa, the reaction product directly enters a distillation tower for separation, unreacted HFO-1234 (E) extracted from the tower top enters a reactor for continuous reaction, and the tower bottom components are subjected to deacidification, dehydration and rectification to obtain a target product HFO-1234 (Z). Sampling is carried out at the outlet of the reactor, organic matters are obtained by water washing, alkali washing and separation, the composition of the organic matters is analyzed by gas chromatography after drying and dewatering, and the result of the reaction for 1000 hours is shown in Table 2.
Comparative example 1
Charging 5mL of commercially available ZrO 99.9% into a tube reactor made of Incan alloy having an inner diameter of 1/2 inch and a length of 40cm 2 Introducing N at 200 DEG C 2 HF =10, flow rate of 1 mixed gas 25mL/min, hold for 2 hours, then gradually raise temperature to 350 ℃ at 2.5 ℃/min, hold for 1 hour at 350 ℃, N 2 And (5) purging and cooling. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 ℃ and a pressure of 0.1MPa, and the materials were collected as in example 1, and the results are shown in Table 1.
Comparative example 2
280.4g of ZrOCl 2 ·8H 2 O and 30.6g Y (NO) 3 ) 3 ·6H 2 And O is respectively prepared into 1mol/L solution, the solution is uniformly mixed, and polyethylene glycol is added while stirring, so that the mass percentage of the polyethylene glycol in the solution is 10%. Dropwise adding 5% ammonia water solution, adjusting pH to 8.5, precipitating, aging for 3 hr, washing with deionized water, and vacuum filtering until AgNO is used 3 No Cl is detected by inspection - . Adding isobutanol into the filtered filter cake, stirring for 0.5 hour, wherein the volume ratio of the filter cake to the alcohol solution is 1: and 3, carrying out dynamic azeotropic distillation when the temperature is raised to 120 ℃ to obtain primary powder. Heating the primary powder to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and calcining for 2h to obtain Y/ZrO 2 Powder, tabletting to obtain 9.2% of Y/ZrO 2 A catalyst.
A tubular reactor made of Incan alloy having an inner diameter of 1/2 inch and a length of 40cm was charged with 5mL of the above catalyst, and N was introduced thereinto at 200 ℃ 2 :HFFlow of mixed gas of =10 and 1, flow rate 25mL/min, hold for 2 hours, then gradually raise temperature to 350 ℃ at 2.5 ℃/min, hold for 1 hour at 350 ℃, N 2 And (5) purging and cooling. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 ℃ and a pressure of 0.1MPa, and the materials were collected as in example 1, and the results are shown in Table 1.
Comparative example 3
Filling 5mL of commercially available AlF having a purity of 99.9% in a tubular reactor made of Incan alloy having an inner diameter of 1/2 inch and a length of 40cm 3 In N at 2 Roasting for 4h at 300 ℃ under protection. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 to 350 ℃ and a pressure of 0.1MPa, and the same materials as in example 1 were collected, and the results are shown in Table 1.
Comparative example 4
120g of Cr (NO) 3 ) 3 ·9H 2 Preparing 1mol/L solution from O, dropwise adding 5% ammonia water solution, adjusting pH to 8.5, precipitating, aging for 3 hr, washing with deionized water, vacuum filtering to neutrality, drying in air at 110 deg.C for 16 hr, tabletting, and adding N 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the chromium-based catalyst.
A tubular reactor made of Incan alloy having an inner diameter of 1/2 inch and a length of 40cm was charged with 5mL of the above catalyst, and N was introduced thereinto at 200 ℃ 2 F =1, flow rate of mixed gas 25mL/min, hold for 2 hours, then gradually raise temperature to 350 ℃ at 2.5 ℃/min, hold for 1 hour at 350 ℃, then N =1 2 And (5) purging and cooling. HFO-1234 (E) was introduced at a flow rate of 75mL/min, a reaction temperature of 300 ℃ and a pressure of 0.1MPa, and the materials were collected as in example 1, and the results are shown in Table 1.
Comparative example 5
Same operation as in example 10, except that AlF was charged 3 The catalyst, results are shown in Table 2.
TABLE 1
TABLE 2
The above examples show that the catalyst provided by the invention has good stability when being used for isomerization reaction of fluorine-containing olefin, the catalyst has no obvious deactivation phenomenon after 1000 hours of reaction, cis-HFO-1234ze has high selectivity and few byproducts.
