CN110841637B - Fluorination catalyst precursor and method for producing fluorination catalyst - Google Patents

Fluorination catalyst precursor and method for producing fluorination catalyst Download PDF

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CN110841637B
CN110841637B CN201911204354.7A CN201911204354A CN110841637B CN 110841637 B CN110841637 B CN 110841637B CN 201911204354 A CN201911204354 A CN 201911204354A CN 110841637 B CN110841637 B CN 110841637B
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chromium chloride
fluorination catalyst
salt
catalyst
pore
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CN110841637A (en
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李义涛
邓龙辉
胡为晴
张宏清
孙明刚
余航
黄永锋
唐火强
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Dongguan HEC Tech R&D Co Ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • B01J35/647—
    • B01J35/651—
    • B01J35/69—
    • 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
    • B01J37/031—Precipitation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • 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
    • 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
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention provides a preparation method of a fluorination catalyst precursor. The method comprises the following steps: (1) carrying out first mixing treatment on a chromium chloride solution and ammonia water, wherein the chromium chloride solution contains a high-molecular pore-forming agent; (2) carrying out second mixing treatment and filtration treatment on an aqueous solution containing nano carbon and a platinum salt or a palladium salt and the mixed solution obtained in the step (1) so as to obtain a filter cake, wherein the aqueous solution further contains at least one of chromium chloride and a porous compound; (3) and baking the filter cake to obtain the fluorination catalyst precursor. Wherein the polymer pore-forming agent is at least one of lignin, cellulose, lignosulfonate and starch. The catalyst prepared by the method has the advantages of high mesoporous proportion, firm macroporous structure, high catalytic activity, high weather resistance and long service life.

Description

Fluorination catalyst precursor and method for producing fluorination catalyst
Technical Field
The invention relates to the field of chemical industry, in particular to a fluorination catalyst precursor and a preparation method of a fluorination catalyst.
Background
R134a, 1,1,1, 2-tetrafluoroethane, is a medium-low temperature environment-friendly refrigerant. At present, the process route adopted in industry is trichloroethylene synthesis. First, the first step is the reaction of trichloroethylene with hydrogen fluoride to produce R133a, and then the reaction of R133a with hydrogen fluoride to produce R134 a. During the storage process of the raw material trichloroethylene, the raw material is easy to be partially decomposed due to contact with metals such as magnesium, aluminum and the like, so that the raw material is acidic. In the production of the acidic trichloroethylene, the equipment such as pipelines and reaction furnaces of a production device can be corroded, and a large amount of rust slag is generated, so that a catalyst on the production device is subjected to metal poisoning, and the activity is reduced. In addition, as the process of stacking and filling the catalyst in the tubular fixed bed reactor is adopted in production, the catalyst stacking easily causes large difference of local reaction temperature, and easily causes the phenomena of catalyst carbon formation and crystal sintering.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the method aims at the influence on the catalyst in the R134a production, the internal pore structure distribution of the catalyst is adjusted in a targeted manner, the channel diffusion effect of the catalyst is increased, and the metal poisoning resistance, high-temperature inactivation resistance and carbon deposition resistance of the catalyst are improved. Meanwhile, the structural distribution in the catalyst is adjusted, and the multistage composite pore distribution is adopted, so that the number of mesopores is increased, and the activity of the catalyst is further improved.
