CN112723981A - Method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene by gas phase fluorination - Google Patents
Method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene by gas phase fluorination Download PDFInfo
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Abstract
The invention discloses a method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene by gas phase fluorination, which comprises the following steps: in the presence of a fluorination catalyst, carrying out fluorination reaction on tetrafluoro-butriene or tetrachloro-butriene and hydrogen fluoride to obtain the E-1,1,1,4,4, 4-hexafluoro-2-butene. The method is mainly used for efficiently and continuously and circularly producing the E-1,1,1,4,4, 4-hexafluoro-2-butene.
Description
Technical Field
The invention relates to a method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene in a gas phase, in particular to a method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene by carrying out catalytic fluorination reaction on tetrafluoro-butanetriene or tetrachloro-butanetriene and hydrogen fluoride in the presence of a fluorination catalyst.
Background
Up to now, the synthesis routes of 1,1,1,4,4, 4-hexafluoro-2-butene mainly include the following:
route one: U.S. Pat. No. 5,5463150 reports liquid phase fluorination of 1, 2-dichloro-1, 1,4,4, 4-pentafluorobutane or 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with KF in sulfolane solvent at 190 ℃ to give 1,1,1,4,4, 4-hexafluoro-2-butene in yields of 89.6% and 82.5%, respectively.
And a second route: U.S. Pat. No. 5,5516,951 reports 1, 1-dichloro-3, 3, 3-trifluoroethane coupled with copper powder and diethylamine to 1,1,1,4,4, 4-hexafluoro-2-butene with a conversion of up to 62% and a selectivity of 1,1,1,4,4, 4-hexafluoro-2-butene of 88%.
And a third route: japanese patent JP2010001244 reports that 1,1, 1-trifluoro-2-bromo-2-chloroethane is used as a starting material, and 1,1,1,4,4, 4-hexafluoro-2-butene is obtained through two-step reaction of zinc powder coupling and zinc powder dechlorination.
And a fourth route: chinese patent CN201310082246.3 reports that hexachlorobutadiene is used as a starting material, and 1,1,1,4,4, 4-hexafluoro-2, 4-butene-2 is obtained by two steps of liquid phase addition reaction of hexachlorobutadiene and HF in the presence of antimony pentachloride or titanium tetrachloride and zinc powder dechlorination reaction of 1,1,1,4,4, 4-hexafluoro-2, 3-dichlorobutene.
The product 1,1,1,4,4, 4-hexafluoro-2-butene of the above technical route is a mixture of Z-1,1,1,4,4, 4-hexafluoro-2-butene and E-1,1,1,4,4, 4-hexafluoro-2-butene, with the following drawbacks: (1) the above routes all involve liquid phase reaction, a large amount of solvents and solid reagents are used for KF, zinc powder and the like, a large amount of waste liquid and waste solids are generated, and the environment is seriously polluted; (2) the fourth route has the problems of serious corrosion and serious pollution, wherein a liquid phase system consisting of antimony pentachloride or titanium tetrachloride and HF has extremely strong corrosion to equipment and devices, and the generated pollution is also extremely serious; (3) the per-pass yield of E-1,1,1,4,4, 4-hexafluoro-2-butene is low, although the ratio of E-1,1,1,4,4, 4-hexafluoro-2-butene is a higher configuration than Z-1,1,1,4,4, 4-hexafluoro-2-butene in the mixed product of 1,1,1,4,4, 4-hexafluoro-2-butene, such as: route one, 1, 2-dichloro-1, 1,4,4, 4-pentafluorobutane as the starting material gave a 1,1,1,4,4, 4-hexafluoro-2-butene yield of 89.6%, a 2-chloro-1, 1,1,4,4, 4-hexafluorobutane as the starting material gave a 1,1,1,4,4, 4-hexafluoro-2-butene yield of 82.5%, a 1,1,1,4,4, 4-hexafluoro-2-butene yield of 54.6% in route two, while route three to route four were longer and the single pass yield was not high. From this, it can be concluded that none of the above technical schemes have high per pass yields of E-1,1,1,4,4, 4-hexafluoro-2-butene.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the background technology and provide the preparation method which has high single-pass yield and high catalyst activity and is easy to realize gas-phase continuous large-scale production of the E-1,1,1,4,4, 4-hexafluoro-2-butene.
