CN110975855B - Catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro-chloromethane, preparation method and application thereof - Google Patents
Catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro-chloromethane, preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane, a preparation method and application thereof, wherein the catalyst takes one or a mixture of more of metal oxide, active carbon and silicon carbide as a catalyst carrier, and one or a plurality of K, rb, cs, ba, co, ni, cu, pd, au as an active component loaded on the catalyst carrier, and the mass loading of the active component is 1-30%. The catalyst of the invention is applied to the reaction of preparing tetrafluoroethylene and hexafluoropropylene by the catalytic pyrolysis of difluoro chloromethane, and has the characteristics of high difluoro chloromethane conversion rate, high hexafluoropropylene selectivity and the like. The catalyst has the advantages of easily available raw materials and simple preparation process.
Description
Technical Field
The invention relates to a catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane, a preparation method and application thereof.
Background
R22 (difluoro chloromethane) is an HCFC refrigerant and is widely applied to the household and commercial fields, but has a damage effect on the atmospheric ozone layer and a certain greenhouse effect potential. The conversion of difluoromethane is currently mainly used as a raw material for producing polytetrafluoroethylene resins and as an intermediate for fire extinguishing agent 1121, as well as for polymer (plastic) physical blowing agents.
Tetrafluoroethane is a monomer for synthesizing polytetrafluoroethylene, and is also a raw material and an important intermediate of a fluorine-containing high polymer material. Hexafluoropropylene is inferior to tetrafluoroethylene in importance, is an important base material for the fluorine industry, is a monomer of a plurality of fluorine-containing copolymers, and is also an intermediate of fluorine-containing compounds.
The current industrial method for producing tetrafluoroethylene by using R22 mainly adopts a pyrolysis method and a steam dilution pyrolysis method. Thermal cracking of HCFC-22 was the earliest developed and commercially practiced process by DuPont in the United states. The HCFC-22 is pyrolyzed in a common tube furnace at normal temperature and normal pressure and 800-900 ℃, when the conversion rate of the HCFC-22 is 35%, the yield of the tetrafluoroethylene is only 30%, and in order to improve the yield of the tetrafluoroethylene, the conversion rate of the HCFC-22 can only be reduced. This process is also reported by ICI company in the early united kingdom, japan well fluorine corporation, ATOCHE company in france. The method has the advantages of simple method, simple equipment, mature technology and easy industrialized production. The method has the defects that the conversion rate of HCFC-22 is low, the production capacity of equipment is low, unreacted HCFC-22 circulates in the equipment to greatly reduce the utilization rate of the equipment, in addition, high-boiling substances in pyrolysis gas are more, and the yield of tetrafluoroethylene is not easy to improve. The HCFC-22 pyrolysis gas not only has complex components, but also tetrafluoroethylene and HCFC-22 and some components have similar boiling points or form azeotropes, which makes separation of tetrafluoroethylene monomer difficult.
When the steam dilution pyrolysis method is thermal cracking, after the difluoromethane chloride is preheated to 400 ℃, the mixture is mixed with superheated steam at 950-1000 ℃ in a molar ratio of 1.5-10, and the mixture enters an adiabatic reactor made of corrosion-resistant materials (such as a platinum-plated nickel pipe), the temperature is 700-900 ℃, and the pressure is 0.01-0.2 MPa, and the method has the defects that a set of superheated steam production equipment is needed and the heat consumption is high.
The preparation method of hexafluoropropylene is mainly obtained by tetrafluoroethylene pyrolysis. The hexafluoropropylene yield of the method is low, and the product is difficult to separate and purify, especially the existence of extremely toxic perfluoro isobutene brings great unsafe factors to industrial production.
