CN107376952B - Preparation method of tetrafluoroethane catalyst - Google Patents
Preparation method of tetrafluoroethane catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000001556 precipitation Methods 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000011261 inert gas Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- -1 aluminum oxyfluoride Chemical compound 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- AHSFRJBERJUGJC-UHFFFAOYSA-N O(F)F.[Na] Chemical compound O(F)F.[Na] AHSFRJBERJUGJC-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- RENNOLBODVTPQJ-UHFFFAOYSA-N [Ca].FOF Chemical compound [Ca].FOF RENNOLBODVTPQJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000003682 fluorination reaction Methods 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a tetrafluoroethane catalyst, which comprises the following steps: (1) adding a metal salt solution and a precipitator into a precipitation tank for reaction to obtain reaction precipitation particles; (2) aging, washing and drying the reaction precipitate particles to obtain a catalyst precursor; (3) roasting the catalyst in a roasting furnace; (4) and activating the roasted catalyst to obtain a final finished product for later use. The invention provides a technical scheme of a preparation method of a tetrafluoroethane catalyst, the method is simple, the labor intensity is low, the prepared catalyst product has good quality and high activity, so that the generation amount of reaction byproducts in subsequent reactions is effectively reduced, meanwhile, equipment and operation process of the treatment process are simple, the operation is automatic, the prepared catalyst has good repeatability, the performance of the catalyst is stable, and the economic benefit is improved.
Description
Technical Field
The invention relates to a preparation method of a tetrafluoroethane catalyst.
Background
1,1,1, 2-tetrafluoroethane (abbreviated as HFC-134a) is widely applied to various refrigeration fields as a substitute of a Freon refrigerant having a destructive effect on the atmospheric ozone layer, and has a high economic value. Companies in the world also spend a great deal of money and resources on developing it and applying for a great deal of patents. Most of the current patents are based on gas phase fluorination processes. The energy consumption during the reaction is very high due to the high reaction temperature required and the low conversion per reaction when using the gas phase fluorination method (Bell. S.L.USP 4129003). In addition, the hydrogen fluoride is greatly excessive in the reaction process, the reaction selectivity is not ideal, and the requirements on the separation and purification conditions of the product are high, so that the investment of production equipment is greatly increased. Chinese patent ZL01141970.9 discloses a fluorination catalyst for preparing 1,1,1, 2-tetrafluoroethane, the structural formula of the fluorination catalyst is CrX0.005-0.5Y0.005-0.3O0.1-1.0F1.0-3.0, wherein X is Mn, Co or Zn, and Y is Mg or Ni. The catalyst has the advantages of high activity, good stability, long service life and the like. However, the catalyst has reduced catalytic efficiency and even is deactivated after being used for a period of time due to high-temperature carbonization of halogenated olefin or alkane and chloroalkane compounds generated after the reaction. The conventional regeneration method of the metal catalyst is to contact the catalyst with a regeneration gas such as air or oxygen at a certain temperature for a certain time. The regeneration method has a good regeneration effect on most metal catalysts, but the regeneration effect is not ideal for the fluorination catalyst with a structure, and the activity of the regenerated catalyst can only reach 50-60% of that of a fresh catalyst. In addition, the fluorination catalyst has problems of rapid deterioration of catalytic activity and low selectivity of the target product due to a low specific surface area. In addition, although this patent discloses a method of activating a catalyst precursor by introducing a mixed gas of nitrogen and hydrogen, the induction period of the treated catalyst is still long and the selectivity to the target product is low. These are not favorable for reducing the preparation cost of the 1,1,1, 2-tetrafluoroethane and improving the product quality and the production efficiency.
Disclosure of Invention
The invention aims to provide a technical scheme of a preparation method of a tetrafluoroethane catalyst aiming at the defects in the prior art, the method is simple, the labor intensity is low, the prepared catalyst product has good quality and high activity, so that the generation amount of reaction byproducts in subsequent reactions is effectively reduced, meanwhile, the equipment and the operation process of the treatment process are simple, the operation is automatic, the repeatability of the prepared catalyst is good, the performance of the catalyst is stable, and the economic benefit is improved.
