CN107552064B - A kind of fluorination catalyst and preparation method thereof - Google Patents
A kind of fluorination catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of fluorination catalyst and its preparation method and application, the fluorination catalyst includes that Cr, Al, In, Ni, La and metallic element X, the metallic element X are selected from least one of Co, Mg, Ce, Fe, Mn, Cu, Y and Ga；The mass ratio of Cr, Al, In, Ni, La and metallic element X are 70~90:5~10:1~3.5:2~4.5:0.5~3:3~5.5 in the fluorination catalyst.The precursor of the fluorination catalyst is prepared by co-precipitation preparation method, and expanding agent ammonium salt is added in preparation process.The large specific surface area of the precursor of fluorination catalyst prepared by the present invention, pore structure is good, catalytic activity is high, is especially suitable for being catalyzed the preparation of R134a after fluorination, by-product control effect is excellent and the service life is long.
Description
Technical field
The present invention relates to a kind of fluorination catalysts and its preparation method and application, and in particular to one kind is used for halogenated hydrocarbons and fluorine
Change the catalyst of the gas phase fluorination of hydrogen, in particular for being catalyzed the catalyst and preparation method thereof for preparing R134a.
Background technique
In fluorine chemical field, since the Ozone Depletion Potential (ODP) of hydrogen fluorohydrocarbon (HFCs) is 0, global warming potential
Value (GWP) is smaller, and refrigeration performance is similar to fluorochlorohydrocarbon (CFCs), is the ideal substitute of CFCs, is widely used in large-scale quotient
Industry refrigerant, foaming agent, extinguishing chemical etc..Gas phase exchange chloride for fluoride is the key reaction of selective synthesis fluorochemical,
Since its is simple and easy to do, economical and practical, have many advantages, such as that pollution is few easy to operate, oneself is through being widely used in the industrial production of hydrofluorocarbon
In the process.
Catalysts for gas phase fluorination is the core for producing fluorohydrocarbon (HFCs) process route, it has now been found that vapor- phase synthesis fluorine
Bulk catalyst for hydrocarbon (HFCs and HFOs) is chromium-based catalysts.Although chromium oxide has toxicity, not yet find at present
The catalyst of the substitution chromium oxide of effect.Chromium-based catalysts for gas phase fluorination synthesizing fluoro hydrocarbon mainly have the basic body catalyst of chromium
With support type chromium-based catalysts, research finds that catalyst formulation directly affects the performance of catalyst, the performance and preparation of catalyst
There are substantial connections for technique, are usually improved during Catalyst Design by changing catalyst pore structure or addition metal promoter
Catalyst performance.As Chinese patent CN1931431A discloses added in Co, Mn, Zn, Fe, Mg, Al, Ni in the catalyst one
The molar ratio of kind or two kinds of elements, chromium and other metallic elements is 1:0.001~0.6, and gained catalyst is easily-activated, has
Good catalyst performance.For another example Chinese patent CN105727929 discloses a kind of fluorination catalyst of bigger serface, contains
Cr, Al, Mg and the 4th kind of metallic element, the 4th kind of metallic element are selected from one of Ga, Cd and Co, two or three, this hair
The fluorination catalyst of bright offer replaces gas phase fluorination suitable for fluorine chlorine, has the advantages that the service life is long, is not easy to tie carbon.This
Outside, many researchs change the pore structure of catalyst by the way that non-metal assistant is added, so that the performance of catalyst is improved, such as China
CN101214448A discloses a kind of chromium-based fluorination catalyst and preparation method thereof, the catalyst during the preparation process ammonium fluoride and
Ammonium acid fluoride, catalyst increase catalyst pore volume and specific surface area in roasting process；For another example CN101214447A is disclosed
A kind of Naluminum fluoride base fluorating catalyst and preparation method thereof, which adds ammonium aluminum fluoride class compound during the preparation process,
Increase specific surface area and the aperture of catalyst.
Although fluorination catalyst has very big progress by years development, but still remain catalyst and be easy carbon distribution, urges
Agent service life short problem, causes by-product in production process to increase, needs regenerated catalyst of frequently stopping, mention production cost
Height, while catalyst activity and selectivity needs to be further increased.Especially refrigerant product R134a during the preparation process,
The problems such as by-product R134 is selectively excessively high, and catalyst activity is lower and easy carbon distribution is serious, urgent need develop it is a kind of it is haveing excellent performance,
Suitable catalysis prepares the catalyst prod of refrigerant R134a.