In order to realize the purpose of the invention, the invention takes tetrafluoro-butatriene or tetrachloro-butatriene as raw material to perform gas phase catalytic fluorination reaction with hydrogen fluoride to obtain E-1,1,1,4,4, 4-hexafluoro-2-butene. The reaction equation is as follows:
a method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene through gas phase fluorination comprises the step of carrying out fluorination reaction on tetrafluoro-butriene or tetrachloro-butriene and hydrogen fluoride in the presence of a fluorination catalyst to obtain the E-1,1,1,4,4, 4-hexafluoro-2-butene, wherein the fluorination catalyst is a chromium-based catalyst, a molybdenum-based catalyst or a tungsten-based catalyst modified by taking any one element of Fe, Co, Ni, Zn, Mg and Al as an auxiliary agent.
The metal element in the fluorination catalyst exists in the form of metal fluoride or metal oxyfluoride; wherein the mass percentage of the auxiliary agent and the main active component Cr, Mo or W is 5-15% and 85-95% respectively.
The preparation method of the fluorination catalyst comprises the following steps: dissolving soluble salt of the main active component and soluble salt of the auxiliary agent in water according to the mass percentage of the main active component and the auxiliary agent, then dropwise adding a precipitator to enable metal ions to be completely precipitated, adjusting the pH value to be 7.0-9.0, enabling the metal ions to be fully precipitated under the stirring condition, aging for 12-36 hours, filtering formed slurry, drying for 6-24 hours at 100-250 ℃, crushing obtained solid, and performing compression molding to obtain a catalyst precursor; roasting the catalyst precursor for 6-24 hours at 300-500 ℃ in a nitrogen atmosphere, and activating for 6-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to prepare the fluorination catalyst.
In the preparation method of the fluorination catalyst, the soluble salt of chromium comprises but is not limited to chromium trichloride, chromium nitrate, chromium acetate and the like; soluble salts of the molybdenum, including, but not limited to, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride, and the like; soluble salts of said tungsten including, but not limited to, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride, and the like; soluble salts of the adjuvant, including but not limited to, at least one or more of nitrate, chloride or acetate salts of the adjuvant; preferably, at least one or more of soluble salts of iron, cobalt and magnesium; the precipitant includes, but is not limited to, at least one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide; preferably, it is selected from ammonia.
The reaction conditions of the fluorination reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-500 ℃, and the ratio of the amount of the tetrafluoro-butatriene or tetrachloro-butatriene to the amount of the hydrogen fluoride is 1: 2 to 30, and the contact time is 5 to 100 s.
The reaction conditions of the fluorination reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 350-500 ℃, and the ratio of the amount of the tetrafluoro-butatriene or tetrachloro-butatriene to the amount of the hydrogen fluoride is 1: 10 to 20, and the contact time is 10 to 50 s.
The reaction conditions of the fluorination reaction are as follows: the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 350-500 ℃, and the ratio of the amounts of the tetrafluoro-triene and the hydrogen fluoride is 1: 10 to 20, and the contact time is 10 to 50 s.
The products of the fluorination reaction are obtained by side products of 1,1,4,4, 4-hexafluoro-2-butene besides the main product of E-1,1,1, 2,4,4, 4-heptafluorobutane and Z-1,1,1,4,4, 4-hexafluoro-2-butene, and the side products of 1,1,1,2,4,4, 4-heptafluorobutane and Z-1,1,1,4,4, 4-hexafluoro-2-butene can be recycled to the reactor of the fluorination reaction for further reaction and are converted into E-1,1, 4,4, 4-hexafluoro-2-butene through the dehydrofluorination reaction of 1,1,2,4,4, 4-heptafluorobutane and the isomerization reaction of Z-1,1, 4, 4-hexafluoro-2-butene, the reaction conditions for converting the byproduct into Z-1,1,1,4,4, 4-hexafluoro-2-butene are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-500 ℃, and the contact time of the 1,1,1,2,4,4, 4-heptafluorobutane or/and Z-1,1,1,4,4, 4-hexafluoro-2-butene is 5-100 s.
