CN109675592B - Metal oxide/C composite fluorination catalyst and preparation method and application thereof - Google Patents
Metal oxide/C composite fluorination catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a metal oxide/C composite fluorination catalyst, a preparation method and application thereof. The metal oxide is Cr2O3/MxOy，Cr2O3And MxOyThe molar ratio of (A) to (B) is 5-9: 1; the mass fraction of C in the composite fluorination catalyst is 1-30%; the M includes Mo. According to the invention, Cr is used as an active component of the fluorination catalyst, Mo is used as a main assistant metal to regulate and control the catalyst performance and the catalyst activity, the obtained composite fluorination catalyst has better catalyst activity and excellent selectivity in fluorination reaction, the conversion rate is high, the reaction condition is mild, and the generation of a main impurity R115 in R125 production and the generation of a main impurity R1122 in R134a production can be controlled, so that the generation of byproducts can be controlled from the source; in addition, the use of the fluorination catalyst can reduce the energy consumption of fluorination reaction, reduce the steps of product separation and purification and reduce the separation and purification.
Description
Technical Field
The invention belongs to the technical field of fluorine chemical industry, and particularly relates to a metal oxide/C composite fluorination catalyst, and a preparation method and application thereof.
Background
In the field of fluorine chemical industry, Hydrofluorocarbons (HFCs) have no destructive effect on the atmospheric ozone layer, are important substitutes for chlorofluorocarbons (CFCs), and are widely used for refrigerants, foaming agents, aerosols and the like. The main products are R125(1,1,1,2, 2-pentafluoroethane), R134a (1,1,1, 2-tetrafluoroethane) and the like, and the reactions are mainly prepared by gas-phase fluorination, and the key technology lies in the development of a gas-phase fluorination catalyst. At present, market mainstream manufacturers mainly use traditional preparation methods, such as a precipitation method, an immersion method, a mixing method and the like, but the conditions that the reaction temperature is high (approximately 300-500 ℃), the energy consumption of the device is high, impurities in reaction byproducts are difficult to separate and the like generally exist, such as: r115 (pentafluoro-monochloroethane) is easy to generate in the production of R125, azeotropy with the pentafluoro-monochloroethane is needed, and extractive distillation is needed; in the production of R134a, R1122 (1, 1-difluoro-2-chloroethylene) as an impurity is produced, azeotropically, and requires conversion or adsorption treatment.
CN107552076A discloses a gas phase fluorination catalyst with a nanocrystalline composite carrier and a preparation method thereof, nanocrystalline metal fluoride is prepared by a sol-gel-ultrasonic method, and a nanocrystalline fluorination catalyst with large specific surface area, high activity and good stability is prepared by carrier loading and is applied to R125 and R134a catalysts, but the reaction temperature and important by-product impurities are not researched, and the influence of the catalyst impurities is not clarified.
CN103601611B discloses a method for removing R1122 in R134a and a preparation method of an adsorbent thereof, the method can effectively reduce the influence of R1122 on the fractionation and purification of products, but the method increases the process difficulty by additionally arranging an adsorption device and equipment for treatment, the adsorbent also needs regeneration treatment, and the generation of impurities is not controlled from the source.
Therefore, the development of a fluorination catalyst which has high catalytic conversion rate and high product selectivity and can be used under mild conditions has important research significance and economic value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of low conversion rate, low product selectivity and harsh use conditions of a fluorination catalyst in the prior art, and provides a metal oxide/C composite fluorination catalyst. The invention provides metal oxide/C composite fluorinationThe catalyst is Cr2O3、MxOyThe catalyst is obtained by compounding (containing Mo) and C, has excellent selectivity and better conversion rate for fluorination reaction, can control the generation of a main impurity R115 in R125 production and the generation of a main impurity R1122 in R134a production, and has good catalytic performance and mild use conditions.
The invention also aims to provide a preparation method of the metal oxide/C composite fluorination catalyst.
The invention also aims to provide the application of the metal oxide/C composite fluorination catalyst in fluorination reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal oxide/C composite fluorination catalyst, wherein the metal oxide is Cr2O3/MxOy，Cr2O3And MxOyThe molar ratio of (A) to (B) is 5-9: 1; the mass fraction of C in the composite fluorination catalyst is 1-30%; said M comprises Mo, x and y are such that MxOyThe valence of (2) is zero.