In a first aspect of the present invention, a method for preparing a fluorinated catalyst precursor is presented. According to an embodiment of the invention, the method comprises: (1) carrying out first mixing treatment on a chromium chloride solution and ammonia water to obtain a mixed solution, wherein the chromium chloride solution contains a high-molecular pore-forming agent; (2) carrying out second mixing treatment and filtration treatment on an aqueous solution containing nano carbon and a platinum salt or a palladium salt and the mixed solution obtained in the step (1) so as to obtain a filter cake, wherein the aqueous solution further contains at least one of chromium chloride and a porous compound; (3) and baking the filter cake to obtain the fluorination catalyst precursor. The polymer pore-forming agent is at least one of lignin, cellulose, lignosulfonate and starch. According to the preparation method of the fluorination catalyst precursor, in the first step, the macroporous carrier is prepared by adopting the high-molecular pore-forming agent, compared with the preparation of the macroporous carrier in the prior art, the distribution of the inner pore diameter of the formed macropore is more regular, the formation of macropores at specific positions can be realized by adding lignin, cellulose, lignosulfonate or starch at different time, and the formed macropore has a firmer structure; in the second step of preparing the mesopores, a nanometer carbon powder is adopted to increase the mesopore structure in the catalyst, platinum and palladium metal are adopted to provide active sites, the activity of the catalyst is improved, a pore channel compound is adopted as a connecting pore channel between the macropores and the mesopores, so that the macropores and the mesopores in the catalyst carrier are communicated, heat or carbon deposit generated in the catalysis process is discharged through the pore channels and the macropores under the action of airflow, the carbon deposit inactivation of the catalyst in the use process is reduced, the inactivation resistance of the catalyst is improved, and meanwhile, the loading capacity of the active metal can be increased due to the existence of the pore channel compound; and thirdly, baking, namely volatilizing lignin, cellulose, lignosulfonate or starch in the macropores and nanocarbon in the mesopores to form a hollow and mutually communicated macroporous and mesoporous multistage composite pore structure, wherein the mesoporous proportion is high, the macroporous structure is firm, and the catalyst is high in catalytic activity, strong in weather resistance and long in service life.
According to an embodiment of the present invention, the method may further include at least one of the following additional technical features:
according to the embodiment of the invention, in the step (1), the concentration of the chromium chloride solution is 5% (by mass, that is, 5g of chromium chloride is contained in 100g of the solution), the mass-to-volume ratio of the polymeric pore-forming agent to the chromium chloride solution is (90-100 g):1L, and for example, 96.7g of lignin, cellulose, lignosulfonate or starch is added to each liter of the chromium chloride solution.
According to an embodiment of the invention, the channeling compound is provided as at least one of polyacrylamide, triethanolamine.
According to an embodiment of the invention, the platinum or palladium salt is provided in the form of a chlorate salt or a nitrate salt.
According to an embodiment of the invention, the platinum or palladium salt is provided in the form of ammonium tetrachloropalladate, ammonium hexachloroplatinate, platinum nitrate or ammonium tetrachloroplatinate.
According to the embodiment of the invention, in the step (2), the mass ratio of the chromium chloride, the nano carbon, the platinum salt or the palladium salt and the pore channel compound in the aqueous solution is (82-93): (3-10): 1-6): 0.5-5. Preferably, the mass ratio of the chromium chloride, the nano-carbon, the platinum salt or the palladium salt and the pore channel compound in the aqueous solution is (82-93): (4-5): (1-6): 1-2). It should be noted that, if the platinum salt or the palladium salt is provided in various forms, the ratio of the platinum salt or the palladium salt is arbitrary; if the pore channel compound is provided by polyacrylamide and triethanolamine, the ratio of polyacrylamide to triethanolamine is arbitrary.
In some embodiments, the aqueous solution comprises chromium chloride, nanocarbon, platinum salt or palladium salt, and the channel compound in a mass ratio of 91: 4.5: 2.7: 1.8.
in some embodiments, the aqueous solution has a mass ratio of chromium chloride, nanocarbon, platinum salt or palladium salt, and the channel compound of 88.5: 4.4: 5.3: 1.8.
according to an embodiment of the invention, the concentration of the chromium chloride solution is 5% (mass ratio, i.e. 5g of chromium chloride in 100g of solution) and the concentration of the aqueous ammonia is 6% (mass ratio, i.e. 6g of NH in 100g of solution)3·H2O), wherein the volume ratio of the chromium chloride solution to the ammonia water is 1: 10-2: 5.
In some embodiments, the volume ratio of the chromium chloride solution to aqueous ammonia is 3: 11.
According to an embodiment of the invention, the second mixing treatment is carried out at a rotation speed of 30r/min for 15 min.
According to the embodiment of the invention, the baking treatment is carried out for 8-24 hours at the temperature of 80-150 ℃, and then carried out for 7-9 hours at the temperature of 200-600 ℃. The inventor finds that the low-temperature baking and the high-temperature baking can prevent trivalent chromium from being oxidized into hexavalent chromium, and meanwhile, the sectional baking can prevent the catalyst from being sintered, so that the internal structure cannot be damaged, and the internal appearance is more stable.