Summary of the invention
In view of the above-mentioned problems, the present invention is in catalyst formulation design process, in conjunction with gas phase fluorine mechanism of catalytic reaction (fluorine chlorine
Exchange reaction), it is contemplated that the synergistic effect of influence and various metals auxiliary agent of the various metal promoters to the reaction, using co-precipitation
Method prepares a kind of catalyst combination formula of multi-element metal auxiliary agent, adds expanding agent in the combination formula to change catalyst pores
Structure, while another metal promoter is added by vacuum-impregnated method, obtained catalyst activity is high, it is not easy to carbon distribution,
Service life greatly prolongs, and when catalysis prepares R134a, by-product is significantly reduced.
On the one hand technical solution of the present invention provides a kind of fluorination catalyst, the fluorination catalyst include Cr, Al,
In, Ni, La and metallic element X, the metallic element X are selected from least one of Co, Mg, Ce, Fe, Mn, Cu, Y and Ga.One
In a little embodiments, metallic element X is selected from least one of Co, Mg, Mn, Y and Ga.
In the present invention, the mass ratio of Cr, Al, In, Ni, La and metallic element X be 70~90:5~10:1~3.5:2~
4.5:0.5~3:3~5.5.In some embodiments, the mass ratio of Cr, Al, In, Ni, La and metallic element X be 73.5~
88.5:5~10:1~3.5:2~4.5:0.5~3:3~5.5；In other embodiments, Cr, Al, In, Ni, La and gold
The mass ratio for belonging to element X is 73.5~88.5:5~9:1~3:2~4:1~3:3~5；Also in some embodiments, Cr,
The mass ratio of Al, In, Ni, La and metallic element X are 73.5~88.5:5~8:1~2.5:2~3.5:1~2.5:3~4.5.
On the other hand technical solution of the present invention provides a kind of method for preparing above-mentioned fluorination catalyst, including following step
It is rapid:
1) it is dissolved in water Cr salt, Al salt, In salt, Ni salt and La salt to obtain mixing salt solution, adds ammonium hydroxide mixed precipitation, mistake
Filter is washed, dry, roasts after adding expanding agent, chromium base presoma is obtained after roasting；
2) it is dissolved in water metallic element X salt to obtain salting liquid, before the chromium base after salting liquid to be added dropwise to vacuum processing
It drives in body, water bath method, it is dry, it roasts, crushes, tabletting obtains catalyst precursor；
3) it is fluorinated above-mentioned presoma to obtain fluorination catalyst.
In preparation method provided by the invention, the Cr salt is selected from chromic nitrate, chromium chloride, chromium sulfate, chrome alum；The Al salt
Selected from aluminum nitrate, aluminium chloride, aluminum sulfate；The In salt is selected from indium nitrate, inidum chloride, indium sulfate；The Ni salt selects nickel chloride, nitre
Sour nickel；The La salt is selected from lanthanum chloride, lanthanum nitrate；The metallic element X salt is selected from nitrate, the chlorate of X.
In preparation method provided by the invention, expanding agent can be added to change the pore structure and specific surface area of catalyst,
The expanding agent is ammonium salt, and specific existence form is inorganic or organic acid salt.In some embodiments, the ammonium salt is
(NH4)2CO3、NH4NO3, at least one of ammonium citrate and ammonium tartrate.But it is not limited to the above-mentioned ammonium salt enumerated, other
The ammonium salt that field commonly can reach same effect can also be used for the present invention.
In preparation method provided by the invention, the sum of the Cr salt, Al salt, In salt, Ni salt and La salt quality and expanding agent
Mass ratio be 1:0.3~0.7.In some embodiments, the sum of the Cr salt, Al salt, In salt, Ni salt and La salt quality with
The mass ratio of expanding agent is 1:0.3~0.5.
In preparation method provided by the invention, in step 1) plus the pH value of ammonium hydroxide mixed precipitation is 9~13.In some implementations
In mode, pH value when precipitating is 8~11；In other embodiments, pH value when precipitating is 8,9,10 or 11.
In preparation method provided by the invention, in step 1) and step 2), the temperature of the drying is 90~130 DEG C.?
In some embodiments, the drying temperature in step 1) and step 2) is 100~120 DEG C.