The preparation method 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, unreacted raw materials (comprising tetrafluoro-butatriene or tetrachloro-butatriene and hydrogen fluoride) are continuously recycled to a reactor to continuously participate in the reaction, and the product E-1,1,1,4,4, 4-hexafluoro-2-butene and the byproduct Z-1,1,1,4,4, 4-hexafluoro-2-butene, 1,1,1,2,4,4, 4-heptafluorobutane are respectively extracted out of the system. Wherein the boiling point of E-1,1,1,4,4, 4-hexafluoro-2-butene is 8.5 ℃ (760 mmHg); the boiling point of Z-1,1,1,4,4, 4-hexafluoro-2-butene is 33.4 ℃ (760 mmHg); the boiling point of the 1,1,1,2,4,4, 4-heptafluorobutane is 29.6-30.6 ℃ (760 mmHg); the boiling point of the tetrafluorobutatriene is-5 ℃ (760 mmHg); the melting point of the tetrachlorobutadiene is 60 ℃ (760 mmHg); the boiling point of hydrogen fluoride is 19.5 ℃ (760mmHg), and the like.
The by-products of the present invention, Z-1,1,1,4,4, 4-hexafluoro-2-butene and 1,1,1,2,4,4, 4-heptafluorobutane, can be converted into E-1,1,1,4,4, 4-hexafluoro-2-butene by further reaction. Such as: the 1,1,1,2,4,4, 4-heptafluorobutane can be converted into E-1,1,1,4,4, 4-hexafluoro-2-butene and Z-1,1,1,4,4, 4-hexafluoro-2-butene by gas-phase catalytic dehydrofluorination reaction in the presence of a chromium-based catalyst, a molybdenum-based catalyst and a tungsten-based catalyst; the Z-1,1,1,4,4, 4-hexafluoro-2-butene is converted into the E-1,1,1,4,4, 4-hexafluoro-2-butene by a gas phase catalytic isomerization reaction in the presence of a chromium-based catalyst, a molybdenum-based catalyst and a tungsten-based catalyst.
The type of reactor used for the reaction of the present invention is not critical, and a tubular reactor or the like 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 synthesizing the E-1,1,1,4,4, 4-hexafluoro-2-butene;
(2) the fluorination catalyst has the characteristics of high activity and long service life;
(3) the invention adopts a gas phase method to prepare the E-1,1,1,4,4, 4-hexafluoro-2-butene, and the materials which are not completely reacted are independently circulated through a gas phase independent circulation process, so that the initial raw materials can be almost completely converted into the E-1,1,1,4,4, 4-hexafluoro-2-butene, meanwhile, the byproducts can be returned to the original reactor and can also be converted into the E-1,1,1,4,4, 4-hexafluoro-2-butene, and finally, the product E-1,1,1,4,4, 4-hexafluoro-2-butene is extracted from a process system, thereby not generating liquid waste and waste gas and realizing green production.
Drawings
FIG. 1 shows a flow diagram of a process for the preparation of E-1,1,1,4,4, 4-hexafluoro-2-butene from tetrafluorobutatriene by gas phase fluorination.
The reference numerals in fig. 1 have the following meanings. Pipeline: 1.2, 3, 5, 7, 8, 10 and 11; a reactor: 4; a first distillation column: 6; a second distillation column: 9.
Detailed Description
The invention is described in further detail with reference to fig. 1, but without limiting the invention.
Fresh tetrafluorobutatriene through a line 1, tetrafluorobutatriene recycled through a line 10, and a mixture of fresh hydrogen fluoride through a line 2, and hydrogen fluoride recycled through a line 8, and a small amount of Z-1,1,1,4,4, 4-hexafluoro-2-butene, 1,1,1,2,4,4, 4-heptafluorobutane are fed together through a line 3 into a reactor 4 filled with a fluorination catalyst to carry out a gas phase fluorination reaction, and the reaction product stream is E-1,1,1,4,4, 4-hexafluoro-2-butene, z-1,1,1,4,4, 4-hexafluoro-2-butene, 1,1,1,2,4,4, 4-heptafluorobutane and unreacted tetrafluorotriene and hydrogen fluoride, and the reaction product flows through a pipeline 5 and enters a first distillation tower 6 for separation; the top component of the first distillation tower 6 is E-1,1,1,4,4, 4-hexafluoro-2-butene and tetrafluorobutanetriene, the bottom component of the tower is Z-1,1,1,4,4, 4-hexafluoro-2-butene, 1,1,1,2,4,4, 4-heptafluorobutane and hydrogen fluoride, the bottom component of the tower is circulated to the reactor 4 through a pipeline 8 and a pipeline 3 for continuous reaction, 1,1,1,2,4,4, 4-heptafluorobutane is subjected to dehydrofluorination reaction in the reactor 4 to obtain E-1,1,1,4,4, 4-hexafluoro-2-butene and Z-1,1,1,4,4, 4-hexafluoro-2-butene, Z-1,1,1,4,4, 4-hexafluoro-2-butene is subjected to isomerization reaction to obtain E-1,1,1,4,4, 4-hexafluoro-2-butene; the tower top component of the first distillation tower 6 enters a second distillation tower 9 through a pipeline 7 for separation; the top component of the second distillation tower 9 is tetrafluoro-butene, the bottom component is E-1,1,1,4,4, 4-hexafluoro-2-butene, the top component circulates to the reactor 4 through the pipeline 10 and the pipeline 3 to continue reacting, and the bottom component is subjected to subsequent deacidification, dehydration and rectification to obtain the target product E-1,1,1,4,4, 4-hexafluoro-2-butene.