In a second aspect of the invention, a fluorination catalyst precursor is provided. According to an embodiment of the invention, the fluorinated catalyst precursor comprises: the chromium chloride substrate is characterized by comprising a chromium oxide substrate, wherein the center of the chromium oxide substrate is provided with a large hole, the surface layer of the chromium chloride substrate is provided with a mesopore, active platinum metal or palladium metal is arranged in the mesopore, and the large hole is connected with the mesopore through a polyacrylamide or triethanolamine pore channel compound. The precursor of the fluorination catalyst has a multi-stage composite pore structure, and has the advantages of high mesoporous proportion, firm macroporous structure, high catalytic activity, high weather resistance and long service life.
According to an embodiment of the present invention, the fluorination catalyst precursor may further include at least one of the following additional technical features:
according to the embodiment of the invention, the mesoporous proportion is 78-95%, and the average pore diameter is 5-9 nm. The proportion of mesoporous of the precursor of the fluorination catalyst according to the embodiment of the invention is far greater than that of the prior art, and the reaction activity center and the reaction activity of the catalyst are improved.
In a third aspect of the invention, the invention provides a method of preparing a fluorination catalyst, according to an embodiment of the invention, the method comprising: the fluorination catalyst precursor, as defined above or prepared according to the method described above, is subjected to an activation treatment in order to obtain a more stable fluorination catalyst. The fluorination catalyst prepared according to the embodiment of the invention has high mesoporous proportion, strong carbon deposition resistance and small loss of active metal.
According to an embodiment of the present invention, the method may further include at least one of the following additional technical features:
according to the embodiment of the invention, the activation treatment is carried out for 11-13 hours at the temperature of 300-400 ℃ by introducing nitrogen and hydrogen fluoride.
In a fourth aspect of the invention, a fluorination catalyst is provided. According to an embodiment of the present invention, the fluorination catalyst is obtained by activating the fluorination catalyst precursor.
According to the embodiment of the invention, the mass of the active platinum metal or palladium metal accounts for 0.5-1.5% of the total mass of the fluorination catalyst.
Drawings
FIG. 1 is a flow diagram of the preparation of a precipitated filter cake according to an embodiment of the present invention; and
FIG. 2 is a schematic diagram showing the change in the internal structure of a catalyst during calcination according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
In the present application, "or" means at least one, such as "platinum salt or palladium salt" means at least one of platinum salt and palladium salt; "lignin, cellulose, lignosulfonate, or starch" refers to at least one of lignin, cellulose, lignosulfonate, or starch.
The inventor finds that the mesoporous structure of the existing chromium-based fluorination catalyst is limited, so that the activity is inhibited; meanwhile, in the use process of the chromium-based fluorination catalyst, the process of stacking and filling the chromium-based fluorination catalyst in a reaction tube is adopted, so that the local temperature difference is large during the reaction of the catalyst, and the phenomena of carbon deposition and sintering deactivation of the catalyst are easily caused; the chlorinated alkane of the raw material C2-C4 is easy to decompose, so that the raw material presents certain acidity, and corrodes a metal container in the production process, so that the catalyst is easy to have the deactivation phenomenon of metal poisoning in the use process.
Based on the recognition of the defects of the prior art, the inventor designs a fluorination catalyst with a specific multistage composite pore structure in an oriented mode, increases the proportion of mesopores of the catalyst, provides an important place for forming an active center of the catalyst, provides an internal diffusion channel of the catalyst by adjusting the macroporous structure in the catalyst, reduces carbon deposition inactivation of the catalyst in use, reduces poisoning phenomena caused by blocking the pore structure in the catalyst by adhesion of other metal ions, improves the inactivation resistance of the catalyst, adjusts the internal macroporous structure of the catalyst, and prevents the occurrence of the phenomenon of collapse and inactivation of the pore structure caused by high temperature in the use process of the catalyst.
The preparation method of the fluorination catalyst having a specific multi-stage composite pore structure proposed by the present invention will be described in detail below:
1. preparation of the macroporous carrier: firstly, at least one of lignin, cellulose, lignosulfonate and starch is added into a chromium chloride solution with the concentration of 5%, and the mixture is fully and uniformly stirred at the rotating speed of 45r/min to obtain a mixed solution. And then adding the mixed solution into 6% ammonia water to obtain a mixed solution containing a macroporous carrier, wherein the volume ratio of the chromium chloride solution to the ammonia water is 1: 10-2: 5.
2. Preparation of mesoporous carrier and loading of active metal: mixing chromium chloride, nano carbon (2-50nm), soluble platinum salt or soluble palladium salt, polyacrylamide or triethanolamine according to the mass fraction of 82-93%, 3-10%, 1-6% and 0.5-5% in pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotation speed to 30r/min, maintaining aging for 15min, filtering, and washing the filter cake to neutrality.