In 1964 Japanese it was proposed that pyrolysis of tetrafluoroethylene with octafluorocyclobutane or mixtures thereof under adiabatic conditions of 700-900 ℃ in the presence of at least 50% water vapor was effective in suppressing the formation of by-products, thereby improving the yield. The method is similar to the process of preparing tetrafluoroethylene by steam pyrolysis of difluoro chloromethane, namely tetrafluoroethylene or the mixture of tetrafluoroethylene and octafluorocyclobutane is pre-mixed with steam preheated to a certain temperature, then quartz tube is introduced to control a certain dilution ratio to carry out adiabatic reaction, the reaction temperature is 700-900 ℃, and the reaction space velocity is generally 3000L/h, so that the space-time yield of hexafluoropropylene is very high and is about 100 times of that of decompression pyrolysis. The presence of water vapor improves the conversion rate of tetrafluoroethylene, the yield of hexafluoropropylene and the generation of perfluoro isobutene, but the heat consumption is larger and the production cost is higher.
Although widely used for the existing technology, the following problems still exist:
1. the energy consumption caused by high reaction temperature is high;
2. the reactor has high corrosion substances such as HCl, HF and the like at high temperature, so the pipe material of the reactor has high requirement, platinum-lined alloy pipes, nichrome pipes and the like can be selected, and Inconel 600 and other nichrome materials are used in general engineering, so that the investment of fixed assets is high;
3. the product is complex, and high-pollution and high-toxicity substance perfluoroisobutylene is easy to generate in a high-temperature section.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoromethane, a preparation method and application thereof. The catalyst of the invention is applied to the reaction of preparing tetrafluoroethylene and hexafluoropropylene by the catalytic pyrolysis of difluoro chloromethane, and has the characteristics of high difluoro chloromethane conversion rate, high hexafluoropropylene selectivity and the like. The catalyst has the advantages of easily available raw materials and simple preparation process.
The catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized in that the catalyst takes one or a mixture of more of metal oxide, active carbon and silicon carbide as a catalyst carrier, and takes one or a plurality of K, rb, cs, ba, co, ni, cu, pd, au as an active component loaded on the catalyst carrier, and the mass loading of the active component is 1-30%.
The catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized in that the metal oxide is Na 2 O、K 2 O、Li 2 O、Ag 2 O、Cu 2 O、BeO、MgO、CaO、BaO、CuO、ZnO、HgO、FeO、Al 2 O 3 、Ti 2 O 3 、Fe 2 O 3 、Mn 2 O 3 、SiO 2 One or a mixture of more than one of the following.
The catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized in that the active components are one or more of K, cs, ba, cu, and the mass loading of the active components is 3-20%.
The catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized by further comprising a metal auxiliary agent loaded on a catalyst carrier, wherein the metal auxiliary agent is one or more than two substances in Pt, ag, fe, ru, and the content of the metal auxiliary agent is not higher than 10% of the total mass of the catalyst carrier and the active components.
The preparation method of the catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized by comprising the following steps: dissolving a precursor of an active component in water, and uniformly stirring to obtain an impregnating solution; the obtained impregnating solution is quickly dropped into the catalyst carrier drop by drop, impregnated for 5-24h at normal temperature, then dried in a baking oven at 60-200 ℃, the dried solid is baked for 2-10h at 200-800 ℃ under inert gas atmosphere, and thenAt H 2 Calcining and reducing at 200-350 ℃ in the atmosphere to convert the precursor of the active component into a metal simple substance form, thus obtaining the catalyst.
The preparation method of the catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized in that the precursor of the active ingredients is one or more of chloride or nitrate in K, rb, cs, ba, co, ni, cu, pd, au.
The preparation method of the catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized in that the mass ratio of the impregnating solution to the catalyst carrier is 1:0.5-2.5, preferably 1:1-2; roasting at 300-600 ℃ in inert gas atmosphere for 3-6h; the inert gas being N 2 One or more of Ar and He.
The preparation method of the catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane is characterized in that nitrogen-containing auxiliary agent is added when the dried solid is roasted in inert gas atmosphere, and the adding amount of the nitrogen-containing auxiliary agent is 0.1-5 times, preferably 0.8-3 times, of the mass of the dried solid; the nitrogen-containing auxiliary agent is one or more of melamine, urea and polybenzimidazole.