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: and (3) washing, alkali washing and drying the reaction product, and then taking a gas sample for gas chromatography analysis. High purity helium and hydrogen fluoride are 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.
GC-MS analysis method: the mass spectrometer is GCMS-QP2010 SE (Shimadzu), and the column temperature is 33 ℃ for 10 minutes; 20 ℃/min to 230 ℃; the temperature was maintained for 10 minutes, the sample inlet and thermal conductivity detector were both maintained at 250 deg.C, and He was introduced at a rate of 10 ml/min as carrier gas.
19F NMR detection method: at 25 ℃, a small amount of a sample to be detected is dissolved by using deuterated chloroform containing trichlorofluoromethane (CFC-11, which is used as an internal standard of a fluorine spectrum) with the mass percentage of 0.5 percent as a solvent, and the sample is subjected to NMR on a Bruker AVANCE 400 (400 MHz) instrument19F NMR detection.
1H NMR detection method: at 25 ℃, deuterated chlorine containing tetramethylsilane (TMS as internal standard of hydrogen spectrum) with the mass percent of 0.1 percent is adoptedA small amount of the sample to be tested was dissolved in the solvent and subjected to the Bruker AVANCE 400 (400 MHz) NMR1And H NMR detection.
The starting material tetrafluorobutatriene is prepared according to the general method of Fluorine Chemistry, 2010, 131: 1173-1181 ".
The starting tetrachlorobutanetriene was prepared according to the literature "Angewandte Chemie International Edition in English, 1968, 7(5), 375-.
Example 1
Preparation of fluorination catalyst: according to the percentage composition of the tungsten element and the cobalt element of 90 percent and 10 percent, dissolving tungsten trichloride and cobalt nitrate in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 24 hours, washing with water, filtering, drying in a 120 ℃ oven for 15 hours, crushing the obtained solid, tabletting and forming to obtain a catalyst precursor, filling 10mL of the catalyst precursor into a Monel material tubular reactor with the inner diameter of 1/2 inches and the length of 30cm, introducing nitrogen, roasting for 12 hours at 350 ℃, wherein the nitrogen airspeed is 200 hours-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2, the total space velocity of the gas is 220h-1And activating for 12 hours, and stopping the mixed gas to prepare the tungsten-based 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 300 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 86.2%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 92.5%, the selectivity for 1,1,1,2,4,4, 4-heptafluorobutane was 7.3%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.2%.
The results of the confirmation of E-1,1,1,4,4, 4-hexafluoro-2-butene and Z-1,1,1,4,4, 4-hexafluoro-2-butene by GC-MS and nuclear magnetic detection were as follows:
(1) e-1,1,1,4,4, 4-hexafluoro-2-butene
Structural formula (I)：
MS m/e: 164 (M+); 145 (M+-F); 126 (M+-F2); 113 (M+-CHF2); 95 (M+-CF3); 75(M+-CHF4); 69 (M+- C3HF3).
19F NMR (377 MHz, Chloroform-d) δ -66.4 (m, F5, F6, F7, F8, F9 and F10, 6F).
1H NMR (400MHz, Chloroform-d) δ 6.95 (m, H11 and H12, 2H).