In order to solve the technical problems, the invention adopts the technical scheme that the preparation method of the tetrafluoroethane catalyst is characterized by comprising the following steps:
(1) adding a metal salt solution and a precipitator into a precipitation tank for coprecipitation treatment, and controlling the metal salt solution and the precipitator by a metering pump according to a molar ratio (2.1-3.7): 1 add to the precipitation tank in, heating device in the precipitation tank simultaneously opens, heat treatment is carried out to the precipitation tank inside, preheat the temperature and keep at 70 ~ 100 ℃, rotatory when rotating electrical machines drives heating coil and stirring rod simultaneously, not only improve heating device's heating rate, make the temperature rise speed in the precipitation tank keep unanimous, and stir the processing to the misce bene in the precipitation tank again, improve the reaction rate of metal salt solution and precipitant, accelerate the preparation rate of catalyst, stir 30 ~ 45min, and improve the pH value in the precipitation tank gradually, until reaching the best pH value of reaction, continue to react 2 ~ 5h again, obtain the reaction precipitation granule.
(2) The reaction precipitation particles obtained by the reaction in the step (1) continue to precipitate and age for 1-1.5 h in the precipitation tank, the particles produced grow up, pure coarse crystals with uniform particle sizes are formed, the reaction precipitation particle structure gradually becomes a stable structure, the reaction precipitation particles are separated from the precipitation tank, the reaction precipitation particles enter the washing tank to be washed, the reaction precipitation particles enter the washing tank, an upper spray rod group and a lower spray rod group spray washing liquid out, the reaction precipitation particles are washed, the purity of the reaction precipitation particles is improved, impurities on the surfaces of the reaction precipitation particles are effectively removed, and finally, moisture on the surfaces of the reaction precipitation particles is removed through drying, so that a catalyst precursor is obtained.
(3) Adding the catalyst precursor into a roasting converter, introducing inert gas for drying protection treatment, heating to 220-280 ℃ at a heating rate of 10-25 ℃ per hour, keeping the temperature for 3-5 hours, heating to 320-450 ℃ at a heating rate of 30-55 ℃ under the condition of continuously introducing the inert gas, keeping the temperature for 8-15 hours, continuously introducing the inert gas for blowing, and cooling to 180 ℃.
(4) Adding the catalyst precursor subjected to roasting treatment into a first reactor for activation treatment, loading the catalyst precursor on a porous carrier to form a catalyst bed layer, simultaneously introducing hydrogen fluoride gas into the first reactor at a rate of 1.5-3.5 g/min, introducing inert gas for drying protection treatment, heating to 200-280 ℃ at a temperature rise rate of 10-35 ℃ per hour, fluorinating for 8-10 h, heating to 350-400 ℃ at a temperature rise rate of 10-25 ℃, continuously introducing the inert gas, cooling to 180 ℃, keeping the temperature for 4-6 h, gradually increasing the flow of the hydrogen fluoride gas, reducing the flow of the inert gas until the hydrogen fluoride gas is completely introduced at the constant temperature for 4-8 h, and ensuring that the activation temperature is 15-45 ℃, so that the activity of the catalyst is improved and the subsequent reaction efficiency is high, reducing the yield of the by-products, and finally cooling to room temperature for later use.
Further, in the step (1), the metal salt solution is one or a mixture of two or more of a nitrate solution, a sulfate solution, an organic acid salt solution or a metal double salt solution, and the precipitant is one or a mixture of two or more of an alkali, a carbonate or an organic acid.
Further, in the step (4), the material of the porous support is fluoride or oxyfluoride, the fluoride is one or a mixture of two or more of aluminum fluoride, sodium fluoride and calcium fluoride, and the oxyfluoride is one or a mixture of two or more of aluminum oxyfluoride, sodium oxyfluoride and calcium oxyfluoride.
Further, in the step (4), the weight ratio of the catalyst precursor to the porous support is 1: (1-5).
