CN108057435B - Preparation method of gas phase fluorination catalyst - Google Patents
Preparation method of gas phase fluorination catalyst Download PDFInfo
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- CN108057435B CN108057435B CN201711103893.2A CN201711103893A CN108057435B CN 108057435 B CN108057435 B CN 108057435B CN 201711103893 A CN201711103893 A CN 201711103893A CN 108057435 B CN108057435 B CN 108057435B
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- phase fluorination
- fluorination catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a gas phase fluorination catalyst, which comprises the following steps: uniformly mixing nanocrystalline gamma-alumina powder, amorphous chromium oxide powder, an organic matter II and graphite, and tabletting and forming to obtain a gas-phase fluorination catalyst precursor; and fluorinating the precursor of the gas-phase fluorination catalyst to obtain the gas-phase fluorination catalyst. Wherein the nanocrystalline gamma-alumina powder is prepared by an aqueous gel-sol method and is added with an organic matter I. The organic matter I and the organic matter II can be decomposed and volatilized by heating to play a pore-forming role, so that the obtained gas-phase fluorination catalyst still has a higher specific surface area after fluorination, shows high activity and high stability, and is particularly suitable for preparing R134a products.
Description
Technical Field
The invention relates to a preparation method of a fluorination catalyst, in particular to a preparation method of a catalyst for gas-phase fluorination reaction of halogenated hydrocarbon and hydrogen fluoride, and especially relates to a preparation method of a gas-phase fluorination catalyst for catalytic preparation of R134 a.
Background
Research in recent years has found that fluorinated hydrocarbons ((HFCs) have an Ozone Depletion Potential (ODP) of 0 and a low Global Warming Potential (GWP), and are widely used in large-scale commercial refrigerants, blowing agents, fire extinguishing agents, etc., the key production process of the mainstream environment-friendly refrigerant (R125, R134a, R1234yf) products in the market at present is a gas-phase fluorination catalytic reaction process, a gas-phase fluorination catalyst is the core of the process route for producing fluorinated hydrocarbons ((HFCs), and the gas-phase fluorination catalyst mainly adopts a chromium-based solid catalyst or an aluminum-based solid catalyst, and a great deal of research has found that the catalytic activity of the fluorination catalyst has a great relationship with the pore volume, the pore diameter and the specific surface area of the catalyst, generally speaking, the high specific surface area, the high pore volume and the appropriate pore diameter can effectively improve the activity and the selectivity of the catalyst, however, the gas phase fluorination catalyst precursor exists mainly in the form of oxide, rather than in a fluorinated state, so that the gas phase fluorination catalyst precursor needs to be subjected to fluorination activation treatment before reaction, and the high exothermic phenomenon in the fluorination activation treatment directly leads to the results of increased catalyst crystal grains, greatly reduced specific surface area and the like, thereby causing the problems of low activity, poor stability, frequent regeneration and activation and the like of the obtained fluorination catalyst, so that the development of the gas phase fluorination catalyst with high temperature resistance and high specific surface area has great significance.
There are many studies in the prior art relating to the improvement of the specific surface area of gas phase fluorination catalysts. For example, chinese patent CN101214449A lujian discloses a fluorination catalyst and a preparation method thereof, in which an aluminum compound, a trivalent chromium compound and an ammonium compound are mixed at a mass ratio of 40-80:10-30:10-30, and the mixture is calcined and fluorinated to prepare the fluorination catalyst. However, the above-mentioned production method has a limited degree of improvement in the specific surface area of the fluorination catalyst, and the specific surface areas of the fluorination catalysts after activation are all 100m2Below/g, and the refrigerant product R134a is not specifically applied, and the effect is unknown.