Claims (13)
1. A method for isomerizing fluoroolefin, which is characterized by comprising the following steps:
the method comprises an isomerization reaction, at least one part of a compound shown in a general formula (I) in a raw material composition is converted into a compound shown in a general formula (II) under the action of a catalyst, wherein:
X 1 is H, X 2 Is H, Y is F;
the catalyst comprises a main catalyst, a cocatalyst and a promoter, wherein the main catalyst comprises zirconium, the cocatalyst comprises at least one selected from copper, cobalt, vanadium, nickel, tin, ruthenium, rubidium and platinum, and the promoter is at least one selected from yttrium, lanthanum, cerium, praseodymium, neodymium, calcium and magnesium;
the preparation method of the catalyst is a precipitation-impregnation method, and comprises the following steps:
(1) Preparing a main catalyst compound and an auxiliary catalyst compound into a mixed solution, adding a dispersing agent and ammonia water into the mixed solution, filtering the solution to obtain a filter cake, putting the filter cake into an alcohol organic solvent, and heating for azeotropic distillation and dehydration to obtain primary powder;
(2) Calcining the primary powder at the temperature of 400-800 ℃ to obtain calcined primary powder, namely zirconia containing a cocatalyst;
(3) Preparing an aqueous solution containing a co-catalyst compound, putting the calcined primary powder into the aqueous solution containing the co-catalyst compound for dipping, and after dipping, molding, drying and roasting to obtain the catalyst.
2. The process for isomerization of fluoroolefins according to claim 1, characterized in that:
the catalyst comprises a main catalyst, a cocatalyst and a promoter, wherein the main catalyst comprises zirconium, the cocatalyst comprises at least one selected from copper, cobalt, nickel, tin and platinum, and the promoter is at least one selected from yttrium, lanthanum and magnesium.
3. The process for isomerization fluoroolefins according to claim 1, characterized by:
the catalyst comprises a main catalyst, a cocatalyst and an auxiliary catalyst, wherein the molar ratio of the main catalyst to the cocatalyst to the auxiliary catalyst is 65-98.99 and is (1-15).
4. The process for isomerization of fluoroolefins according to claim 3, characterized in that:
the catalyst comprises a main catalyst, a cocatalyst and an auxiliary catalyst, wherein the molar ratio of the main catalyst to the cocatalyst to the auxiliary catalyst is 80-96.9.
5. The process for isomerization fluoroolefins according to claim 1, characterized by: the isomerization reaction is carried out in the gas phase.
6. The process for isomerization fluoroolefins according to claim 5, characterized by:
the isomerization reaction is carried out in gas phase, and the space velocity is 100-1800 h -1 。
7. The process for isomerization fluoroolefins according to claim 6, characterized by:
the isomerization reaction is carried out in a gas phase, and the space velocity is 150 to 900h -1 。
8. The process for isomerization fluoroolefins according to claim 1, characterized by: the temperature of the isomerization reaction is 200-500 ℃.
9. The process for isomerization fluoroolefins according to claim 8, characterized by: the temperature of the isomerization reaction is 250-350 ℃.
10. The process for isomerization fluoroolefins according to claim 1, characterized by:
the method also comprises the following steps before the isomerization reaction:
(1) In the presence of a chromium-based catalyst at a temperature of 200 to 400 ℃, CF 3 Gas phase reaction of CH = CHCl with HF to give a gas phase comprising CF 3 CH = CHF and CF 3 CH 2 CHF 2 The material (2);
(2) In the presence of an aluminum-based catalyst, at a temperature of 300 to 450 ℃, CF 3 CH 2 CHF 2 Gas phase dehydrofluorination to CF 3 CH＝CHF。
11. The process for isomerization of fluoroolefins according to claim 1, characterized in that: the isomerization reaction is carried out in the presence of an inert gas.
12. The process for isomerization fluoroolefins according to claim 1, characterized by: the isomerization reaction is carried out in the presence of a gas comprising oxygen.
13. The process for isomerization fluoroolefins according to claim 1, characterized by:
the dispersing agent is selected from at least one of polyethylene glycol, polyvinyl alcohol, phenolic resin, carboxymethyl cellulose and sorbitan oleate;
the alcohol organic solvent is at least one selected from methanol, ethanol, propanol, butanol, isopropanol, isobutanol and tert-amyl alcohol.
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