The application of the catalyst is characterized in that the catalyst is filled in a fixed bed reactor, and the raw material of difluoro chloromethane is introduced into the fixed bed reactor under the condition that the catalytic cracking temperature is 500-900 ℃ to carry out the reaction of preparing tetrafluoroethylene and hexafluoropropylene by catalytic cracking.
The application of the catalyst is characterized in that the difluoro chloromethane raw material introduced into the fixed bed reactor is also doped with nitrogen diluent gas, the feeding volume ratio of the difluoro chloromethane to the nitrogen is 1:1-12, and the volume airspeed of the mixed gas of the difluoro chloromethane and the nitrogen is 100/h-1000/h; the catalytic cracking temperature is 500-700 ℃.
Compared with the prior art, the invention has the advantages that:
1) When the catalyst is applied to the reaction for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro chloromethane, the reaction temperature can be reduced, the energy consumption can be reduced, the byproducts with high pollution and high toxicity can be reduced, and the requirements of the reactor pipe can be reduced. Not only has theoretical value, but also has very strong practical value and very great industrial application prospect.
2) The catalyst carrier adopted by the invention has the characteristics of high temperature resistance, acid corrosion resistance, high strength, high hardness, good wear resistance, small friction coefficient and the like, effectively overcomes the corrosion of strong acid substances such as HCl generated in the process of thermal cracking of difluoromethane, solves the problem of sintering carbon deposition of the catalyst at the high temperature of reaction, and has higher practicability. The catalyst carrier adopted by the invention effectively resists the problem of high reaction temperature, moreover, the preferable strong adsorption performance of the catalyst carrier surface increases the contact time of difluoro-Carbene (CF) so that the difluoro-carbene dimerizes to generate tetrafluoroethylene, and then the difluoro-carbene dimerizes to generate hexafluoropropylene, thereby improving the selectivity of hexafluoropropylene.
3) In the preparation process of the catalyst, a nitrogen-containing auxiliary agent is added for roasting, so that nitrogen atoms are introduced into a limited carrier framework, dislocation, bending, dislocation and other defect sites with unpaired electrons are generated in the middle of a carrier layer, meanwhile, the introduction of the nitrogen atoms can form local functional groups on the surface of a carrier material, so that the surface of the carrier has certain alkalinity, and nitrogen can provide a pair of extra-nuclear electrons, thereby enhancing the conductivity, the polarity, the electron transmission performance and the like. And the interaction between the carrier and the active component is influenced, the activity and the stability of the catalyst are improved, the HCl removal performance of difluoro-chloromethane can be effectively improved, the probability of difluoro-carbene generation is increased, the generation of reaction byproducts is effectively reduced, the reaction conversion rate is improved, and the selectivity of tetrafluoroethylene and hexafluoropropylene is improved.
Description of the embodiments
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
Weighing 10g of 18-40 mesh wood carbon, and placing the wood carbon in a drying oven to be dried for 8 hours at 100 ℃; 1.86g of barium acetate was weighed and dissolved in 40g of water to obtain a standard impregnating solution having a concentration of 0.025g of Ba/g of solution.
Weighing 1g of dried wood carbon, quickly and uniformly dripping 2g of impregnating solution into the wood carbon, placing the wood carbon at a ventilation position for impregnating for 24 hours at normal temperature, placing the wood carbon into a baking oven at 120 ℃ for drying for 12 hours after the impregnating is finished, roasting for 5 hours at 500 ℃ under nitrogen atmosphere, and then placing the wood carbon into H 2 And (3) reducing for 5 hours at 350 ℃ in the atmosphere to obtain the 5% Ba/AC catalyst (namely, the loading of Ba on wood carbon is 5%).