Disclosure of Invention
Aiming at the problems that the specific surface area is greatly reduced after the gas-phase fluorination catalyst precursor is subjected to fluorination activation treatment in the prior art, so that the obtained fluorination catalyst is low in activity, poor in stability, frequent in regeneration activation and the like, the invention provides the novel preparation method of the gas-phase fluorination catalyst, and the obtained gas-phase fluorination catalyst still has high specific surface area after fluorination, shows high activity and high stability, and is particularly suitable for preparing R134a products.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a gas phase fluorination catalyst, comprising:
s1: uniformly mixing nanocrystalline gamma-alumina powder, amorphous chromium oxide powder, an organic matter II and graphite, and tabletting and forming to obtain a gas-phase fluorination catalyst precursor;
s2: and fluorinating the precursor of the gas-phase fluorination catalyst to obtain the gas-phase fluorination catalyst.
Further, the mass ratio of the amorphous chromium oxide powder, the nanocrystalline gamma-alumina powder, the organic matter II and the graphite in the step S1 is 65-98.8:1-15:0.1-10: 0.1-10.
Further, in step S1, the organic substance II is one or more selected from amphoteric cellulose, polyoxyethylene diamine, quaternary ammonium iodide, polyethylene glycol, and polyvinylpyrrolidone.
Further, the nanocrystalline γ -alumina powder in step S1 is prepared by the following method: adding metal aluminum salt, metal auxiliary agent and organic matter I into a solvent, stirring for dissolving, condensing and refluxing, then dropwise adding a water solution of a precipitator, reacting and crystallizing to obtain a liquid sol, then drying to obtain a solid gel, and finally roasting to obtain nanocrystalline gamma-alumina powder; wherein the mass metal of the organic matter I accounts for 1-20% of the mass of the aluminum salt.
Further, the metal auxiliary agent comprises alkaline earth metal and rare metal, wherein the alkaline earth metal is selected from one or more of Mg, Ca and Ba, and the rare metal is selected from one or more of La, Y and Ce.
Further, the organic matter I comprises alcohol, organic acid and saccharide, and the mass ratio of the alcohol to the organic acid to the saccharide is 10-30:40-80: 10-30.
Further, the alcohol is selected from one or more of ethanol, ethylene glycol, propanol, glycerol, isopropanol, butanol and butanediol; the organic acid is selected from one or more of acetic acid, tartaric acid and citric acid; the saccharide is selected from one or more of glucose, sucrose and fructose.
Further, the time for dripping the precipitant solution is controlled to be 1-60 min; the drying conditions are as follows: firstly, vacuum drying for 8-12 h at 25-50 ℃, and then vacuum drying for 2-4h at 110 ℃; the roasting conditions are as follows: roasting for 3-8h at the temperature of 350-550 ℃ under the nitrogen atmosphere.
On the other hand, the invention also provides a gas-phase fluorination catalyst prepared by the preparation method of the gas-phase fluorination catalyst and application of the gas-phase fluorination catalyst in the fluorination reaction for preparing R134 a.
Detailed description of the invention
1. Preparation of nanocrystalline gamma-alumina powder
The nanocrystalline gamma-alumina powder used in the above-mentioned preparation method of the vapor phase fluorination catalyst of the present invention is obtained by the following preparation method: adding metal aluminum salt, metal auxiliary agent and organic matter I into a solvent, stirring for dissolving, condensing and refluxing, then dropwise adding a precipitator solution, reacting and crystallizing to obtain liquid sol, then drying to obtain solid gel, and finally roasting to obtain the nanocrystalline gamma-alumina powder.
Further, the metal auxiliary agent comprises alkaline earth metal and rare metal, wherein the alkaline earth metal is selected from one or more of Mg, Ca and Ba, and the rare metal is selected from one or more of La, Y and Ce.
Preferably, the metal additive is a mixture of Mg and La. But are not limited to the above combinations, combinations of other alkaline earth metals and rare metals, for example, Mg and Ce, Ba and La, Mg and Y, Ca and La, and the like, may also be used in the present invention.
Further, the organic substance I accounts for 1 to 20% by mass, preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and particularly preferably 2 to 5% by mass of the metal aluminum salt.