The inventor of the invention discovers, through research, that the Cr is used as an active component of a fluorination catalyst, Mo is used as an auxiliary metal to regulate the performance and the activity of the catalyst, and graphite C is compounded, so that the obtained metal oxide/C composite fluorination catalyst has better catalyst activity and excellent selectivity in fluorination reaction, high conversion rate and mild reaction conditions, and can control the generation of a main impurity R115 in R125 production and the generation of a main impurity R1122 in R134a production; in addition, the use of the fluorination catalyst can reduce the energy consumption of fluorination reaction, reduce the steps of product separation and purification, reduce the investment of separation and purification devices and equipment, reduce the production cost and bring obvious economic benefits.
Preferably, M further comprises one or more of Al, Mg, Zn, Y or Ni; the mole fraction of Mo in M is not less than 10%.
When other metals are selected as auxiliary metals to act with Mo synergistically, the catalyst performance and the catalyst activity can be better regulated and controlled, and the reaction selectivity and the conversion rate are further improved.
Preferably, Cr2O3And MxOyIs 8: 1.
Preferably, the mass fraction of C in the composite fluorination catalyst is 25%.
The preparation method of the metal oxide/C composite fluorination catalyst comprises the following preparation steps:
s1: dissolving Cr salt to obtain metal salt solution;
s2: adding a surfactant, a cosurfactant and an oil phase into a metal salt solution, and stirring and mixing to obtain an emulsion;
s3: adjusting the pH value of the emulsion to 10-14, stirring and reacting for 2-8 h, demulsifying, performing suction filtration, and washing to obtain a solid substance;
s4: and adding ammonium molybdate and C into the solid, drying, roasting at 150-400 ℃ in an inert atmosphere, and fluorinating to obtain the metal oxide/C composite fluorination catalyst.
The invention prepares the fluorine catalyst by using a micro-emulsion method, and regulates the particle size and microstructure of the fluorine catalyst by matching the surface catalyst and the surface-assisted catalyst, thereby improving the catalytic activity of the fluorine catalyst.
In addition, because the Mo element has strong activity, the chloride or nitrate can directly react with water, and can not directly dissolve and react with emulsion, so that ammonium molybdate is selected as a raw material, added after the emulsion polymerization reaction, and finally roasted and fluorinated to obtain the metal oxide/C composite fluorination catalyst.
The average particle size of the obtained fluorination catalyst is 20-80 nm through testing.
Cr salts conventional in the art may be used in the present invention.
Preferably, the Cr salt is CrCl3Or Cr (NO)3)3One or two of them.
Preferably, the ammonium molybdate is ammonium ortho-molybdate ((NH)4)2MoO4) Ammonium paramolybdate ((NH)4)6Mo7O24) Ammonium dimolybdate ((NH)4)2Mo2O7）、Ammonium tetramolybdate ((NH)4)2Mo4O13) One or more of them.
Preferably, the concentration of the metal in the metal salt solution is 0.2-2 mol/L.
More preferably, the concentration of the metal in the metal salt solution is 0.8-1.4 mol/L.
Preferably, when M further includes one or more of Al, Mg, Zn, Y, or Ni, S1 further includes a step of dissolving one or more of Al salt, Mg salt, Zn salt, Y salt, or Ni salt to obtain a metal salt solution.
Al salts, Mg salts, Zn salts, Y salts, Ni salts, which are conventional in the art, can be used in the present invention.
Preferably, the Al salt is AlNO3Or Al2(SO4)3One or two of them.
Preferably, the Mg salt is MgCl2Or Mg (NO)3)2One or two of them.
Preferably, the Zn salt is ZnCl2Or Zn (NO)3)2One or two of them.
Preferably, the Y salt is YCl3Or Y (NO)3)3One or two of them.
Preferably, the Ni salt is NiCl2Or Ni (NO)3)2One or two of them.
The dosage of the surfactant, the cosurfactant and the oil phase in the invention is conventional dosage, so as to realize better emulsification. In order to further regulate and control to obtain more proper particle size and microstructure, the dosage relationship of the surfactant, the cosurfactant, the oil phase and the metal salt can be further optimized.
Preferably, the mass ratio of the surfactant to the cosurfactant in S2 is 1: 2-2: 1.
More preferably, the mass ratio of the surfactant to the co-surfactant in S2 is 1: 1.
The ratio of surfactant to co-surfactant will affect the solubility of the metal salt in the oil phase, under which conditions the surfactant and co-surfactant are used in the least amount and the most dissolved metal salt.
Preferably, the mass ratio of the total of the surfactant and the cosurfactant, the oil phase and the metal salt is 1.0-2.0: 1.5-3.0: 1.
The types of surfactants, co-surfactants and oil phases are conventional in the art.
Preferably, the surfactant is a nonionic surfactant.
