CN108906115B - Catalyst for synthesizing 1,2,3,3,4, 4-hexafluoro-cyclobutene, preparation method and application thereof - Google Patents
Catalyst for synthesizing 1,2,3,3,4, 4-hexafluoro-cyclobutene, preparation method and application thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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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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Abstract
The invention relates to a catalyst for synthesizing 1,2,3,3,4, 4-hexafluoro cyclobutene, a preparation method and application thereof. The catalyst of the invention takes one or more of alkali metal salt, transition metal salt and rare earth metal salt as active components, prepares impregnation liquid according to a certain proportion, adds catalyst carrier after the dissolution is finished, and stands for impregnation for 12-24 h. Filtering the impregnated catalyst, drying at 80-250 ℃ for 12-36h, and roasting at 300-450 ℃ for 12-36h to obtain the isomerization catalyst. The isomerization catalyst is particularly suitable for the reaction of preparing 1,2,3,3,4, 4-hexafluoro-cyclobutene by isomerizing hexafluoro-1, 3-butadiene, and has the advantages of mild reaction conditions, no high polymer and high yield of target products. The isomerization preparation method provided by the invention is simple, and the catalyst preparation method has high reaction activity and high selectivity.
Description
Technical Field
The invention relates to a catalyst, in particular to a catalyst, a preparation method thereof and application thereof in preparing 1,2,3,3,4, 4-hexafluoro cyclobutene through gas phase reaction.
Background
1,2,3,3,4, 4-hexafluorocyclobutene is a fluorine-containing olefin compound with wide application, and is mainly applied to the fields of foaming agents, refrigerants, gas etching, fluorine-containing fine chemical synthesis and the like. Since the molecular structure of the hexachlorocyclobutene does not contain chlorine atoms, the Ozone Depletion Potential (ODP) of the hexachlorocyclobutene is zero, the Global Warming Potential (GWP) of the hexachlorocyclobutene is 119, the atmospheric lifetime of the hexachlorocyclobutene is 1.02a, and the hexachlorocyclobutene is one of ideal substitutes for HCFC and HFC compounds.
The synthesis route of 1,2,3,3,4, 4-hexafluorocyclobutene mainly has three routes: 1) hexachloro-1, 3-butadiene is used as a raw material. The method is mainly carried out by adopting a liquid phase method, wherein a fluorinating reagent is used for carrying out fluorine-chlorine exchange reaction on raw materials to synthesize hexafluoro-1, 3-butadiene, and then a ring-closing reaction is carried out to obtain a target product 1,2,3,3,4, 4-hexafluoro cyclobutene. A phase transfer catalyst is needed in the reaction process, and the overall yield is 68%; 2) hexafluoro-1, 3-butadiene is used as a raw material. The route is carried out by adopting a gas phase catalysis method, and the target product 1,2,3,3,4, 4-hexafluoro cyclobutene is produced in the reaction process (the yield of the target product can reach more than 80 percent), and the linear dimerization and trimerization byproducts of the hexafluoro-1, 3-butadiene are also generated; 3) chlorotrifluoroethylene is used as a raw material. The process comprises the steps of adding a polymerization inhibitor to cyclize raw materials to obtain hexafluorodichlorocyclobutane, and removing chlorine atoms through elimination reaction to obtain the target product 1,2,3,3,4, 4-hexafluorocyclobutene, wherein the reaction conversion rate is only about 30%.
In the synthesis route, the process for synthesizing the 1,2,3,3,4, 4-hexafluoro cyclobutene by taking the hexafluoro-1, 3-butadiene as the raw material through the gas-phase catalytic reaction has the advantages of high yield, continuous and stable reaction and the like, and is suitable for industrial production. The Prober and Miller directly catalyze and synthesize 1,2,3,3,4, 4-hexafluorocyclobutene at the temperature of 150-180 ℃ by taking hexafluoro-1, 3-butadiene as a raw material, the yield of a target product reaches 80%, but more dimers (C) are generated in the reaction process8F12) And trimer (C)12F18) These polymers are viscous and exhibit a certain inhibitory effect on the cyclization reaction. The reaction process is optimized by Haszeldi R.N. and the like, and the reaction temperature is 500 ℃, the reaction yield is highest when the retention time is 5-15s, and the reaction yield reaches about 90%. Although these synthesis processes can achieve a high yield of the target product, the reaction temperature is generally high, and the polymer by-product generated at high temperature may affect the service life of the catalyst, so that it is necessary to develop a novel catalyst to solve the problems of the prior art.
Disclosure of Invention
Aiming at the defects of the gas phase catalysis process, the invention provides the isomerization catalyst for synthesizing the 1,2,3,3,4, 4-hexafluoro-cyclobutene, and the catalyst has the advantages of simple preparation process, mild isomerization reaction temperature, high target product selectivity, no generation of polymer by-products, long service life and the like, and can meet the requirements of industrial application.