Further, the organic matter I comprises alcohol, organic acid and saccharide, and the mass ratio of the alcohol to the organic acid to the saccharide is 10-30:40-80:10-30, preferably 15-30:50-70:10-25, and more preferably 20-30:55-65: 15-20.
Further, the alcohol is selected from one or more of ethanol, ethylene glycol, propanol, glycerol, isopropanol, butanol and butanediol; the organic acid is selected from one or more of acetic acid, tartaric acid and citric acid; the saccharide is selected from one or more of glucose, sucrose and fructose.
Preferably, the organic substance I is a mixture of isopropanol, tartaric acid and glucose.
Further, the time for dripping the aqueous solution of the precipitator is controlled within 1-60min, preferably 2-50min, and more preferably 5-30 min.
Further, the precipitant is one or more selected from ammonia water, ammonium carbonate and urea.
Further, the drying conditions of the liquid sol are as follows: vacuum drying is carried out for 8-12 h at 25-50 ℃, and then vacuum drying is carried out for 2-4h at 110 ℃.
Further, the roasting conditions are as follows: roasting for 3-8h at the temperature of 350-550 ℃ under the nitrogen atmosphere.
2. Preparation of amorphous chromium oxide powder
The amorphous chromium oxide powder used in the above-described process for the preparation of the gas phase fluorination catalyst of the present invention can be prepared by any conventional method.
Preferably, the amorphous chromium oxide powder is prepared by the following preparation method:
dissolving metal chromium salt, metal auxiliary agent and organic matter I in water, stirring and dissolving at room temperature to obtain a metal salt mixed solution, adding the metal salt mixed solution into a precipitator aqueous solution by using a peristaltic pump, aging, filtering, drying and roasting to obtain amorphous chromium oxide particles, and crushing and sieving (40-120 meshes) to obtain amorphous chromium oxide powder.
Further, the metal chromium salt is selected from chromium nitrate, chromium chloride, chromium sulfate or chrome alum.
Further, the metal auxiliary agent is selected from one or more of Zn, Mg, Al, Fe, Co, Ni and La.
Preferably, the metal auxiliary agent is Mg, Al, Zn and La.
Further, the mass of the organic matter I accounts for 1-10%, preferably 1-8%, more preferably 2-5% of the mass of the chromium salt.
Further, the organic matter I is a mixture of alcohol, organic acid and saccharide, and the mass ratio of the alcohol, the organic acid and the saccharide is 10-30:40-80:10-30, preferably 15-30:50-70:10-25, and more preferably 20-30:55-65: 15-20.
Further, the alcohol is selected from one or more of ethanol, ethylene glycol, propanol, glycerol, isopropanol, butanol and butanediol; the organic acid is selected from one or more of acetic acid, tartaric acid and citric acid; the saccharide is selected from one or more of glucose, sucrose and fructose.
Preferably, the organic substance I is a mixture of ethanol, citric acid and sucrose.
Further, the precipitant is one or more selected from ammonia water, ammonium carbonate and urea.
Further, the drying conditions are as follows: drying at 100 ℃ and 120 ℃ for 12 h.
Further, the roasting is carried out in inert gas, the roasting temperature is 200-400 ℃, and the roasting time is 3-10 h.
3. Preparation of gas phase fluorination catalyst
The preparation method of the gas phase fluorination catalyst comprises the following steps: uniformly mixing nanocrystalline gamma-alumina powder, amorphous chromium oxide powder, an organic matter II and graphite, and tabletting to obtain a catalyst precursor; and fluorinating the catalyst precursor to obtain the gas-phase fluorination catalyst.
Further, the mass ratio of the amorphous chromium oxide powder to the nanocrystalline gamma-alumina powder to the organic matter II to the graphite is 65-98.8:1-15:0.1-10:0.1-10, preferably 75-93.8: 5-12: 0.2-5: 1-8, and more preferably 81-90: 8-12: 0.5-2: 1.5-5.
Further, the organic substance II is one or more selected from amphoteric cellulose, polyoxyethylene diamine, quaternary ammonium type ammonium iodide, polyethylene glycol, and polyvinylpyrrolidone (PVP).