(2) Z-1,1,1,4,4, 4-hexafluoro-2-butene
Structural formula (xvi):
MS m/e: 164 (M+); 145 (M+-F); 113 (M+-CHF2); 95 (M+-CF3); 75(M+-CHF4); 69 (M+- C3HF3).
19F NMR (377 MHz, Chloroform-d) δ -60.6 (t, J=0.86 Hz, F5, F6, F7, F8, F9 and F10, 6F).
1H NMR (400MHz, Chloroform-d) δ 6.28 (dm, JH-H=12Hz, H11 and H12, 2H).
example 2
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 350 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 95.4%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.6%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.4%.
Example 3
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.2%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.8%.
Example 4
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 450 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.0%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.0%.
Example 5
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 500 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.8%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.2%.
Example 6
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 2, the contact time is 20s, 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 tetrafluorobutatriene was 52.1%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.8%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.2%.
Example 7
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 10, the contact time is 20s, 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 tetrafluorobutatriene was 97.4%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.7%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.3%.
Example 8
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 30, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.7%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.3%.
Example 9
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 5s, 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 tetrafluorobutatriene was 73.6%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.4%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.6%.
Example 10
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 10s, 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 tetrafluorobutatriene was 93.4%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 99.3%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 0.7%.
Example 11
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time was 50s, and the reaction pressure was 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.7%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.3%.
Example 12
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 100s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 97.3%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 2.7%.
Example 13
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 100s, and the reaction pressure is 0.3 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 tetrafluorobutatriene was 86.9%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 96.2%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 3.8%.
Example 14
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 100s and the reaction pressure is 0.5 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 tetrafluorobutatriene was 66.9%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 95.1%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 4.9%.
Example 15
Preparation of fluorination catalyst: the catalyst was prepared according to the procedure of example 1, with the cobalt element being replaced by iron element, and the other conditions being unchanged.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.9%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.1%.
Example 16
Preparation of fluorination catalyst: the catalyst was prepared according to the method of example 1, replacing cobalt element by nickel element, and the other conditions were not changed.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.4%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.6%.
Example 17
Preparation of fluorination catalyst: the catalyst was prepared according to the procedure of example 1, replacing the cobalt element by the zinc element, and the other conditions were not changed.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.5%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.5%.
Example 18
Preparation of fluorination catalyst: the catalyst was prepared according to the procedure of example 1, replacing the cobalt element by magnesium element, and the other conditions were not changed.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.4%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.6%.
Example 19
Preparation of fluorination catalyst: the catalyst was prepared according to the procedure of example 1, replacing the cobalt element by aluminum element, and the other conditions were not changed.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.1%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.9%.
Example 20
Preparation of fluorination catalyst: the catalyst was prepared according to the procedure of example 1, replacing the element tungsten with the element molybdenum, otherwise unchanged.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.6%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 1.4%.
Example 21
Preparation of fluorination catalyst: the catalyst was prepared according to the method of example 1, replacing the element tungsten with the element chromium, and the other conditions were unchanged.
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 400 ℃, and the mass ratio of the tetrafluoro-butriene to the hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrafluorobutatriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 98.0%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 2.0%.
Example 22
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, and the mass ratio of tetrachloro-butatriene to hydrogen fluoride is 1: 20, the contact time is 20s, 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 tetrachlorotriene was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 96.8%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 3.2%.
Example 23
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,2,4,4, 4-heptafluorobutane is 20s, 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 1,1,1,2,4,4, 4-heptafluorobutane was 100%, the selectivity for E-1,1,1,4,4, 4-hexafluoro-2-butene was 97.2%, and the selectivity for Z-1,1,1,4,4, 4-hexafluoro-2-butene was 2.8%.
From the results of example 23, it can be seen that 1,1,1,2,4,4, 4-heptafluorobutane, which is a by-product of the fluorination reaction of tetrafluorobutatriene or tetrachlorobutatriene, can be recycled to the fluorination reaction to continue the reaction, and the conversion to E-1,1,1,4,4, 4-hexafluoro-2-butene continues.
Example 24
A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the Z-1,1,1,4,4, 4-hexafluoro-2-butene is 20s, 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 Z-1,1,1,4,4, 4-hexafluoro-2-butene was 100% and the selectivity of E-1,1,1,4,4, 4-hexafluoro-2-butene was 100%.