In preparation method provided by the invention, in step 1) and step 2), the time of the drying is 4~12h.Some
In embodiment, the drying time in step 1) and step 2) is 7~10h.
In preparation method provided by the invention, the roasting is carried out in inert gas, in step 1) and step 2)
The temperature of the roasting is 300~400 DEG C.In some embodiments, the temperature roasted in step 1) and step 2) is 300~
350℃；In other embodiments, step 1) and the middle temperature roasted of step 2) are 320~350 DEG C.
In preparation method provided by the invention, the time of roasting described in step 1) and step 2) is 2~6h.In some realities
It applies in mode, the calcining time in step 1) and step 2) is 3h, 4h or 5h.
In preparation method provided by the invention, graphite additive is added with when tabletting in powder, wherein the quality of graphite is
The 1%~5% of gross mass.The specific surface area of the precursor obtained after tabletting is 370~420m2/ g, pore volume be 0.4~
0.5mL/g, average pore size are 5.0~6.0nm.
In preparation method provided by the invention, the fluorination in the step 3) is under the mixed gas of inert gas and HF
It carries out, fluorination temperature is 200~350 DEG C.In some embodiments, fluorination temperature is 300~350 DEG C.
Fluorination catalyst provided by the invention suitable for fluorine chlorine replace gas phase fluorination, be especially suitable for R125 and
The preparation of R134a, and when preparing R134a, by-product control effect is more excellent.
Water used in embodiments of the present invention is deionized water.
Heretofore described " inert gas " refers in roasting and the fluorinated gas for not participating in reaction in the process, such as
Nitrogen, argon gas etc..
Drying of the present invention, referring to makes water or solvent gasification in material by means of energy, and takes away steam generated
Process.Drying mode used by some embodiments of the invention is drying drying.It should be pointed out that can achieve same effect
Drying means further include but be not limited to drying, vacuum drying, freeze-drying, pneumatic conveying drying, microwave drying, infrared drying and
Dielectric dry etc..
Term " washing " of the present invention refers to through certain effect to weaken or eliminate between impurity and material
Interaction, makes the combination of impurity and material be changed into the combination of impurity and solvent, is finally detached from impurity and material.The present invention
Some embodiments in refer to the process of and rinsed material to pH ≈ 7 with water, ethyl alcohol.
Terminology used in the present invention " filtering " indicate under gravity or other external forces by medium by fluid with it is non-
The operation of fluid separation, the medium includes but is not limited to filter paper, gauze, filter core, semi-permeable membrane, strainer etc., theoretically, containing more
The material of pore structure can become the medium of filtering；The equipment of filtering includes but is not limited to vacuum or decompressor, pressurization dress
It sets, centrifugal device etc..
Unless explicitly stated otherwise in contrast, otherwise, all ranges that the present invention quotes include end value.For example, " roasting
Temperature is 300~400 DEG C ", indicate that the value range of temperature when roasting is 300 DEG C≤T≤400 DEG C.
Terminology used in the present invention "one" or "an" describes element and component described herein.It does so only
It is for convenience, and to provide general meaning to the scope of the present invention.This description should be read to include one or extremely
It is one few, and the odd number also includes plural number, unless it is obvious that it is meant otherwise.
Number in the present invention is approximation, no matter whether uses the wordings such as " about " or " about ".The numerical value of number has
It is possible that the differences such as 1%, 2%, 5%, 7%, 8%, 10%.It is any to have whenever disclosing a number with N value
The number of N+/- 1%, N+/- 2%, N+/- 3%, N+/- 5%, N+/- 7%, N+/- 8% or the value of N+/- 10% can be by clearly public
It opens, adds deduct wherein " +/- " refers to, and the range between N-10% to N+10% is also disclosed.
Unless otherwise defined, the otherwise meaning of all scientific and technical terminologies used herein and common skill of the art
As art personnel are generally understood.Although similar or equivalent method and material also can be used with approach described herein and material
In the implementation or test of embodiment of the present invention, but suitable method and material is described below.What is be mentioned above is all
Publication, patent application, patent and other bibliography are incorporated herein in a manner of being cited in full text, and remove non-quoted physical segment
It falls.If conflict occurs, it is subject to this specification and its included definition.In addition, material, method and embodiment are only illustrative
, it is no intended to it is limited.