Preferably, the amphoteric cellulose is quaternary ammonium carboxymethyl cellulose, and the quaternary ammonium carboxymethyl cellulose is one or more selected from the group consisting of glycidyl trioctyl ammonium chloride-carboxymethyl cellulose (EPTO-CMC), glycidyl dimethyltetradecyl ammonium chloride-carboxymethyl cellulose (MEQ-CMC), and trimethyl lignin ammonium chloride-carboxymethyl cellulose (TLQAS-CMC).
Preferably, the quaternary ammonium carboxymethyl cellulose is EPTO-CMC.
But not limited to, the quaternary ammonium type carboxymethyl cellulose listed above, and other amphoteric celluloses commonly used in the art to achieve the same effect may also be used in the present invention.
Preferably, the quaternary ammonium type ammonium iodide is N- [3- (p-perfluorononenoxybenzoyl) propyl ] -N, N, N-trimethyl ammonium iodide. But are not limited to the N- [3- (p-perfluorononenoxybenzoyl) propyl ] -N, N, N-trimethyl ammonium iodide listed above, other quaternary ammonium type ammonium iodides commonly used in the art to achieve the same effect may also be used in the present invention.
Further, the fluorination is carried out under the mixed gas of inert gas and HF, and the fluorination temperature is 300-400 ℃. Preferably, the fluorination temperature is 300-350 ℃.
4. Gas phase fluorination catalyst
The gas-phase fluorination catalyst prepared by the preparation method provided by the invention has the specific surface area of 130-150 m2(ii) in terms of/g. In some embodiments, the gas phase fluorination catalyst has a specific surface area of 130m2/g、135m2/g、140m2G or 145m2/g。
Definition of terms
The "water" used in the embodiments of the present invention is deionized water.
The "inert gas" used in the present invention refers to a gas which does not participate in the reaction during the calcination and fluorination, such as nitrogen, argon, etc.
The drying in the invention refers to a process of gasifying water or solvent in the material by energy and taking away generated steam. The drying mode employed in some embodiments of the present invention is oven drying. It should be noted that drying methods that can achieve the same effect also include, but are not limited to, oven drying, vacuum drying, freeze drying, air flow drying, microwave drying, infrared drying, high frequency drying, and the like.
The term "washing" as used herein means that the impurities are separated from the material by reducing or eliminating the interaction between the impurities and the material, so that the combination of the impurities and the material is converted into the combination of the impurities and the solvent. Some embodiments of the invention refer to the process of washing the material with water, ethanol to pH ≈ 7.
The term "filtration" as used herein means the separation of fluids from non-fluids by a medium under the action of gravity or other external forces, including but not limited to filter paper, gauze, filter elements, semi-permeable membranes, screens, etc., and in theory, materials containing porous structures may be the media of filtration; filtration devices include, but are not limited to, vacuum or pressure reduction devices, pressurization devices, centrifugation devices, and the like.
All ranges cited herein are inclusive, unless expressly stated to the contrary. For example, "calcination time 3-8 h" means a calcination time in the range of 3h ≦ 8 h.