3. And (3) catalyst molding: placing the filter cake in the step 2 in an oven under nitrogen atmosphere at 80-150 ℃ for heating and drying for 8-24H, and then placing the filter cake in a roasting furnace at 200-600 ℃ under H2Roasting for 7-9h in the atmosphere. And after roasting is finished, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor.
4. And (2) loading the prepared catalyst precursor into a tubular reactor, introducing nitrogen and hydrogen fluoride, and activating at 400 ℃ for 11-13 hours to obtain the fluorination catalyst with a specific multistage composite pore structure.
FIG. 1 is a flow diagram of a precipitated filter cake preparation according to an embodiment of the present invention; FIG. 2 is a schematic diagram showing the change in the internal structure of a catalyst during calcination according to an embodiment of the present invention.
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The 5% chromium chloride solution used in the following examples was prepared by laboratory personnel, for example, 158.5g of chromium chloride was weighed into 3011.5g of water to obtain a 5% chromium chloride solution.
Example 1
1. Preparation of the macroporous carrier: firstly, 290g of lignin is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the lignin was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing 1.4Kg of chromium chloride, 2-50nm of nano carbon, 2-50nm of ammonium tetrachloroplatinate and 1.8 percent of polyacrylamide according to the mass fraction of 91 percent, 4.5 percent, 2.7 percent and 1.8 percent, adding the mixture into 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotating speed to 30r/min, carrying out filtration after maintaining aging for 15min, and washing a filter cake to be neutral.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere for heating at 120 ℃ for drying for 12H, placing the dried filter cake into a roasting furnace, and placing the roasting furnace in a H furnace2Roasting at 450 ℃ for 8h under the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 1.
Example 2
1. Preparation of the macroporous carrier: firstly, 290g of sodium lignosulphonate is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with sodium lignosulfonate was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing 1.4Kg of chromium chloride, 2-50nm of nano carbon, 2-50nm of ammonium hexachloroplatinate and 1.8 percent of polyacrylamide according to the mass fraction of 91 percent, 4.5 percent, 2.7 percent and 1.8 percent, adding the mixture into 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotating speed to 30r/min, carrying out filtration after maintaining aging for 15min, and washing a filter cake to be neutral.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere for heating at 120 ℃ for drying for 12H, placing the dried filter cake into a roasting furnace, and placing the roasting furnace in a H furnace2Roasting at 350 ℃ for 8h in the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 2.
Example 3
1. Preparation of the macroporous carrier: firstly, 290g of starch is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the starch was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing 1.4Kg of chromium chloride, 2-50nm of nano carbon, 2.7% of platinum nitrate and 1.8% of triethanolamine in proportion of 91%, 4.5%, 2.7% and 1.8% by mass, adding into 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotating speed to 30r/min, maintaining aging for 15min, filtering, and washing the filter cake to be neutral.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 100 ℃, drying for 24H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 450 ℃ for 8h in the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 3.
Example 4
1. Preparation of the macroporous carrier: firstly, 290g of cellulose is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the cellulose was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing 1.4Kg of chromium chloride, 2-50nm of nano carbon, ammonium hexachloropalladate and 1.8 percent of triethanolamine according to the mass fraction of 91 percent, 4.5 percent, 2.7 percent and 1.8 percent, adding the mixture into 26L of pure water, stirring and mixing the mixture evenly, then adding the mixed solution containing the macroporous carrier, adjusting the rotating speed to 30r/min, carrying out filtration after maintaining aging for 15min, and washing a filter cake to be neutral.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 100 ℃, drying for 16H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 450 ℃ for 8h in the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 4.
Example 5
1. Preparation of macroporous carrier: firstly, 290g of cellulose is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the cellulose was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing 1.4Kg of chromium chloride, 2-50nm of nano carbon, ammonium tetrachloropalladate and 1.8% of triethanolamine according to the mass fraction of 91%, 4.5%, 2.7% and 1.8% into 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotation speed to 30r/min, maintaining aging for 15min, filtering, and washing the filter cake to neutrality.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in the nitrogen atmosphere for heating at 80 ℃ and drying for 20H, placing the dried filter cake into a roasting furnace, and putting the roasting furnace in a H mode2Roasting at 550 ℃ for 8h in the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 5.