More preferably, the nonionic surfactant is one or more of polyoxyethylene alkylphenol NP-10, OP-9 or SOPE-10.
Preferably, the cosurfactant is one or more of n-butyl alcohol, n-hexyl alcohol and n-heptyl alcohol.
More preferably, the co-surfactant is n-hexanol.
Preferably, the oil phase is n-hexane.
Preferably, ammonia gas is introduced into S3 to adjust the pH; the introduction rate of the ammonia gas is 0.1-1.0L/h.
The invention utilizes ammonia gas to adjust the pH value, thereby optimizing the particle size.
More preferably, the introduction rate of the ammonia gas is 0.3-0.5L/h.
Preferably, the pH of the emulsion in S3 is 12-13.
The particle size can be further optimized by further adjusting and controlling the pH.
Conventional demulsification means known in the art may be used in the present invention.
Preferably, the demulsification process in the S3 is as follows: demulsifying at 40-80 deg.C.
More preferably, the demulsification process in the step S3 is as follows: demulsifying at 60 deg.C.
Preferably, the roasting time in S4 is 2-16 h.
Preferably, the roasting temperature in S4 is 200-450 ℃;
more preferably, the roasting temperature is 250-350 ℃, and the roasting time is 4-12 h.
Fluorination methods conventional in the art can be used in the present invention.
The application of the metal oxide/C composite fluorination catalyst in fluorination reaction is also in the protection scope of the invention.
Preferably, the fluorination reaction is a fluorination reaction to produce R125 or R134 a.
Compared with the prior art, the invention has the following beneficial effects:
the inventor of the invention discovers, through research, that Cr is used as an active component of a fluorination catalyst, Mo is used as a main auxiliary metal to regulate and control the performance of the catalyst, and the obtained metal oxide/C composite fluorination catalyst has better catalyst activity and excellent selectivity in fluorination reaction, high conversion rate and mild reaction conditions, and can control the generation of a main impurity R115 in R125 production and the generation of a main impurity R1122 in R134a production, thereby realizing the control of the generation of byproducts from the source; in addition, the use of the fluorination catalyst can reduce the energy consumption of fluorination reaction, reduce the steps of product separation and purification, reduce the investment of separation and purification devices and equipment, reduce the production cost and bring obvious economic benefits.
Drawings
FIG. 1 is a graph showing the particle size distribution of the metal compound in the emulsion provided in example 1;
FIG. 2 is a graph showing the particle size distribution of the metal compound in the emulsion provided in example 2;
FIG. 3 is a graph showing the particle size distribution of the metal compound in the emulsion provided in example 3;
FIG. 4 is a graph showing the particle size distribution of the metal compound in the emulsion provided in example 4.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
This example provides a metal oxide/C composite fluorination catalyst, the metal oxide is Cr2O3/ MoO3，Cr2O3And MoO3The molar ratio of (2) is 9:1, and the mass fraction of C is 20%. Prepared by the following method.
S1: 23.98 g of CrCl are weighed out3·6H2Dissolving O in 112.50 mL of deionized water, and mixing to obtain a metal salt solution, wherein CrCl is contained in the metal salt solution3The concentration of (2) is 0.8 mol/L.
S2: adding 80g of surfactant 0P-9, 66 g of cosurfactant n-hexanol and 261g of oil phase n-hexane into the metal salt solution, stirring and mixing to obtain clear and transparent emulsion;
s3: introducing ammonia gas into the microemulsion at the speed of 0.5L/h for reaction, stopping introducing ammonia gas when the pH =11, continuing stirring for reaction for 5 hours, heating to the temperature of the microemulsion system of 60 ℃ for demulsification, sampling to determine that the average particle size of the metal compound in the emulsion is about 44 nm (as shown in figure 1), performing vacuum filtration, washing the surfactant and chloride ions by deionized hydrous ethanol, and drying in an oven at the temperature of 120 ℃ to obtain a cured product.
S4: mixing the cured material, ammonium orthomolybdate (12.36 g) and graphite C (2.09 g), roasting at 350 ℃ for 4 hours under the protection of nitrogen, and introducing hydrogen fluoride for fluorination for 10 hours to obtain Cr2O3/ MoO3a/C composite fluorination catalyst.
Example 2
This example provides a metal oxide/C composite fluorination catalyst, the metal oxide is Cr2O3/ MoO3-Al2O3-ZnO，Cr2O3And (MoO)3-Al2O3-ZnO) in a molar ratio of 8:1, MoO3-Al2O3MoO in-ZnO3Is 50% of Al2O3The molar fraction of (2) is 25%, the molar fraction of ZnO is 25%, and the mass fraction of C is 15%. Tong (Chinese character of 'tong')Prepared by the following method.