The terms "a" or "an" are used herein to describe elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. Such description should be understood to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
The numbers in this disclosure are approximate, regardless of whether the word "about" or "approximately" is used. The numerical value of the number may have differences of 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number with a value of N is disclosed, any number with a value of N +/-1%, N +/-2%, N +/-3%, N +/-5%, N +/-7%, N +/-8% or N +/-10% is explicitly disclosed, wherein "+/-" means plus or minus, and a range between N-10% and N + 10% is also disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific paragraph is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The invention has the beneficial effects that:
1) according to the invention, when the nanocrystalline gamma-alumina powder and amorphous chromium oxide are prepared, the organic matter I and the metal auxiliary agent are added, on one hand, the organic matter I can highly disperse the precipitated particles and the metal auxiliary agent, so that excessive precipitation of the precipitated particles in the precipitation process and the agglomeration rate of the metal auxiliary agent in the reaction heat release process are prevented; on the other hand, in the roasting stage, the organic matter I is heated and volatilized to play a pore-forming role, and meanwhile, the metal auxiliary agent can effectively reduce the collapse rate of the pore channel; the synergistic effect of the two is beneficial to the catalyst to keep high specific surface area, original aperture and morphology after high-temperature treatment;
2) according to the preparation method of the gas phase fluorination catalyst, an organic matter II is added, and the organic matter II can be heated, decomposed and volatilized to play a pore-forming role and a lubricating and bonding role, so that the activity and the service life of the gas phase fluorination catalyst are improved;
3) when the catalyst prepared by the invention is applied to the preparation of R134a, the catalyst shows high activity and high stability, and the conversion rate of the raw material R133a is still kept about 27% after the catalyst continuously reacts for 1050 hours.
Drawings
FIG. 1: lifetime diagrams for vapor phase fluorination catalysts prepared in example 3 and comparative example 3
Detailed Description
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications within the spirit of the invention will become apparent to those skilled in the art, and further description of the invention will be made with reference to the embodiments illustrated in the drawings.
Example 1-1 preparation of nanocrystalline gamma-alumina powder
25.03g of Al (NO)3)3·9H2O、1.35g MgCl2、0.21gLaCl3Dissolving 1g of organic matter I (0.26g of isopropanol, 0.56g of tartaric acid and 0.18g of glucose) in 500mL of ethanol solvent, carrying out reflux treatment for 2h under stirring at 80 ℃, then dropwise adding an ammonium carbonate aqueous solution for 10min, then maintaining the reaction temperature for crystallization for 12h to obtain a liquid sol, then carrying out vacuum drying on the liquid sol at 110 ℃ for 12h to obtain a solid gel, and finally roasting at 550 ℃ for 3h to obtain nanocrystalline gamma-alumina powder serving as a carrier for later use.
Examples 1-2 preparation of nanocrystalline gamma-alumina powders
25.03g of Al (NO)3)3·9H2Dissolving O in 500mL of ethanol solvent, carrying out reflux treatment for 2h under stirring at 80 ℃, then dropwise adding an ammonium carbonate aqueous solution for 10min, then maintaining the reaction temperature for crystallization for 12h to obtain liquid sol, then carrying out vacuum drying on the liquid sol at 110 ℃ for 12h to obtain solid gel, and finally roasting at 550 ℃ for 3h to obtain the nanocrystalline gamma-alumina powder.
EXAMPLE 2 preparation of amorphous chromium oxide powder
50.02g of CrCl are weighed out3·6H2O、1.85gMgCl2、2.81g AlCl3、1.53gZnCl3、0.21g LaCl3Dissolving 2.49g of organic matter I (0.68g of ethanol +1.42g of citric acid +0.39g of sucrose) in 900mL of deionized water to obtain a mixed salt solution, mixing the mixed salt solution with ammonia water until the pH value of the solution is 10, filtering and washing the solution to obtain a sample, drying the sample in an oven at 110 ℃ for 6 hours, transferring the sample to a roasting oven, and performing N-phase precipitation on the dried sample2Roasting at 350 deg.C for 3 hr, pulverizing and sieving to obtainAmorphous chromium oxide powder for use.
Example 3
Mixing, tabletting and molding 92% of amorphous chromium oxide powder, 5% of nanocrystalline gamma-alumina powder prepared in example 1-1, 1% of EPTO-CMC and 2% of graphite to obtain a gas-phase fluorination catalyst precursor; then the gas phase fluorination catalyst precursor is loaded into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the gas phase fluorination catalyst.
Example 4
Mixing 85% of amorphous chromium oxide powder, 10% of nanocrystalline gamma-alumina powder prepared in example 1-1, 2% of polyoxyethylene diamine and 3% of graphite, tabletting and molding to obtain a gas-phase fluorination catalyst precursor; then the gas phase fluorination catalyst precursor is loaded into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the gas phase fluorination catalyst.