Example 6
1. Preparation of the macroporous carrier: firstly, 290g of lignin is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with sodium lignosulfonate was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing chromium chloride (1.4Kg), nano carbon (2-50nm), ammonium tetrachloropalladate, ammonium tetrachloroplatinate, triethanolamine and polyacrylamide according to the mass fraction of 88.5%, 4.4%, 2.65%, 0.9% and 0.9% in 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotating speed to 30r/min, aging for 15min, filtering, and washing the filter cake to be neutral.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 80 ℃, drying for 24H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 600 ℃ for 8h in the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 6.
Comparative example 1
1. Preparation of the macroporous carrier: firstly, 290g of lignin is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the lignin was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing chromium chloride (1.4Kg), ammonium tetrachloropalladate, ammonium tetrachloroplatinate, triethanolamine and polyacrylamide in the weight ratio of 92.6%, 2.8%, 0.9% and 0.9% into 26L of pure water, stirring and mixing homogeneously, adding the above mixed liquid containing macroporous carrier, regulating the rotation speed to 30r/min, ageing for 15min, filtering, washing the filter cake to neutrality.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 80 ℃, drying for 24H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 600 ℃ for 8h under the atmosphere. And after roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 7.
Comparative example 2
1. Preparation of macroporous carrier: firstly, 290g of lignin is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the lignin was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing 1.4Kg of chromium chloride, 2-50nm of nano carbon, ammonium tetrachloropalladate and ammonium tetrachloroplatinate in a mass fraction of 90.1%, 4.5%, 2.7% and 2.7% in 26L of pure water, stirring and mixing uniformly, adding the mixed solution containing the macroporous carrier, adjusting the rotation speed to 30r/min, maintaining aging for 15min, filtering, and washing a filter cake to be neutral.
3. Forming a catalyst: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 80 ℃, drying for 24H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 600 ℃ for 8h under the atmosphere. And after roasting is finished, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 8.
Comparative example 3
1. Preparation of the macroporous carrier: firstly, 290g of lignin is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the wood-mixed chromium chloride solution was added to 11L of 6% ammonia water to obtain a mixed solution containing a macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing chromium chloride (1.4Kg), nano carbon (2-50nm), triethanolamine and polyacrylamide according to the mass fraction of 93.5%, 4.7%, 0.9% and 0.9% in 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotation speed to 30r/min, aging for 15min, filtering, and washing the filter cake to be neutral.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 80 ℃, drying for 24H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 600 ℃ for 8h in the atmosphere. After roasting is finished, crushing, adding a small amount of graphite for tabletting,and obtaining a catalyst precursor sample 9.
Comparative example 4
1. The first step is as follows: first, 3L of 5% chromium chloride solution was measured and added to 11L of 6% ammonia water to obtain a mixed solution.
2. The second step: mixing chromium chloride (1.4Kg), nano carbon (2-50nm), ammonium tetrachloropalladate, ammonium tetrachloroplatinate, triethanolamine and polyacrylamide according to the mass fraction of 88.5%, 4.4%, 2.65%, 0.9% and 0.9% in 26L of pure water, stirring and mixing uniformly, then adding the above mixed solution, adjusting the rotation speed to 30r/min, maintaining aging for 15min, filtering, and washing the filter cake to neutrality.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere, heating to 80 ℃, drying for 24H, placing in a roasting furnace after drying, and placing in a H furnace2Roasting at 600 ℃ for 8h in the atmosphere. After roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 10.
Comparative example 5
1. Preparation of the precipitate: first, 3L of a 5% chromium chloride solution was added to 11L of 6% ammonia water, and the mixture was sufficiently stirred at a rotation speed of 45 r/min. After maintaining aging for 15min, filtration was performed and the filter cake was washed to neutrality.
2. And (3) catalyst molding: placing the filter cake obtained in the step 1 in an oven in nitrogen atmosphere to heat at 120 ℃ for 12H, drying, then placing in a roasting furnace, and putting in H2Roasting at 450 ℃ for 8h in the atmosphere. After roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 11.
Comparative example 6
1. Preparation of the macroporous carrier: firstly, 290g of lignin is weighed and added into 3L of chromium chloride solution with the concentration of 5 percent, and the mixture is fully and evenly stirred at the rotating speed of 45 r/min. Then, the chromium chloride solution mixed with the lignin was added to 11L of 6% ammonia water to obtain a mixed solution containing the macroporous carrier.