The technical scheme adopted by the invention is as follows:
a preparation method of an isomerization catalyst comprises dissolving one or more of alkali metal salt, transition metal salt and rare earth metal salt as active components in water to prepare an impregnation solution, adding a catalyst carrier, standing and impregnating for 12-24 h; filtering the impregnated catalyst, drying at 80-250 ℃ for 12-36h, and roasting at 300-450 ℃ for 12-36h to obtain the isomerization catalyst.
The salts of the active component comprise soluble halide, nitrate, sulfate, carbonate, acetate and double salt.
The active components are cerium salt, nickel salt, copper salt, lanthanum salt and magnesium salt, the salts are nitrate, the loading amount of the active components is 0.1-20%, and the concentration of the impregnation liquid is 0.1-1 mol/L.
The catalyst carrier comprises a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, a 10x molecular sieve, a 13x molecular sieve, a Y-type molecular sieve, a carbon molecular sieve and a high molecular polymer molecular sieve.
The catalyst carrier comprises a 3A molecular sieve, a 4A molecular sieve and a 5A molecular sieve, and the active component is cerium salt or/and nickel salt.
The drying is carried out at 80-200 ℃ for 12-24 h.
The roasting is carried out for 12-24 hours at the temperature of 300-400 ℃.
The isomerization catalyst prepared by the method.
The catalyst is applied to the reaction of isomerizing hexafluoro-1, 3-butadiene to prepare 1,2,3,3,4, 4-hexafluoro-cyclobutene.
A preparation method of 1,2,3,3,4, 4-hexafluoro cyclobutene uses hexafluoro-1, 3-butadiene as a raw material, and performs isomerization reaction in the presence of the catalyst under the gas phase condition to obtain the 1,2,3,3,4, 4-hexafluoro cyclobutene, wherein the reaction temperature is 25-100 ℃, and the total space velocity is controlled within 50-500h‐1。
The reaction temperature is preferably 25-80 ℃, and the total space velocity is controlled within 50-300h-1。
The catalyst is used for preparing 1,2,3,3,4, 4-hexafluorocyclobutene through isomerization reaction, and has the advantages of moderate reaction temperature, high selectivity of target products, no generation of polymers, good stability and long service life.
Advantageous effects
1) The catalyst has simple preparation process and good repeatability;
2) the catalyst has the advantages of high specific surface area, mild reaction conditions and high selectivity of target products;
3) the catalyst has good stability and long service life in the isomerization reaction of synthesizing 1,2,3,3,4, 4-hexafluoro cyclobutene.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments.
Example 1 (sample 1)
Weighing Ce (NO) according to the total loading of 0.5 percent (calculated by CeO)3)3Adding distilled water into the powder to prepare an impregnation solution, adding a certain amount of 5A molecular sieve after all the metal salts are completely dissolved, standing and impregnating for 12 hours. Filtering the impregnated catalyst, drying at 80 ℃ for 12h, and roasting at 300 ℃ for 12h for later use;
example 2 (sample 2)
Weighing Ce (NO) according to the total loading of 1 percent (calculated as CeO and NiO, CeO/NiO is 1/1)3)3、Ni(NO3)2Adding distilled water into the powder to prepare an impregnation solution, adding a certain amount of 4A molecular sieve after all the metal salts are completely dissolved, standing and impregnating for 24 hours. Filtering the impregnated catalyst, drying at 100 ℃ for 24h, and roasting at 350 ℃ for 24h for later use;
example 3 (sample 3)
Weighing Cu (NO) according to the total loading of 0.5 percent (calculated as CuO)3)2Adding distilled water to the powder to prepare a steeping liquid, adding a certain amount of 10x molecular sieve after all the metal salts are completely dissolved, standing and steeping for 12 hours. Filtering the impregnated catalyst, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 24h for later use;
example 4 (sample 4)
According to the total loading of 1 percent (CuO and La)2O3Measured as CuO/La2O3Weighing Cu (NO) 1/13)2、La(NO3)3Adding distilled water into the powder to prepare an impregnation solution, adding a certain amount of 13x molecular sieve after all the metal salts are completely dissolved, standing and impregnating for 12 hours. Filtering the impregnated catalyst, drying at 150 ℃ for 12h, and roasting at 350 ℃ for 12h for later use;
example 5 (sample 5)
Weighing Ni (NO) according to the total loading of 0.5 percent (calculated by NiO)3)2Adding distilled water into the powder to prepare an impregnation solution, adding a certain amount of NaY type molecular sieve after all the metal salts are completely dissolved, standing and impregnating for 24 hours. Filtering the impregnated catalyst, drying at 200 ℃ for 12h, and roasting at 250 ℃ for 24h for later use;
example 6 (sample 6)
Weighing Ni (NO) according to the total loading of 1 percent (calculated by NiO and MgO, NiO/MgO ═ 1/1)3)2、Mg(NO3)2Adding distilled water into the powder to prepare an impregnation solution, adding a certain amount of 10x molecular sieve after all the metal salts are completely dissolved, standing and impregnating for 12 hours. Filtering the impregnated catalyst, drying at 200 ℃ for 24h, and roasting at 300 ℃ for 12h for later use;
example 7 (isomerization reaction)
A304 stainless steel reactor was charged with 385ml of catalyst. The reaction temperature is 50 ℃, and the space velocity of hexafluoro-1, 3-butadiene is 150h-1And washing, alkali washing and drying the reaction product, and then carrying out quantitative analysis by GC.