The beneficial effects of the present invention are:
1) in catalyst formulation design process of the invention, Determination of multiple metal elements is added on the basis of chromium base, passes through tune
The formula combination of metallic element in catalyst is saved, catalyst active center is changed, using the synergistic effect of other metallic elements, is closed
At catalyst catalytic activity with higher, be conducive to improve target product yield, thus in commercial process
Energy consumption, save the cost can largely be reduced.
2) present invention adds expanding agent ammonium salt in catalyst preparation process, and catalyst precursor is in roasting, ammonium salt class
Compound is thermally decomposed to generate volatile matter so that the specific surface area of catalyst increases, the size of pore volume and average pore size and point
Cloth more evenly, changes catalyst pore structure, is conducive to the progress of exchange chloride for fluoride.
3) when catalyst of the invention is applied to synthesis R134a gas phase fluorination, by-product can greatly be reduced
The selectivity of R134 solves the problems, such as that industrial target product R134a is difficult to separate with its isomer R134, improves product
Quality, while reducing energy consumption.
4) catalyst provided by the invention has a longer life expectancy, and can keep higher catalytic activity in a long time,
When applied to synthesis R134a, the conversion ratio of continuous catalytic reaction 1000h, R133a still remain in 30% or more.
Detailed description of the invention
Fig. 1: the life diagram of the fluorination catalyst of comparative example 1 and embodiment 1
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of the inventive concept, several deformations for making and
It improves, belongs to protection scope of the present invention, in order to further describe the present invention, with reference to the accompanying drawing with for specific embodiment
It is bright.
Comparative example 1
Weigh 50g CrCl3·6H2O、2.83g AlCl3、0.33g InCl3、0.63g NiCl2、0.10g LaCl3Dissolution
In 900mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=10, filtration washing obtains sample, and sample is thrown
It is transferred to roaster after entering 110 DEG C of baking oven dry 6h, in N2320 DEG C of high-temperature roasting 3h in atmosphere, the sample comminution sieving after roasting
And graphite additive row is added and is uniformly mixed, compression molding obtains catalyst precursor.
Weigh 1.59g MgCl2It is dissolved in 110mL deionized water, solution is added dropwise to the chromium base after being vacuum-treated
In presoma, liquid is then evaporated in water-bath, the dry 9h in 100 DEG C of baking ovens, finally in N in tube furnace2Under atmosphere
In 320 DEG C of roasting 3h, the sample comminution after roasting is sieved and graphite is added and is uniformly mixed, and compression molding obtains complex catalyst precursor
Body.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 353.56m2/ g, pore volume are
0.417mL/g, average pore size 4.728nm.
Comparative example 2
Weigh 50g CrCl3·6H2O、3.4g AlCl3、0.22g InCl3、0.76g NiCl2、0.1g LaCl3It is dissolved in
In 1000mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=11, filtration washing obtains sample, plunges the sample into
After 120 DEG C of baking oven dry 8h, adds 36.8g ammonium tartrate and be transferred to roaster, in N2330 DEG C of high-temperature roasting 4h in atmosphere, roasting
Chromium base presoma is obtained after burning.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 340 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 405.621m2/ g, pore volume
For 0.472mL/g, average pore size 5.253nm.
Embodiment 1
Weigh 50g CrCl3·6H2O、3.4g AlCl3、0.44g InCl3、1.01g NiCl2、0.61g LaCl3Dissolution
In 1000mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=11, filtration washing obtains sample, and sample is thrown
After entering 120 DEG C of baking oven dry 8h, 24g (NH is added4)2CO3And it is transferred to roaster, in N2330 DEG C of high-temperature roasting 4h in atmosphere, roasting
Chromium base presoma is obtained after burning.
Weigh 1.37g MgCl2It is dissolved in 100mL deionized water, solution is added dropwise to the chromium base after being vacuum-treated
In presoma, liquid is then evaporated in water-bath, the dry 8h in 110 DEG C of baking ovens, finally in N in tube furnace2Under atmosphere
In 320 DEG C of roasting 5h, the sample comminution after roasting is sieved and graphite is added and is uniformly mixed, and compression molding obtains complex catalyst precursor
Body.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 340 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 400.48m2/ g, pore volume are
0.453mL/g, average pore size 5.444nm.