Furthermore, in the step (3) and the step (4), the introducing speed of the inert gas is 0.5-1.5L/min, the activity of the catalyst is effectively improved by effectively controlling the introducing speed of the inert gas, and the prepared catalyst has good stability.
Further, the inert gas is one or a mixture of nitrogen and helium.
Compared with the prior art, the preparation method of the catalyst has the advantages of simple process, low labor intensity, obviously improved quality of the finished catalyst product, obviously improved surface performance and effectively prolonged service life. Meanwhile, the specific surface area, the pore volume and the pore diameter of the catalyst prepared by the process are improved to a great extent, the activity of the catalyst is greatly improved, and the yield of byproducts can be effectively inhibited in the subsequent preparation of tetrafluoroethane. In addition, the catalyst has stable activity by roasting the catalyst, and the activity of the catalyst is improved by activation treatment, so that the energy of the catalyst is larger, the contact area between the catalyst and the raw material in the tetrafluoroethane reaction is increased, the yield of the product and the reaction rate are improved, the yield and variety of byproducts are reduced, and the subsequent product purification is facilitated.
The invention provides a technical scheme of a preparation method of a tetrafluoroethane catalyst, the method is simple, the labor intensity is low, the prepared catalyst product has good quality and high activity, so that the generation amount of reaction byproducts in subsequent reactions is effectively reduced, meanwhile, equipment and operation process of the treatment process are simple, the operation is automatic, the prepared catalyst has good repeatability, the performance of the catalyst is stable, and the economic benefit is improved.
Detailed Description
The invention relates to a preparation method of a tetrafluoroethane catalyst, which comprises the following steps:
(1) adding a metal salt solution and a precipitant into a precipitation tank for coprecipitation treatment, wherein the metal salt solution is one or a mixture of more than two of nitrate solution, sulfate solution, organic acid salt solution or metal complex salt solution, the precipitant is one or a mixture of more than two of alkalis, carbonates or organic acids, and the metal salt solution and the precipitant are controlled by a metering pump according to a molar ratio (2.1-3.7): 1 add to the precipitation tank in, heating device in the precipitation tank simultaneously opens, heat treatment is carried out to the precipitation tank inside, preheat the temperature and keep at 70 ~ 100 ℃, rotatory when rotating electrical machines drives heating coil and stirring rod simultaneously, not only improve heating device's heating rate, make the temperature rise speed in the precipitation tank keep unanimous, and stir the processing to the misce bene in the precipitation tank again, improve the reaction rate of metal salt solution and precipitant, accelerate the preparation rate of catalyst, stir 30 ~ 45min, and improve the pH value in the precipitation tank gradually, until reaching the best pH value of reaction, continue to react 2 ~ 5h again, obtain the reaction precipitation granule.
(2) The reaction precipitation particles obtained by the reaction in the step (1) continue to precipitate and age for 1-1.5 h in the precipitation tank, the particles produced grow up, pure coarse crystals with uniform particle sizes are formed, the reaction precipitation particle structure gradually becomes a stable structure, the reaction precipitation particles are separated from the precipitation tank, the reaction precipitation particles enter the washing tank to be washed, the reaction precipitation particles enter the washing tank, an upper spray rod group and a lower spray rod group spray washing liquid out, the reaction precipitation particles are washed, the purity of the reaction precipitation particles is improved, impurities on the surfaces of the reaction precipitation particles are effectively removed, and finally, moisture on the surfaces of the reaction precipitation particles is removed through drying, so that a catalyst precursor is obtained.
(3) Adding the catalyst precursor into a roasting converter, introducing inert gas for drying protection treatment, heating to 220-280 ℃ at a heating rate of 10-25 ℃ per hour, keeping the temperature for 3-5 hours, heating to 320-450 ℃ at a heating rate of 30-55 ℃ under the condition of continuously introducing the inert gas, keeping the temperature for 8-15 hours, continuously introducing the inert gas for blowing, and cooling to 180 ℃.