Example 5
Mixing 81% of amorphous chromium oxide powder, 13% of nanocrystalline gamma-alumina powder prepared in example 1-1, 1% of quaternary ammonium type ammonium iodide and 5% of graphite, tabletting and molding to obtain a gas-phase fluorination catalyst precursor; then the gas phase fluorination catalyst precursor is loaded into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the gas phase fluorination catalyst.
Comparative example 1
Mixing 92% amorphous chromium oxide powder, 5% nanocrystalline gamma-alumina powder prepared in example 1-2, 1% EPTO-CMC, 2% graphite, tabletting and forming a vapor phase fluorination catalyst precursor; then the gas phase fluorination catalyst precursor is loaded into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the gas phase fluorination catalyst.
Comparative example 2
Mixing 97% of amorphous chromium oxide powder, 1% of EPTO-CMC and 2% of graphite, tabletting and forming a gas-phase fluorination catalyst precursor; then the gas phase fluorination catalyst precursor is loaded into a reactor, and the gas mixture of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the gas phase fluorination catalyst.
Comparative example 3
Mixing and tabletting 98% of amorphous chromium oxide compound and 2% of graphite to form a gas-phase fluorination catalyst precursor; then the gas phase fluorination catalyst precursor is loaded into a reactor, and the mixed gas of nitrogen and HF is introduced for fluorination at 350 ℃ to prepare the gas phase fluorination catalyst.
Example 6 Performance testing and evaluation
The gas phase fluorination catalysts prepared in examples 3 to 5 and comparative examples 1 to 3 were analyzed for their comparative areas using a specific surface area and pore structure tester, respectively, and the test results are shown in table 1.
The gas phase fluorination catalysts prepared in examples 3 to 5 and comparative examples 1 to 3 were used in the evaluation experiment for synthesizing R134a under the following conditions: 20mL of the prepared gas phase fluorination catalyst is loaded into a self-made fixed bed reactor, and the reaction temperature is controlled to be 310-360 ℃. R133a and HF were fed into the reactor, the flow rate of R133a was 30g/h and the flow rate of HF was 62 g/h. R133a and HF enter a reactor to react after being mixed, and the product gas is washed by water and alkali to remove HCl and HF and then is analyzed by gas chromatography. The conversion of R133a and the selectivity of R134a are shown in Table 2.
The gas phase fluorination catalysts prepared in example 3 and comparative example 3 were subjected to life test, and the test results are shown in FIG. 1.
TABLE 1 specific surface area of gas phase fluorination catalyst
| Numbering | Nanocrystalline gamma-alumina | Organic matter II | Specific surface area, m2/g |
| Example 3 | Example 1-1 preparation | EPTO-CMC | 140.85 |
| Example 4 | Example 1-1 preparation | Polyoxyethylene diamines | 144.11 |
| Example 5 | Example 1-1 preparation | Quaternary ammonium type ammonium iodide | 136.75 |
| Comparative example 1 | Examples 1-2 preparation | EPTO-CMC | 103.12 |
| Comparative example 2 | / | EPTO-CMC | 109.64 |
| Comparative example 3 | / | / | 89.38 |
As can be seen from the data in Table 1, the specific surface area of the gas phase fluorination catalysts prepared in examples 3-5 was as high as 136.75m2(more than g), the specific surface area of the vapor phase fluorination catalyst prepared in example 3 is 100m, as compared with that of comparative examples 1 to 32Increase the concentration to 140m2(ii) in terms of/g. Show that the gas phase fluorination catalyst prepared by the embodiment can still be treated at high temperatureTo maintain a high specific surface area.
Table 2 evaluation of gas phase fluorination catalyst for synthesis of R134a experimental results
As can be seen from the data in table 2, when the gas phase fluorination catalysts prepared in the examples were used to catalyze reactions, the conversion of R133a increased from 26% to 30% or more, which indicates that the gas phase fluorination catalysts prepared in the examples of the present invention have higher activity.