From the results of example 24, it can be seen that Z-1,1,1,4,4, 4-hexafluoro-2-butene, which is a byproduct of the fluorination reaction of tetrafluorobutatriene or tetrachlorobutatriene, can be recycled to the fluorination reaction to continue the reaction, and the conversion to E-1,1,1,4,4, 4-hexafluoro-2-butene continues.
Claims (10)
1. A method for preparing E-1,1,1,4,4, 4-hexafluoro-2-butene by gas phase fluorination, which is characterized by comprising the following steps: in the presence of a fluorination catalyst, carrying out fluorination reaction on tetrafluoro-butatriene or tetrachloro-butatriene and hydrogen fluoride to obtain E-1,1,1,4,4, 4-hexafluoro-2-butene, wherein the fluorination catalyst is a catalyst which is modified by taking any one element of Fe, Co, Ni, Zn, Mg and Al as an auxiliary agent and takes Cr, Mo or W as an active component.
2. The method of claim 1, wherein: wherein the mass percentage of the auxiliary agent and the main active component Cr, Mo or W is 5-15% and 85-95% respectively.
3. The method of claim 2, wherein: the metal element in the fluorination catalyst is in the form of metal fluoride or metal oxyfluoride.
4. The method of claim 3, wherein: the preparation method of the fluorination catalyst comprises the following steps: dissolving soluble salt of the active component and soluble salt of the auxiliary agent in water according to the mass percentage of the active component and the auxiliary agent, then dropwise adding a precipitator to enable metal ions to be completely precipitated, adjusting the pH value to be 7.0-9.0, enabling the metal ions to be fully precipitated under the stirring condition, aging for 12-36 hours, filtering the formed slurry, drying for 6-24 hours at 100-250 ℃, crushing the solid, and performing compression molding to obtain a catalyst precursor; and roasting the catalyst precursor for 6-24 hours at 300-500 ℃ in a nitrogen atmosphere, and activating for 6-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to prepare the fluorination catalyst.
5. The method of claim 4, wherein: wherein the soluble salt of chromium is selected from chromium trichloride, chromium nitrate, chromium acetate; the soluble salt of molybdenum is selected from molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride; the soluble salt of tungsten is selected from tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride; the soluble salt of the auxiliary agent is selected from at least one or more of nitrate, chloride and acetate of the auxiliary agent; the precipitant is at least one or more selected from ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide.
6. The method of claim 5, wherein: the soluble salt of the auxiliary agent is selected from at least one or more of soluble salts of iron, cobalt and magnesium; the precipitant is selected from ammonia water.
7. The method of claim 1, wherein: the reaction conditions of the fluorination reaction are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-500 ℃, and the ratio of the amount of the tetrafluoro-butatriene or tetrachloro-butatriene to the amount of the hydrogen fluoride is 1: 2 to 30, and the contact time is 5 to 100 s.
8. The method of claim 7, wherein: the reaction conditions are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 350-500 ℃, and the ratio of the amount of the tetrafluoro-butatriene or tetrachloro-butatriene to the amount of the hydrogen fluoride is 1: 10 to 20, and the contact time is 10 to 50 s.
9. The method of claim 8, wherein: the reaction conditions are as follows: the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 350-500 ℃, and the ratio of the amounts of the tetrafluoro-triene and the hydrogen fluoride is 1: 10 to 20, and the contact time is 10 to 50 s.
10. The method according to any one of claims 1 to 9, wherein: the products of the fluorination reaction are obtained by side products of 1,1,1,4,4, 4-hexafluoro-2-butene and Z-1,1, 2,4,4, 4-hexafluoro-2-butene besides the main products of E-1,1,1, 2,4, 4-heptafluorobutane, and the side products of 1,1,1,2,4,4, 4-heptafluorobutane and Z-1,1,1,4,4, 4-hexafluoro-2-butene are recycled to the reactor of the fluorination reaction for continuous reaction, the conversion to E-1,1,1,4,4, 4-hexafluoro-2-butene is carried out by dehydrofluorination of 1,1,1,2,4,4, 4-heptafluorobutane and isomerization of Z-1,1,1,4, 4-hexafluoro-2-butene.
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| WO2023205375A1 (en) * | 2022-04-22 | 2023-10-26 | The Chemours Company Fc, Llc | Fluorobutene compositions comprising e-1,1,1,4,4,4-hexafluoro-2-butene and uses thereof |
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