The prepared 5% Ba/AC catalyst is applied to the catalytic cracking reaction of difluoro chloromethane, and the experimental operation process is as follows: 2mL of the catalyst was measured in a constant temperature zone of a reaction tube having an inner diameter of 8mm, and in N 2 Heating to 500 ℃ under atmosphere, and introducing the raw materials R22 and N after the temperature is stable 2 Mixed gas (N) 2 The feeding volume ratio of the catalyst to the raw material R22 is 9:1), and R22 and N are under normal pressure 2 The gas volume space velocity of the mixed gas is 900/h. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example two
Weighing 10g of 18-40 mesh wood carbon, and placing the wood carbon in a drying oven to be dried for 8 hours at 100 ℃; 2.6g of potassium nitrate was weighed and dissolved in 20g of water to obtain a standard impregnating solution having a concentration of 0.05g K/g of solution.
Weighing 1g of dried wood carbon, diluting 1g of impregnating solution with distilled water to 1.5g, quickly and uniformly dripping into the wood carbon, placing the wood carbon in a ventilation place for impregnating for 24 hours at normal temperature, placing the wood carbon in a baking oven at 120 ℃ for drying for 12 hours after the impregnation is finished, roasting for 4 hours at 600 ℃ under nitrogen atmosphere, and then placing the wood carbon in H 2 Reducing for 5h at 300 ℃ in the atmosphere to obtain the 5% K/AC catalyst.
The 5% K/AC catalyst prepared above was applied to the catalytic cracking reaction of difluoromethane, and the experimental evaluation procedure was repeated in example one, except that the reaction temperature was replaced with "550℃and the remaining reaction conditions were the same as in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example III
Weighing 10g of 18-40 mesh wood carbon, and placing the wood carbon in a drying oven to be dried for 8 hours at 100 ℃; 2.6g of potassium nitrate was weighed and dissolved in 20g of water to obtain a standard impregnating solution having a concentration of 0.05g K/g of solution.
Weighing 1g of dried wood carbon, quickly and uniformly dripping 2g of impregnating solution into the wood carbon, placing the wood carbon at a ventilation position for impregnating for 24 hours at normal temperature, placing the wood carbon in a baking oven at 120 ℃ for drying for 12 hours after the impregnating is finished, adding 1.5g of urea into the dried solid, roasting for 6 hours at 350 ℃ under nitrogen atmosphere, and then carrying out H treatment 2 Reducing for 4 hours at 350 ℃ in the atmosphere to obtain the 10% K/AC-N catalyst.
The 10% K/AC-N catalyst prepared as described above was used in a difluoromethane catalytic cracking reaction, and the experimental procedure was repeated in example one, except that the reaction temperature was changed to 600℃and R22 and N at normal pressure 2 The gas volume space velocity of the mixture was replaced by 400/h ", and the remaining reaction conditions were the same as in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example IV
Weighing 10g of 18-40 mesh silicon carbide, and placing the silicon carbide in a drying oven to be dried for 8 hours at 100 ℃; 2.92g of copper nitrate was weighed and dissolved in 20g of water to obtain a standard impregnating solution having a concentration of 0.05g of Cu/g of solution.
Weighing 1g of dried silicon carbide, diluting 1g of impregnating solution with deionized water to 2g, then quickly and uniformly dripping the solution into the silicon carbide, placing the solution at a ventilation position for impregnating for 24 hours at normal temperature, placing the silicon carbide in a baking oven at 120 ℃ for drying for 12 hours after the impregnation is finished, then roasting the silicon carbide at 450 ℃ for 6 hours under nitrogen atmosphere, and then carrying out H treatment 2 Reducing for 5h at 350 ℃ in the atmosphere to obtain the 5% Cu/SiC catalyst.
The prepared 5% Cu/SiC catalyst is applied to the difluoro chloromethane catalytic cracking reaction, and the experimental operation process is repeated in the third embodiment, wherein the reaction temperature is replaced by 650 ℃, and the rest of reaction conditions are the same as those in the third embodiment. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example five
Weighing 10g of 18-40 mesh alumina, and placing the alumina in a drying oven to be dried for 8 hours at 100 ℃; 2.9g of copper nitrate was weighed and dissolved in 20g of water to obtain a standard impregnating solution having a concentration of 0.05g of Cu/g of solution.