(4) Adding the catalyst precursor subjected to roasting treatment into a first reactor for activation treatment, and loading the catalyst precursor on a porous carrier to form a catalyst bed layer, wherein the material of the porous carrier is fluoride or oxyfluoride, the fluoride is one or a mixture of more than two of aluminum fluoride, sodium fluoride and calcium fluoride, the oxyfluoride is one or a mixture of more than two of aluminum oxyfluoride, sodium oxyfluoride and calcium oxyfluoride, and the weight ratio of the catalyst precursor to the porous carrier is 1: (1-5), simultaneously introducing hydrogen fluoride gas into the first reactor at a rate of 1.5-3.5 g/min, introducing inert gas for drying and protecting, wherein the introduction rate of the inert gas is 0.5-1.5L/min, the inert gas is one or a mixture of nitrogen and helium, the activity of the catalyst is effectively improved by effectively controlling the introduction rate of the inert gas, the stability of the prepared catalyst is good, then heating to 200-280 ℃ at a heating rate of 10-35 ℃ per hour, fluorinating for 8-10 h, then heating to 350-400 ℃ at a heating rate of 10-25 ℃, continuously introducing the inert gas, cooling to 180 ℃, keeping the temperature for 4-6 h, gradually increasing the flow of the hydrogen fluoride gas, reducing the flow of the inert gas until the hydrogen fluoride is completely introduced at a constant temperature of 4-8 h, and ensuring that the activation temperature is 15-45 ℃, thereby improving the activity performance of the catalyst, ensuring high subsequent reaction efficiency, reducing the yield of by-products and finally cooling to room temperature for later use.
Compared with the prior art, the preparation method of the catalyst has the advantages of simple process, low labor intensity, obviously improved quality of the finished catalyst product, obviously improved surface performance and effectively prolonged service life. Meanwhile, the specific surface area, the pore volume and the pore diameter of the catalyst prepared by the process are improved to a great extent, the activity of the catalyst is greatly improved, and the yield of byproducts can be effectively inhibited in the subsequent preparation of tetrafluoroethane. In addition, the catalyst has stable activity by roasting the catalyst, and the activity of the catalyst is improved by activation treatment, so that the energy of the catalyst is larger, the contact area between the catalyst and the raw material in the tetrafluoroethane reaction is increased, the yield of the product and the reaction rate are improved, the yield and variety of byproducts are reduced, and the subsequent product purification is facilitated.
The invention provides a technical scheme of a preparation method of a tetrafluoroethane catalyst, the method is simple, the labor intensity is low, the prepared catalyst product has good quality and high activity, so that the generation amount of reaction byproducts in subsequent reactions is effectively reduced, meanwhile, equipment and operation process of the treatment process are simple, the operation is automatic, the prepared catalyst has good repeatability, the performance of the catalyst is stable, and the economic benefit is improved.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (4)
1. A preparation method of a tetrafluoroethane catalyst is characterized by comprising the following steps:
(1) adding a metal salt solution and a precipitator into a precipitation tank for coprecipitation treatment, and controlling the metal salt solution and the precipitator by a metering pump according to a molar ratio (2.1-3.7): 1, adding the mixture into a precipitation tank, starting a heating device in the precipitation tank, heating the interior of the precipitation tank, keeping the preheating temperature at 70-100 ℃, simultaneously driving a heating coil and a stirring rod to rotate simultaneously by a rotating motor, not only improving the heating rate of the heating device to keep the temperature rise rate in the precipitation tank consistent, but also stirring the mixed materials in the precipitation tank to improve the reaction rate of a metal salt solution and a precipitator, accelerating the preparation rate of a catalyst, stirring for 30-45 min, gradually improving the p H value in the precipitation tank until the optimum p H value of the reaction is reached, and continuing the reaction for 2-5 h to obtain reaction precipitation particles;