2. Preparation of mesoporous carrier and loading of active metal: mixing chromium chloride (1.4Kg), nano carbon (2-50nm), ammonium tetrachloroplatinate and polyacrylamide in the mass fraction of 94.3%, 2.8%, 2.0% and 0.9% into 26L of pure water, stirring and mixing uniformly, then adding the mixed solution containing the macroporous carrier, adjusting the rotation speed to 30r/min, aging for 15min, filtering, and washing the filter cake to neutrality.
3. And (3) catalyst molding: placing the filter cake obtained in the step 2 in an oven in nitrogen atmosphere for heating at 120 ℃ for drying for 12H, placing the dried filter cake into a roasting furnace, and placing the roasting furnace in a H furnace2Roasting at 450 ℃ for 8h in the atmosphere. After roasting, crushing, adding a small amount of graphite, and tabletting to obtain a catalyst precursor sample 12.
The catalyst prepared above was loaded into a tubular reactor, and nitrogen and hydrogen fluoride were introduced to activate at 350 ℃ for 12 hours. After activation, each catalyst sample was sampled and labeled accordingly, and then the reactor was purged with trichloroethylene, R133a and hydrogen fluoride for evaluation for a period of time. Finally, the activated catalyst sample and the evaluated catalyst sample are subjected to pore size measurement, carbon content measurement and active metal (Pt or Pd) content measurement respectively.
After activation, the average pore diameter, the mesoporous ratio, the carbon content, and the active metal loading of each catalyst sample are shown in table 1.
Table 1:
sample numbering Average pore diameter/nm Proportion of micropores Proportion of mesopores Proportion of macropore Carbon content Content of active metal
1 6.5 5.9％ 81.7％ 12.4％ 2.20％ 1.36％
2 5.4 2.1％ 94.3％ 3.6％ 1.83％ 1.38％
3 8.7 4.2％ 79.4％ 16.4％ 1.93％ 1.29％
4 7.7 6.3％ 81.1％ 12.8％ 2.21％ 1.32％
5 6.8 4.5％ 84.8％ 10.7％ 1.98％ 1.27％
6 7.9 2.7％ 91.6％ 5.7％ 2.17％ 1.35％
7 68.6 15.6％ 46.3％ 38.1％ 2.32％ 1.31％
8 10.5 14.0％ 73.4％ 12.6％ 1.79％ 1.12％
9 5.9 13.2％ 76％ 10.8％ 1.82％ 0
10 2.4 15.6％ 82.1％ 2.1％ 1.82％ 1.24％
11 2.4 30.2％ 67.3％ 2.5％ 2.52％ 0
12 8.3 18.5％ 79.3％ 13.2％ 1.69％ 0.83％
As can be seen from table 1, in comparison with example 6 (sample No. 6), comparative example 2 (sample No. 8) only did not add the porous compound, and the active metal content decreased from 1.35% to 1.12%, indicating that the presence of the porous compound increased the active metal loading.
After the evaluation, the average pore diameter, the mesoporous ratio, the carbon content, and the active metal loading of each catalyst sample are shown in table 2.
Table 2:
Figure BDA0002296624210000091
Figure BDA0002296624210000101
the activity and lifetime data for each catalyst sample was evaluated as shown in table 3 below.