S1: 25.58 g of CrCl were weighed3·6H2O、0.89g Zn(NO3)2·6H2O and 1.13g of Al2(SO4)3·9H2Dissolving O in 102 mL of deionized water, and mixing to obtain a metal salt solution, wherein the concentration of metal ions in the solution is 1.0 mol/L;
s2: adding 100g of surfactant NP-10, 82g of cosurfactant n-butanol and 208g of oil phase n-hexane into a metal salt solution, and stirring and mixing to obtain a clear and transparent emulsion;
s3: introducing ammonia gas into the microemulsion at the speed of 0.7L/h for reaction, stopping introducing ammonia gas when the pH =14, continuing stirring for reaction for 5 hours, heating to the temperature of the microemulsion system of 40 ℃ for demulsification, sampling to determine the average particle size of metal compounds in the emulsion to be 64 nm (as shown in figure 2), performing vacuum filtration, washing the surfactant and chloride ions by deionized hydrous ethanol, and drying in an oven at the temperature of 120 ℃ to obtain a cured substance;
s4: mixing the condensate, ammonium orthomolybdate (7.42 g) and graphite C (2.75 g), roasting for 3 hours at 400 ℃ under the protection of nitrogen, and then introducing hydrogen fluoride for fluorination for 10 hours to obtain the metal oxide/C composite fluorination catalyst.
Example 3
This example provides a metal oxide/C composite fluorination catalyst, the metal oxide is Cr2O3/ MoO3-Al2O3-ZnO-MgO，Cr2O3And (MoO)3-Al2O3-ZnO-MgO) in a molar ratio of 6:1, MoO3-Al2O3MoO in-ZnO-MgO3Is 50% of Al2O3The molar fraction of (3) is 14%, the molar fraction of ZnO is 14%, the molar fraction of MgO is 22%, and the mass fraction of C is 5%. Prepared by the following method.
S1: 22.38g of CrCl are weighed out3·6H2O、0.75g AlCl3·9H2O、0.59g Zn(NO3)2·6H2O and 0.61g MgSO4·6H2Dissolving O in 76 mL of deionized water, and mixing to obtain a metal salt solution, wherein the concentration of metal ions in the solution is 1.2 mol/L;
s2: adding 40g of surfactant SOPE-10, 68 g of co-surfactant n-heptanol and 192g of oil phase n-hexane into a metal salt solution, and stirring and mixing to obtain a clear and transparent emulsion;
s3: introducing ammonia gas into the microemulsion at the speed of 0.4L/h for reaction, stopping introducing ammonia gas when the pH =12, continuing stirring for reaction for 5 hours, heating to the temperature of the microemulsion system of 80 ℃ for demulsification, sampling to determine the average particle size of metal compounds in the emulsion to be 78 nm (as shown in figure 3), performing vacuum filtration, washing the surfactant and chloride ions by deionized hydrous ethanol, and drying in an oven at the temperature of 120 ℃ to obtain a cured substance;
s4: mixing the condensate, ammonium orthomolybdate (8.65 g) and graphite C (0.49 g), roasting for 16 hours at the temperature of 150 ℃ under the protection of nitrogen, and then introducing hydrogen fluoride for fluorination for 10 hours to obtain the metal oxide/C composite fluorination catalyst.
Example 4
This example provides a metal oxide/C composite fluorination catalyst, the metal oxide is Cr2O3/ MoO3-Al2O3-Y2O3，Cr2O3And (MoO)3-Al2O3-Y2O3) In a molar ratio of 8:1, MoO3-Al2O3-Y2O3Medium MoO3Is 54% by mole, Al2O3In a molar fraction of 23%, Y2O3The molar fraction of (3) is 23% and the mass fraction of C is 25%. Prepared by the following method.
S1: 27.71 g of CrCl are weighed out3·6H2O and 1.13g AlCl3·9H2O、0.87g、YCl3.6H2And mixing the O in 183 mL of deionized water to obtain a metal salt solution, wherein the concentration of metal ions in the salt solution is 0.6 mol/L.