Weighing 1g of dried alumina particles, diluting 1g of impregnating solution with deionized water to 2g, then quickly and uniformly dripping the solution into alumina, placing the alumina in a ventilation place for impregnating for 24 hours at normal temperature, placing the alumina in a baking oven at 120 ℃ for drying for 12 hours after the impregnation is finished, then roasting for 5 hours at 500 ℃ in nitrogen atmosphere, and then adding the alumina into H 2 Reducing for 5h at 300 ℃ under atmosphere to obtain 5 percent Cu/Al 2 O 3 A catalyst.
5% Cu/Al prepared as described above 2 O 3 The catalyst was used in the catalytic cracking reaction of difluoromethane, and the experimental procedure was repeated in example one, except that the reaction temperature was changed to 700 ℃. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example six
Weighing 10g of 18-40 mesh barium oxide, and placing the barium oxide in a drying oven to be dried for 8 hours at 100 ℃; 2.9g of copper nitrate was weighed and dissolved in 40g of water to obtain a standard impregnating solution having a concentration of 0.025g of Cu/g of solution.
Weighing 1g of dried barium oxide, quickly and uniformly dripping 2g of impregnating solution into the barium oxide, placing the barium oxide at a ventilation position for impregnating for 24 hours at normal temperature, placing the barium oxide in a baking oven at 120 ℃ for drying for 12 hours after the impregnation is finished, roasting for 6 hours at 400 ℃ under nitrogen atmosphere, and then placing the barium oxide in H 2 Reducing for 6 hours at 300 ℃ in the atmosphere to obtain the 5 percent Cu/BaO catalyst.
The 5% Cu/BaO catalyst prepared above was applied to the difluoromethane-chloride catalytic cracking reaction, and the experimental procedure was repeated in example one, except that the "feed volume ratio of N2 to raw material R22 was replaced by 12:1", and the remaining reaction conditions were the same as in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example seven
Weighing 10g of 18-40 mesh alumina, and placing the alumina in a drying oven to be dried for 8 hours at 100 ℃; 5.8g of copper nitrate was weighed and dissolved in 20g of water to obtain a standard impregnating solution having a concentration of 0.10g of Cu/g of solution.
Weighing 1g of dried alumina, quickly and uniformly dripping 2g of impregnating solution into the alumina, placing the alumina at a ventilation position for impregnating for 24 hours at normal temperature, placing the alumina in a baking oven at 120 ℃ for drying for 12 hours after the impregnation is finished, roasting for 4 hours at 500 ℃ under nitrogen atmosphere, and then placing the alumina in H 2 Reducing for 3h at 350 ℃ in atmosphere to obtain 20 percent Cu/Al 2 O 3 A catalyst.
20% Cu/Al prepared as described above 2 O 3 The catalyst is applied to the catalytic cracking reaction of difluoro chloromethane, and the experimental operation process is repeated in the third example, wherein the difference is that R22 and N are under normal pressure 2 The gas volume space velocity of the mixed gas is replaced by 1200/h, N 2 The feed volume ratio to raw material R22 was replaced with 6:1". The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example eight
A 20% Rb/AC catalyst was prepared as follows:
1) Dissolving RbCl in water to prepare a standard dipping solution with the concentration of 0.1g Rb/g solution;
2) Weighing 10g of 18-40 mesh wood carbon, drying at 100deg.C in a drying oven for 8 hr, weighing 1g of dried wood carbon, quickly and uniformly dripping 2g of soaking solution into wood carbon, soaking at normal temperature for 24 hr, drying the wood carbon in a 120deg.C oven for 12 hr, roasting at 500deg.C under nitrogen atmosphere for 5 hr, and collecting the product, and drying at room temperature for 24 hr 2 Reducing for 5h at 350 ℃ in the atmosphere to obtain the 20% Rb/AC catalyst.
The 20% Rb/AC catalyst prepared above was applied to the catalytic cracking reaction of difluoromethane, and experimental evaluation procedure was repeated in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example nine
A5% Cs/AC catalyst (i.e., cs loading on wood carbon is 5%) was prepared by repeating example one, except that the prepared impregnating solution was replaced with a standard impregnating solution having a concentration of 0.025g Cs/g solution, and the remaining catalyst preparation conditions were repeated example one, to finally prepare a 5% Cs/AC catalyst.