(2) continuing to precipitate and age the reaction precipitation particles obtained by the reaction in the step (1) in a precipitation tank for 1-1.5 hours to enable the produced particles to grow up to form pure coarse crystals with uniform particle sizes, gradually changing the structure of the reaction precipitation particles into a stable structure, separating the reaction precipitation particles from the precipitation tank, allowing the reaction precipitation particles to enter a washing tank for washing treatment, spraying washing liquid by an upper spray rod group and a lower spray rod group when the reaction precipitation particles enter the washing tank, washing the reaction precipitation particles, improving the purity of the reaction precipitation particles, effectively removing impurities on the surfaces of the reaction precipitation particles, and finally drying to remove moisture on the surfaces of the reaction precipitation particles to obtain a catalyst precursor;
(3) adding a catalyst precursor into a roasting converter, introducing inert gas for drying protection treatment, heating to 220-280 ℃ at a heating rate of 10-25 ℃ per hour, keeping the temperature for 3-5 hours, heating to 320-450 ℃ at a heating rate of 30-55 ℃ under the condition of continuously introducing the inert gas, keeping the temperature for 8-15 hours, continuously introducing the inert gas for blowing, cooling to 180 ℃, and controlling the introduction rate of the inert gas to be 0.5-1.5L/min;
(4) adding the catalyst precursor subjected to roasting treatment into a first reactor for activation treatment, loading the catalyst precursor on a porous carrier to form a catalyst bed layer, wherein the porous carrier is made of fluoride or oxyfluoride, the fluoride is one or a mixture of more than two of aluminum fluoride, sodium fluoride and calcium fluoride, the oxyfluoride is one or a mixture of more than two of aluminum oxyfluoride, sodium oxyfluoride and calcium oxyfluoride, simultaneously introducing hydrogen fluoride gas into the first reactor at a rate of 1.5-3.5 g/min, introducing inert gas for drying protection treatment, the introduction rate of the inert gas is 0.5-1.5L/min, heating to 200-280 ℃ at a heating rate of 10-35 ℃ per hour, fluorinating for 8-10 hours, heating to 350-400 ℃ at a heating rate of 10-25 ℃, and continuously introducing inert gas, cooling to 180 ℃, keeping the temperature constant for 4-6 h, gradually increasing the flow of the hydrogen fluoride gas, reducing the flow of the inert gas until the hydrogen fluoride gas is completely introduced, keeping the temperature constant for 4-8 h, and ensuring that the activation temperature is 15-45 ℃, so that the activity performance of the catalyst is improved, the subsequent reaction efficiency is high, the yield of byproducts is reduced, and finally the temperature is reduced to room temperature for later use.
2. The process according to claim 1 for producing a tetrafluoroethane catalyst, which comprises: in the step (1), the metal salt solution is one or a mixture of two or more of a nitrate solution, a sulfate solution, an organic acid salt solution or a metal double salt solution, and the precipitant is one or a mixture of two or more of an alkali, a carbonate or an organic acid.
3. The process according to claim 1 for producing a tetrafluoroethane catalyst, which comprises: in the step (4), the weight ratio of the catalyst precursor to the porous support is 1: (1-5).
4. The process according to claim 1 for producing a tetrafluoroethane catalyst, which comprises: the inert gas is one or a mixture of nitrogen and helium.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648846A (en) * | 2009-09-15 | 2010-02-17 | 浙江三美化工股份有限公司 | Producing process for synthesizing 1, 1, 1, 2-tetrafluoroethane by liquid phase-gas phase method |
| CN103304368A (en) * | 2012-03-07 | 2013-09-18 | 中化蓝天集团有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane, and preparation method of catalyst of 1,1,1,2-tetrafluoroethane |
| CN105936515A (en) * | 2015-12-30 | 2016-09-14 | 衢州学院 | Synthesis method of 1,1,1,2- tetrafluoroethane catalyst precursor and catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101648846A (en) * | 2009-09-15 | 2010-02-17 | 浙江三美化工股份有限公司 | Producing process for synthesizing 1, 1, 1, 2-tetrafluoroethane by liquid phase-gas phase method |
| CN103304368A (en) * | 2012-03-07 | 2013-09-18 | 中化蓝天集团有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane, and preparation method of catalyst of 1,1,1,2-tetrafluoroethane |
| CN105936515A (en) * | 2015-12-30 | 2016-09-14 | 衢州学院 | Synthesis method of 1,1,1,2- tetrafluoroethane catalyst precursor and catalyst |
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