Table 3:
Figure BDA0002296624210000102
from the results of examples 1 to 6, it can be seen that the catalyst prepared by the method of the present application has a high proportion of mesopores, little carbon deposition after catalytic reaction (the carbon deposition proportion is less than 10%), and little loss of active metal. In the comparative example 1, no nano carbon is added, the mesoporous proportion is greatly reduced, and the content of active metal is greatly reduced after evaluation; in the comparative example 2, no pore channel compound is added, the carbon deposition content is obviously increased (the carbon deposition content is increased from 1.79 percent to 3.52 percent, the carbon deposition content is increased by 96.6 percent), and the active metal content is reduced; in the comparative example 3, soluble palladium or platinum is not added, the content of active metal is low, the content of carbon deposit is high (the carbon content is increased from 1.82% to 3.21%, the carbon deposit content is increased by 76.4%), and the catalytic activity is low; in comparative example 4, no specific macropores and no specific macropores, mesopores and supported active metals are prepared in comparative example 5, that is, the catalysts of comparative examples 4 and 5 are not regulated to form a composite pore structure, and after catalytic reaction, the carbon deposition level is remarkably increased (the carbon content of comparative example 4 is increased from 1.82% to 4.5%, the carbon deposition is increased by 147%, the carbon content of comparative example 5 is increased from 2.52% to 6.4%, and the carbon deposition is increased by 154%); in comparative example 6, the proportion of nanocarbon, ammonium tetrachloroplatinate and polyacrylamide is reduced, the proportion of the prepared catalyst mesopores is reduced, the content of active metals is reduced, the carbon content is obviously increased after evaluation (the carbon content is increased from 1.69% to 2.89%, the carbon content is increased by 71%), and the conversion rate of R133a and the selectivity of R134a are not high during evaluation.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (14)

1. A method for preparing a fluorinated catalyst precursor, comprising:
(1) performing first mixing treatment on a chromium chloride solution and ammonia water to obtain a mixed solution, wherein the chromium chloride solution contains a high-molecular pore-forming agent;
(2) carrying out second mixing treatment and filtration treatment on an aqueous solution containing nano carbon and a platinum salt or a palladium salt and the mixed solution obtained in the step (1) so as to obtain a filter cake, wherein the aqueous solution further contains at least one of chromium chloride and a porous compound;
(3) baking the filter cake to obtain the fluorination catalyst precursor;
wherein, the macromolecule pore-forming agent is at least one of lignin, cellulose, lignosulfonate and starch, and the pore channel compound is provided by at least one of polyacrylamide or triethanolamine.
2. The method according to claim 1, wherein in the step (1), the concentration of the chromium chloride solution is 5%, and the mass-volume ratio of the polymeric pore-forming agent to the chromium chloride solution is (90-100 g): 1L;
optionally, the concentration of the chromium chloride solution is 5%, the concentration of the ammonia water is 6%, and the volume ratio of the chromium chloride solution to the ammonia water is 1: 10-2: 5.
3. The method as claimed in claim 1, wherein in step (2), the mass ratio of the chromium chloride, the nano-carbon, the platinum salt or the palladium salt and the pore channel compound in the aqueous solution is (82-93): (3-10): 1-6): 0.5-5.
4. The method as claimed in claim 1, wherein in step (2), the mass ratio of the chromium chloride, the nano-carbon, the platinum salt or the palladium salt and the pore channel compound in the aqueous solution is (82-93): (4-5): 1-6): 1-2.
5. The method of claim 1, wherein the platinum or palladium salt is provided in the form of a chlorate salt or a nitrate salt.
6. The method of claim 1, wherein the platinum or palladium salt is provided in the form of ammonium tetrachloropalladate, ammonium hexachloroplatinate, platinum nitrate, or ammonium tetrachloroplatinate.
7. The method according to claim 1, wherein the second mixing treatment is carried out at a rotation speed of 30r/min for 15 min.
8. The method according to claim 1, wherein the baking treatment is carried out at a temperature of 80 to 150 ℃ for 8 to 24 hours, and then at 200 to 600 ℃ for 7 to 9 hours.
9. A fluorinated catalyst precursor prepared according to the method of any one of claims 1-8, comprising: the chromium oxide substrate is characterized in that a macroporous structure is arranged in the center of the chromium oxide substrate, a mesoporous structure is arranged on the surface layer of the chromium oxide substrate, active platinum metal or palladium metal is arranged in the mesopores, and the macropores are connected with the mesopores through a pore passage formed by polyacrylamide or triethanolamine.
10. The fluorination catalyst precursor of claim 9, wherein the proportion of mesopores is 78-95% and the average pore diameter is 5-9 nm.
11. A process for the preparation of a fluorination catalyst, characterized in that a fluorination catalyst precursor is subjected to an activation treatment in order to obtain a fluorination catalyst, said fluorination catalyst precursor being as defined in any one of claims 9 to 10.
12. The method for producing a fluorination catalyst according to claim 11, wherein the activation treatment is carried out at 300 to 400 ℃ for 11 to 13 hours in a mixed gas atmosphere of nitrogen and hydrogen fluoride.
13. Fluorination catalyst, characterized in that it is obtained by the process according to claim 11 or 12.
14. The fluorination catalyst of claim 13 wherein the active platinum metal or palladium metal comprises from 0.5% to 1.5% by weight of the total mass of the fluorination catalyst.
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