The 5% Cs/AC catalyst prepared above was applied to a difluoromethane catalytic cracking reaction, and experimental evaluation procedure was repeated in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Examples ten
A 5% Co/AC-N catalyst (i.e., co loading on nitrogen-doped wood carbon of 5%) was prepared, the preparation method of which was repeated for example three, except that: the prepared impregnating solution was replaced with a standard impregnating solution having a Co/g solution concentration of 0.025g (the standard impregnating solution was CoCl) 2 Aqueous solution), to finally produce a 5% Co/AC-N catalyst.
The prepared 5% Co/AC-N catalyst is applied to the catalytic cracking reaction of difluoromethane, and the experimental evaluation process is repeated in the third example. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example eleven:
an 8% Ni/AC-N catalyst (i.e., ni loading on nitrogen-doped wood carbon was 8%) was prepared, and the preparation method was repeated for example III, except that: the prepared impregnating solution is replaced by Ni (NO) 3 ) 2 An aqueous solution, finally preparing 8% Ni/AC-N catalyst.
The 8% Ni/AC-N catalyst prepared above is applied to the catalytic cracking reaction of difluoromethane, and the experimental evaluation process is repeated in example III. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Embodiment twelve:
a 3% Pd/BaO catalyst (i.e., 3% loading of Pd on BaO) was prepared, and the preparation method was repeated as in example six except that: replacement of the formulated impregnation with PdCl at different concentrations 2 And (3) obtaining the 3% Pd/BaO catalyst.
The 3% Pd/BaO catalyst prepared above is applied to the catalytic cracking reaction of difluoromethane, and the experimental evaluation process is repeated in the sixth example. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Embodiment thirteen:
a 5% Au/SiC catalyst (i.e., au loading on SiC of 5%) was prepared, the preparation method of which was repeated in example four except that: replacement of the formulated impregnating solution with AuCl 3 And (3) obtaining the aqueous solution, and finally obtaining the 5% Au/SiC catalyst.
The prepared 5% Au/SiC catalyst is applied to the difluoro chloromethane catalytic cracking reaction, and the experimental evaluation process is repeated in the sixth example. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Fourteen examples:
a 5% Ba/MgO catalyst (i.e., 5% Ba loading on MgO) was prepared, the preparation method of which was repeated in example one, except that: and (3) replacing the active carbon carrier with MgO to finally prepare the 5% Ba/MgO catalyst.
The prepared 5% Ba/MgO catalyst is applied to the catalytic cracking reaction of difluoro chloromethane, and the experimental evaluation process is repeated in the first example. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example fifteen:
a 5% Cu/CaO catalyst (i.e., 5% Cu loading on CaO) was prepared, the preparation of which was repeated in example four, except that: and replacing the SiC carrier with CaO to finally prepare the 5% Cu/CaO catalyst.
The prepared 5% Cu/CaO catalyst is applied to the difluoro chloromethane catalytic cracking reaction, and the experimental evaluation process is repeated in the fourth example. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example sixteen:
preparation of 5% Cu/Mn 2 O 3 Catalyst (i.e. Cu in Mn) 2 O 3 Upper part of the cylinderThe preparation method is repeated in example five, except that the loading is 5 percent: substitution of alumina support for Mn 2 O 3 Finally obtain 5% Cu/Mn 2 O 3 A catalyst.
5% Cu/Mn prepared as described above 2 O 3 The catalyst is applied to the catalytic cracking reaction of the difluoro chloromethane, and the experimental evaluation process is repeated in the fifth example. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example seventeenth:
preparing 3% Ru-5% Ba/AC catalyst (i.e. loading 3% Ru on 5% Ba/AC catalyst),
preparation method of 5% Ba/AC catalyst example one is repeated, and the difference from example one is that Ru auxiliary agent is added into the catalyst, wherein the precursor of Ru auxiliary agent adopts RuCl 2 The aqueous solution is added by an immersion method, and the mass addition amount of Ru is 3%.