Embodiment 2
Weigh 50g CrCl3·6H2O、4.53g AlCl3、0.22g InCl3、0.88g NiCl2、0.41g LaCl3Dissolution
In 1050mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=10, filtration washing obtains sample, and sample is thrown
After entering 100 DEG C of baking oven dry 10h, 32g NH is added4NO3And it is transferred to roaster, in N2340 DEG C of high-temperature roasting 5h in atmosphere, roasting
After obtain chromium base presoma.
Weigh 0.92g MnCl2It is dissolved in 110mL deionized water, solution is added dropwise to the chromium base after being vacuum-treated
In presoma, liquid is then evaporated in water-bath, the dry 9h in 120 DEG C of baking ovens, finally in N in tube furnace2Under atmosphere
In 350 DEG C of roasting 4h, the sample comminution after roasting is sieved and graphite is added and is uniformly mixed, and compression molding obtains complex catalyst precursor
Body.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 330 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 395.86m2/ g, pore volume are
0.481mL/g, average pore size 5.1445nm.
Embodiment 3
Weigh 50g CrCl3·6H2O、5.1g AlCl3、0.55g InCl3、0.76g NiCl2、0.51g LaCl3Dissolution
In 1100mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=12, filtration washing obtains sample, and sample is thrown
After entering 110 DEG C of baking oven dry 7h, adds 18.4g ammonium tartrate and be transferred to roaster, in N2350 DEG C of high-temperature roasting 4h in atmosphere,
Chromium base presoma is obtained after roasting.
Weigh 1.01g YCl4It is dissolved in 100mL deionized water, solution is added dropwise to the chromium base after being vacuum-treated
In presoma, liquid is then evaporated in water-bath, the dry 10h in 110 DEG C of baking ovens, finally in N in tube furnace2Under atmosphere
In 330 DEG C of roasting 3h, the sample comminution after roasting is sieved and graphite is added and is uniformly mixed, and compression molding obtains complex catalyst precursor
Body.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 320 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 379.21m2/ g, pore volume are
0.454mL/g, average pore size 5.394nm.
Embodiment 4
Weigh 50g CrCl3·6H2O、2.83g AlCl3、0.77g InCl3、0.63g NiCl2、0.61g LaCl3Dissolution
In 100mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=11, filtration washing obtains sample, and sample is thrown
After entering 120 DEG C of baking oven dry 9h, adds 24.32g ammonium citrate and be transferred to roaster, in N2320 DEG C of high-temperature roasting 3h in atmosphere,
Chromium base presoma is obtained after roasting.
Weigh 1.14g CoCl2It is dissolved in 100mL deionized water, solution is added dropwise to the chromium base after being vacuum-treated
In presoma, liquid is then evaporated in water-bath, the dry 8h in 120 DEG C of baking ovens, finally in N in tube furnace2Under atmosphere
In 340 DEG C of roasting 5h, the sample comminution after roasting is sieved and graphite is added and is uniformly mixed, and compression molding obtains complex catalyst precursor
Body.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 330 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 403.44m2/ g, pore volume are
0.473mL/g, average pore size 5.564nm.
Embodiment 5
Weigh 50g CrCl3·6H2O、5.67g AlCl3、0.66g InCl3、1.13g NiCl2、0.2g LaCl3Dissolution
In 1200mL deionized water, mixed salt solution is mixed with ammonium hydroxide to pH value of solution=10, filtration washing obtains sample, and sample is thrown
After entering 110 DEG C of baking oven dry 10h, 24g NH is added4NO3And it is transferred to roaster, in N2340 DEG C of high-temperature roasting 4h in atmosphere, roasting
After obtain chromium base presoma.
Weigh 1.16g GaCl3It is dissolved in 110mL deionized water, solution is added dropwise to the chromium base after being vacuum-treated
In presoma, liquid is then evaporated in water-bath, the dry 7h in 100 DEG C of baking ovens, finally in N in tube furnace2Under atmosphere
In 330 DEG C of roasting 4h, the sample comminution after roasting is sieved and graphite is added and is uniformly mixed, and compression molding obtains complex catalyst precursor
Body.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 385.95m2/ g, pore volume are
0.464mL/g, average pore size 5.224nm.