TABLE 1 results of GC analysis of the isomerization reaction products of different samples
TABLE 2 conversion, target product selectivity and yield
| Sample (I) | Conversion of raw material,% | Target product selectivity,% | Yield of the target product,% |
| 1 | 78.9 | 98.0 | 78.4 |
| 2 | 83.8 | 86.9 | 72.8 |
| 3 | 55.3 | 63.5 | 35.1 |
| 4 | 74.2 | 16.7 | 12.4 |
| 5 | 79.3 | 59.5 | 47.2 |
| 6 | 31.8 | 52.5 | 16.7 |
Example 8 (evaluation of catalyst Life)
A catalyst life evaluation experiment was conducted under the reaction conditions of example 7 using the sample of example 1 as a catalyst.
Table 3 evaluation of catalyst life experimental data
| Reaction time, h | Conversion of raw material,% | Yield of the target product,% |
| 100 | 77.4 | 76.6 |
| 200 | 78.2 | 77.4 |
| 300 | 77.9 | 77.1 |
| 400 | 77.9 | 76.3 |
| 500 | 78.1 | 77.3 |
| 600 | 78.3 | 77.5 |
| 700 | 78.8 | 78.0 |
| 800 | 77.4 | 76.6 |
| 900 | 76.9 | 76.1 |
| 1000 | 77.8 | 77.0 |
As can be seen from the data in Table 1, in the isomerization reaction of sample 1, the content of the target product 1,2,3,3,4, 4-hexafluorocyclobutene is up to 77.3%, the content of the other isomerization product hexafluoro-2-butyne is 1.2%, and the product has no dimer and trimer of hexafluoro-1, 3-butadiene. The data in table 2 show that the catalyst prepared by the invention is used for the isomerization reaction for synthesizing 1,2,3,3,4, 4-hexafluoro-cyclobutene, and the yield of the target product is as high as 78.4%. The data in Table 3 show that the catalyst prepared by the invention has stable catalytic activity in a life evaluation experiment, the catalytic performance is not obviously reduced after 1000 hours, and the service life of the catalyst is obviously longer. The reaction temperature in the prior art is high, the maximum temperature reaches 500 ℃, more polymers are generated, and olefins and polymers are easy to coke at high temperature, which have great influence on the service life of the catalyst. The isomerization reaction in the invention can be carried out under very mild conditions, no polymer is generated, and the catalyst has great advantages in service life.
Claims (7)
1. Use of an isomerization catalyst in the isomerization of hexafluoro-1, 3-butadiene to 1,2,3,3,4, 4-hexafluoro-cyclobutene, said isomerization catalyst being prepared by: dissolving cerium salt serving as an active component in water to prepare an impregnation solution, adding a catalyst carrier, standing and impregnating for 12-24 hours; filtering the impregnated catalyst, drying at 80-250 ℃ for 12-36h, and roasting at 300-450 ℃ for 12-36h to obtain the isomerization catalyst, wherein the catalyst carrier is a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, a 10x molecular sieve, a 13x molecular sieve, a Y-type molecular sieve, a carbon molecular sieve or a high molecular polymer molecular sieve.
2. The use according to claim 1, wherein the salt of the active ingredient is a soluble halide, nitrate, sulphate, carbonate, acetate or double salt.
3. The use of claim 2, wherein the salt is nitrate, the loading amount of the active component is 0.1-20% in terms of CeO, and the concentration of the impregnation solution is 0.1-1 mol/L.
4. The use of claim 1, the catalyst support being a 3A molecular sieve, a 4A molecular sieve or a 5A molecular sieve.
5. The use of claim 1, wherein the drying is drying at 80-200 ℃ for 12-24h, and the roasting is roasting at 300-400 ℃ for 12-24 h.
6. According to any one of claims 1 to 5The application takes hexafluoro-1, 3-butadiene as a raw material, and the 1,2,3,3,4, 4-hexafluoro cyclobutene is obtained by isomerization reaction under the gas phase condition and in the presence of an isomerization catalyst, wherein the reaction temperature is 25-100 ℃, and the total space velocity is controlled within 50-500h-1。
7. The use of claim 6, wherein the reaction temperature is 25-80 ℃, and the total space velocity is controlled within 50-300h-1。
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