The 3% Ru-5% Ba/AC catalyst prepared above is applied to the catalytic cracking reaction of difluoromethane, and the experimental evaluation process is repeated in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Example eighteenth:
an 8% Fe-5% Ba/AC catalyst was prepared (i.e., 8% Fe was further supported on the 5% Ba/AC catalyst),
preparation method of 5% Ba/AC catalyst example one was repeated, differing from example one in that the catalyst was added with Fe auxiliary agent, wherein the precursor of Fe auxiliary agent was Fe (NO) 3 ) 2 The aqueous solution is added by an immersion method, and the mass addition amount of Fe is 8%.
The 8% Fe-5% Ba/AC catalyst prepared above is applied to the catalytic cracking reaction of difluoromethane, and the experimental evaluation process is repeated in example one. The reaction evaluation time, the conversion of R-22 and the selectivity of tetrafluoroethylene and hexafluoropropylene are shown in Table 1 below.
Table 1 conversion of the different catalysts in the catalytic cracking reaction of R22 and selectivity of tetrafluoroethylene, hexafluoropropylene are as follows:
as can be seen from Table 1, the catalyst of the present invention is used in the reaction for producing R22 by catalytic cracking, achieves higher conversion at lower temperature in the thermodynamic range, and greatly improves the selectivity of hexafluoropropylene in the presence of Ba or Cu elements.
The catalyst has the advantages of low reaction temperature, sintering resistance, good corrosion resistance and the like, improves the conversion rate of reactants at a lower temperature in a thermodynamic range, and improves the selectivity of hexafluoropropylene.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (6)
1. The application of the catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis of difluoro-chloromethane is characterized in that the catalyst is filled into a fixed bed reactor, and the difluoro-chloromethane raw material is introduced into the fixed bed reactor under the condition that the catalytic pyrolysis temperature is 500-900 ℃ for carrying out the reaction of preparing tetrafluoroethylene and hexafluoropropylene by catalytic pyrolysis;
the catalyst is 5% K/AC-N, 5% Cu/SiC, 5% Cu/Al 2 O 3 、5%Cu/BaO、5%Co/AC-N、3%Pd/BaO、5%Cu/CaO、5%Cu/Mn 2 O 3 ；
The preparation steps of the catalyst are as follows: dissolving a precursor of an active component in water, and uniformly stirring to obtain an impregnating solution; the obtained impregnating solution is quickly dropped into the catalyst carrier drop by drop, impregnated for 5-24H at normal temperature, then dried in a baking oven at 60-200 ℃, and the dried solid is baked for 2-10H at 200-800 ℃ under inert gas atmosphere, and then is baked in H 2 Calcining and reducing at 200-350 ℃ in the atmosphere to convert the precursor of the active component into a metal simple substance form, thus obtaining the catalyst; when the catalyst carrier is defined as active carbon, nitrogen-containing auxiliary agent is added when the dried solid is baked under inert gas atmosphere.
2. The use according to claim 1, characterized in that the mass ratio of the impregnation liquid to the catalyst support is 1:0.5-2.5; roasting at 300-600 ℃ in inert gas atmosphere for 3-6h; the inert gas being N 2 One or more of Ar and He.
3. The use according to claim 2, characterized in that the mass ratio of the impregnation liquid to the catalyst support is 1:1-2.
4. Use according to claim 1, characterized in that the nitrogen-containing auxiliary agent is added in an amount of 0.1-5 times the mass of the dried solid; the nitrogen-containing auxiliary agent is one or more of melamine, urea and polybenzimidazole.
5. The method according to claim 4, wherein the nitrogen-containing auxiliary is added in an amount of 0.8 to 3 times the mass of the dried solid.
6. The use according to claim 1, wherein the difluoromethane raw material fed into the fixed bed reactor is further doped with nitrogen diluent gas, the feeding volume ratio of the difluoromethane to the nitrogen is 1:1-12, and the volume space velocity of the mixed gas of the difluoromethane and the nitrogen is 100/h-1000/h; the catalytic cracking temperature is 500-700 ℃.
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