Embodiment 6
Fluorination catalyst prepared by comparative example 1, Examples 1 to 3 is used to synthesize the evaluation experimental of R134a respectively, is commented
Valence condition is as follows: being packed into 10mL fluorination catalyst in self-control fixed bed, reaction temperature control is 310~350 DEG C.Lead in reactor
Enter R133a and HF, the flow of R133a is 32g/h, and HF flow is 68g/h.R133a and HF enter reactor reaction after mixing,
Product gas washing, alkali cleaning use gas chromatographic analysis after removing HCl and HF.The conversion ratio and R134a selectivity that table 1 is R133a.
Catalyst prepared by comparative example 1 and embodiment 1 carries out life test, and test result is shown in attached drawing 1.Test data is aobvious
Show, when catalyst prepared by embodiment 1 is applied to synthesis R134a, continuous catalytic reaction 1000h, the conversion ratio of raw material R133a is still
It so is maintained at 30% or more, shows that catalyst provided by the invention has a longer life expectancy, can keep in a long time higher
Catalytic activity.
Evaluation experimental result of 1 fluorination catalyst of table to synthesis R134a
As the data in table 1 it is found that provided in the present invention containing other metallic elements synergistic effect fluorination catalyst,
Expanding agent is added, after preparing under specific process conditions, there is preferable catalytic action, raw material to the synthesis of R134a
The conversion ratio of R133a reaches 29% or more, and can't detect the presence of by-product R134, and the content of by-product R143a also declines
One percentage point, shows that catalyst of the invention can effectively control the generation of by-product.
Claims (9)
1. a kind of fluorination catalyst, which is characterized in that the fluorination catalyst includes Cr, Al, In, Ni, La and metallic element X,
The metallic element X is selected from least one of Co, Mg, Ce, Fe, Mn, Cu, Y and Ga；Cr, Al in the fluorination catalyst,
The mass ratio of In, Ni, La and metallic element X are 70~90:5~10:1~3.5:2~4.5:0.5~3:3~5.5；
The preparation method of the fluorination catalyst, comprising the following steps:
1) it is dissolved in water Cr salt, Al salt, In salt, Ni salt and La salt to obtain mixing salt solution, adds ammonium hydroxide mixed precipitation, filter,
Washing, it is dry, it is roasted after adding expanding agent, chromium base presoma is obtained after roasting；
2) it is dissolved in water metallic element X salt to obtain salting liquid, the chromium base presoma after salting liquid to be added dropwise to vacuum processing
In, water bath method is dry, roasts, and crushes, and tabletting obtains catalyst precursor；
3) it is fluorinated above-mentioned presoma to obtain fluorination catalyst.
2. fluorination catalyst according to claim 1, which is characterized in that the Cr salt, Al salt, In salt, Ni salt and La salt
The mass ratio of quality sum and expanding agent is 1:0.3~0.7.
3. fluorination catalyst according to claim 1 or 2, which is characterized in that the expanding agent is selected from (NH4)2CO3、
NH4NO3, at least one of ammonium citrate and ammonium tartrate.
4. fluorination catalyst according to claim 1, which is characterized in that add the pH of ammonium hydroxide mixed precipitation described in step 1)
Value is 9~13.
5. fluorination catalyst according to claim 1, which is characterized in that drying temperature described in step 1) and step 2)
It is 90~130 DEG C, drying time is 4~12h.
6. fluorination catalyst according to claim 1, which is characterized in that the temperature of roasting described in step 1) and step 2)
Degree is 300~400 DEG C, and the time of roasting is 2~6h.
7. fluorination catalyst according to claim 1, which is characterized in that be added in powder when tabletting in the step 2)
Graphite additive, wherein the quality of graphite is the 1%~5% of gross mass.
8. fluorination catalyst according to claim 1, which is characterized in that the fluorination in the step 3) is in inert gas
With carry out under the mixed gas of HF, fluorination temperature is 200~350 DEG C.
9. the application of fluorination catalyst as described in claim 1, which is characterized in that the fluorination catalyst is for being catalyzed preparation
In the fluorination reaction of R134a.
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| CN108722449A (en) * | 2018-05-04 | 2018-11-02 | 同济大学 | A kind of hydrofluorocarbon dehydrofluorination prepares the catalyst and preparation method and applications of Fluorine containing olefine |
| CN109261175A (en) * | 2018-10-18 | 2019-01-25 | 乳源东阳光氟有限公司 | A kind of hydrogenation-dechlorination loading type Pd/AlF3Catalyst and its preparation method and application |
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