S2: adding 162 g of surfactant 0P-9, 162 g of cosurfactant n-hexanol and 315 g of oil phase n-hexane into a metal salt solution, stirring and mixing to obtain a clear and transparent emulsion;
s3: introducing ammonia gas into the microemulsion at the speed of 0.5L/h for reaction, stopping introducing ammonia gas when the pH =13, continuing stirring for reaction for 5 hours, heating to the temperature of the microemulsion system of 60 ℃ for demulsification, sampling to determine the average particle size of the metal compounds in the emulsion to be 28 nm (as shown in figure 4), performing vacuum filtration, washing the surfactant and chloride ions by deionized hydrous ethanol, and drying in an oven at the temperature of 120 ℃ to obtain a cured substance;
s4: mixing the condensate, ammonium orthomolybdate (8.65 g) and graphite C (3.09 g), roasting at 350 ℃ for 4 hours under the protection of nitrogen, and then introducing hydrogen fluoride for fluorination for 10 hours to obtain the metal oxide/C composite fluorination catalyst.
Comparative example 1
This comparative example provides a fluorination catalyst Cr2O3The catalyst is prepared by the following method, wherein the mass fraction of C is 25%.
Mixing 10.3g of high-purity analytical grade chromium hydroxide with 2.5g of graphite, roasting for 4 hours at 350 ℃ under the protection of nitrogen, and then introducing hydrogen fluoride for fluorination for 10 hours to obtain the catalyst.
The performance of the catalysts provided in examples 1-4 and comparative example 1 were tested. The specific method comprises the following steps: synthesizing R125 by taking PCE as a raw material; the test results are shown in Table 1.
Table 1 results of performance testing of catalysts provided in examples 1-4 and comparative example 1
The performance of the catalysts provided in examples 1-4 and comparative example 1 were tested. The specific method comprises the following steps: synthesizing R134a by taking R133a as a raw material; the test results are shown in Table 2.
Table 2 results of performance testing of catalysts provided in examples 1-4 and comparative example 1
As can be seen from the results in tables 1 and 2, the catalyst provided in each example has good catalyst activity, excellent selectivity when used in fluorination reaction, high conversion rate, mild reaction conditions, and controllable formation of the main impurity R115 in R125 production and the main impurity R1122 in R134a production, thereby achieving control of formation of by-products from the source; in addition, the use of the fluorination catalyst can reduce the energy consumption of fluorination reaction, reduce the steps of product separation and purification, reduce the investment of separation and purification devices and equipment, reduce the production cost and bring obvious economic benefits.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. The metal oxide/C composite fluorination catalyst is characterized in that the metal oxide is Cr2O3/MxOy，Cr2O3And MxOyThe molar ratio of (A) to (B) is 5-9: 1; the mass fraction of C in the composite fluorination catalyst is 15-30%; said M comprises Mo, x and y are such that MxOyThe valence of (2) is zero.
2. The metal oxide/C composite fluorination catalyst of claim 1 wherein said M further comprises one or more of Al, Mg, Zn, Y or Ni; the mole fraction of Mo in M is not less than 10%.
3. The metal oxide/C composite fluorination catalyst of claim 1 wherein Cr is2O3And MxOyIs 8: 1.
4. The metal oxide/C composite fluorination catalyst of claim 1 wherein the mass fraction of C in said composite fluorination catalyst is 25%.
5. The method for preparing the metal oxide/C composite fluorination catalyst according to any one of claims 1 to 4, comprising the following steps:
s1: dissolving Cr salt to obtain metal salt solution;
s2: adding a surfactant, a cosurfactant and an oil phase into a metal salt solution, and stirring and mixing to obtain an emulsion;
s3: adjusting the pH value of the emulsion to 10-14, stirring and reacting for 2-8 h, demulsifying, performing suction filtration, and washing to obtain a solid substance;
s4: and adding ammonium molybdate and C into the solid, drying, roasting at 150-400 ℃ in an inert atmosphere, and fluorinating to obtain the metal oxide/C composite fluorination catalyst.
6. The method according to claim 1, wherein the Cr salt is CrCl3Or Cr (NO)3)3One or two of them; the ammonium molybdate is one or more of ammonium orthomolybdate, ammonium paramolybdate, ammonium dimolybdate or ammonium tetramolybdate.
7. The method of claim 1, wherein when M further comprises one or more of Al, Mg, Zn, Y, or Ni, S1 further comprises a step of dissolving one or more of Al salt, Mg salt, Zn salt, Y salt, or Ni salt to obtain a metal salt solution.
8. The preparation method according to claim 5, wherein the mass ratio of the surfactant to the co-surfactant in S2 is 1: 2-2: 1; the mass ratio of the total of the surfactant and the cosurfactant, the oil phase and the metal salt is 1.0-2.0: 1.5-3.0: 1.
9. The method according to claim 1, wherein ammonia gas is introduced into S3 to adjust pH; the introduction rate of the ammonia gas is 0.1-1.0L/h.
10. Use of the metal oxide/C composite fluorination catalyst according to any of claims 1 to 4 in fluorination reactions.
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