From the test results in fig. 1, it can be seen that the conversion of the raw material R133a remained at about 27% after 1050 hours of continuous reaction in the gas phase fluorination catalyst prepared in example 3, while the conversion of the raw material R133a decreased to 20% in the gas phase fluorination catalyst prepared in comparative example 3, indicating that the gas phase fluorination catalyst prepared in example 3 has more stable catalytic activity and longer service life.
Claims (6)
1. A method for preparing a gas phase fluorination catalyst, comprising:
s1: uniformly mixing nanocrystalline gamma-alumina powder, amorphous chromium oxide powder, an organic matter II and graphite, and tabletting and forming to obtain a gas-phase fluorination catalyst precursor;
s2: fluorinating the gas-phase fluorination catalyst precursor to obtain a gas-phase fluorination catalyst;
in the step S1, the organic matter II is one or more selected from amphoteric cellulose, polyoxyethylene diamine, quaternary ammonium type ammonium iodide, polyethylene glycol and polyvinylpyrrolidone;
the nanocrystalline gamma-alumina powder in step S1 is prepared by the following method: adding metal aluminum salt, metal auxiliary agent and organic matter I into a solvent, stirring for dissolving, condensing and refluxing, then dropwise adding a water solution of a precipitator, reacting and crystallizing to obtain a liquid sol, then drying to obtain a solid gel, and finally roasting to obtain nanocrystalline gamma-alumina powder; wherein the mass of the organic matter I accounts for 1-20% of the mass of the metal aluminum salt; the metal auxiliary agent comprises alkaline earth metal and rare metal, wherein the alkaline earth metal is selected from one or more of Mg, Ca and Ba, and the rare metal is selected from one or more of La, Y and Ce; the organic matter I comprises alcohol, organic acid and saccharide, and the mass ratio of the alcohol to the organic acid to the saccharide is 10-30:40-80: 10-30;
the amorphous chromium oxide powder described in step S1 is obtained by the following preparation method:
dissolving metal chromium salt, metal auxiliary agent and organic matter I in water, stirring and dissolving at room temperature to obtain a metal salt mixed solution, adding the metal salt mixed solution into a precipitator aqueous solution by using a peristaltic pump, aging, filtering, drying and roasting to obtain amorphous chromium oxide particles, and crushing and sieving to obtain amorphous chromium oxide powder; wherein the metal auxiliary agent is selected from one or more of Zn, Mg, Al, Fe, Co, Ni and La; the organic matter I comprises alcohol, organic acid and saccharide, and the mass ratio of the alcohol to the organic acid to the saccharide is 10-30:40-80: 10-30.
2. The method for preparing a vapor phase fluorination catalyst according to claim 1, wherein the mass ratio of the amorphous chromium oxide powder, the nanocrystalline γ -alumina powder, the organic substance II and the graphite in step S1 is 65-98.8:1-15:0.1-10: 0.1-10.
3. The method for producing a gas-phase fluorination catalyst according to claim 1, wherein the alcohol is one or more selected from the group consisting of ethanol, ethylene glycol, propanol, glycerol, isopropanol, butanol and butanediol; the organic acid is selected from one or more of acetic acid, tartaric acid and citric acid; the saccharide is selected from one or more of glucose, sucrose and fructose.
4. The method for preparing a gas phase fluorination catalyst according to claim 1, wherein the time for dropping the precipitant solution is controlled to be 1 to 60 min; the drying conditions are as follows: firstly, vacuum drying for 8-12 h at 25-50 ℃, and then vacuum drying for 2-4h at 110 ℃; the roasting conditions are as follows: roasting for 3-8h at the temperature of 350-550 ℃ under the nitrogen atmosphere.
5. The gas-phase fluorination catalyst produced by the process for producing a gas-phase fluorination catalyst according to any one of claims 1 to 4.
6. Use of the gas phase fluorination catalyst of claim 5 wherein said gas phase fluorination catalyst is used in a fluorination reaction to catalyze the production of R134 a.
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