CN107376952A - A kind of preparation method of HFC-134a catalyst - Google Patents
A kind of preparation method of HFC-134a catalyst Download PDFInfo
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- CN107376952A CN107376952A CN201710432486.XA CN201710432486A CN107376952A CN 107376952 A CN107376952 A CN 107376952A CN 201710432486 A CN201710432486 A CN 201710432486A CN 107376952 A CN107376952 A CN 107376952A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000001376 precipitating effect Effects 0.000 claims abstract description 13
- 238000001994 activation Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002222 fluorine compounds Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- IPHGXIXTTVTVGZ-UHFFFAOYSA-N [F].[O-2].[Ca+2] Chemical compound [F].[O-2].[Ca+2] IPHGXIXTTVTVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 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
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- LQTYZHKQBRWECE-UHFFFAOYSA-N [O-2].[Na+].[F].[Na+] Chemical compound [O-2].[Na+].[F].[Na+] LQTYZHKQBRWECE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000003682 fluorination reaction Methods 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- -1 alkenyl halide Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UOBPHQJGWSVXFS-UHFFFAOYSA-N [O].[F] Chemical compound [O].[F] UOBPHQJGWSVXFS-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000004044 response Effects 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
-
- B01J35/60—
-
- B01J35/61—
-
- 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
Abstract
The invention discloses a kind of preparation method of HFC-134a catalyst, step are as follows：(1) metal salt solution and precipitating reagent are added into stillpot to be reacted to obtain reaction precipitation particle；(2) after reaction precipitation particle being carried out into aging, washing and drying process, catalyst precarsor is obtained；(3) calcination process is carried out to catalyst in roaster；(4) activation process is carried out to the catalyst after roasting to obtain final finished standby.The invention provides a kind of technical scheme of the preparation method of HFC-134a catalyst, method is simple, labor intensity is low, catalyst product quality after preparation is good, active height, so as to effectively reduce the byproduct of reaction growing amount in subsequent reactions, simultaneously the handling process equipment and operating process it is all fairly simple, operation automation, the catalyst being prepared it is reproducible, and the stable performance of catalyst, improves economic benefit.
Description
Technical field
The present invention relates to a kind of preparation method of HFC-134a catalyst.
Background technology
1,1,1,2- HFC-134as (abbreviation HFC-134a) are as the freon refrigeration for having destruction to atmospheric ozone layer
The substitute of agent, various refrigeration fields are widely used in, there is very high economic value.Each major company also spends greatly in the world
The financial resources and material resources of amount are developed to it, and have applied for a large amount of patents.The patent of the overwhelming majority is to be based on gas phase fluorination at present
Method.During due to being prepared with gaseous fluoridizing method, required reaction temperature is very high, and the conversion ratio per secondary response is again very low, reaction
During energy consumption greatly (Bell.S.L.USP 4129003).Hydrogen fluoride is significantly excessive in other course of reaction, and reacts
Selective and undesirable, separation and purification condition to product require very high, so that the investment of production equipment greatly increases.In
State patent of invention ZL01141970.9 discloses a kind of fluorination catalyst prepared available for HFA 134a, the fluorination
Catalyst structure formula is CrX0.005-0.5Y0.005-0.3O0.1-1.0F1.0-3.0, and wherein X is Mn, Co or Zn, Y be Mg or
Ni.The active height of the catalyst, the advantages that stability is good, and service life is long.However, because generating after alkenyl halide or reaction
The reasons such as alkane, alkyl chloride hydrocarbon compound high temperature cabonization, catalytic efficiency reduces even the catalyst in use for some time
Inactivation.The conventional regeneration method of metallic catalyst be by catalyst and regeneration gas such as air or oxygen at a certain temperature
Contact certain time.The renovation process is preferable for the regeneration effect of most metals catalyst, but structured for having
For fluorination catalyst, regeneration effect is unsatisfactory, and the activity of the catalyst after regeneration is only capable of reach fresh catalyst 50%
~60%.In addition, also the catalytic activity of catalyst is caused to decay fast, target there is making fluorination catalyst specific surface area relatively low
The problems such as selectivity of product is low.Although in addition, it which disclose by the mixed gas for being passed through nitrogen and hydrogen to catalyst
The method that precursor carries out activation process, but the induction period of the catalyst after the processing is still longer, the choosing for target product
Selecting property is relatively low.These are unfavorable for reducing the preparation cost of 1,1,1,2- HFC-134as, improved product quality and production efficiency.
The content of the invention
Present invention aims at provide a kind of preparation of HFC-134a catalyst for the deficiency present in prior art
The technical scheme of method, method is simple, labor intensity is low, and the catalyst product quality after preparation is good, active height, so as to effectively drop
Byproduct of reaction growing amount in low subsequent reactions, while the equipment of the handling process and operating process are all fairly simple, operation
Automation, reproducible, and the stable performance of catalyst for the catalyst being prepared, improves economic benefit.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is a kind of preparation side of HFC-134a catalyst
Method, it is characterised in that comprise the following steps：
(1), metal salt solution and precipitating reagent are added in stillpot and carry out co-precipitation processing, and passes through measuring pump control
Metal salt solution and precipitating reagent processed are according to mol ratio (2.1~3.7)：1 is added in stillpot, while the heating dress in stillpot
Unlatching is put, processing is internally heated to stillpot, preheating temperature is maintained at 70~100 DEG C, while electric rotating machine drives heating
Rotated while coil pipe and stirring rod, not only improve the rate of heat addition of heater so that the temperature rise rate in stillpot is kept
Unanimously, and again the mixed material in stillpot is stirred, improves the reaction rate of metal salt solution and precipitating reagent,
Accelerate the preparation speed of catalyst, stir 30~45min, and gradually step up the pH value in stillpot, until reaching reaction
Optimal pH value, 2~5h of reaction is further continued for, obtains reaction precipitation particle.
(2), the reaction precipitation particle that step (1) reaction obtains is continued to precipitate 1~1.5h of aging in stillpot, made
The particle growth that must be produced, form the pure coarse crystal of even particle size so that reaction precipitation grain structure gradually becomes surely
Determine structure, then reaction precipitation particle is separated out of stillpot, enter and carrying out washing treatment, reaction precipitation particle are carried out in sink
Upper spray boom group and lower spray boom group spray out cleaning solution while entering in sink, and reaction precipitation particle is washed
Processing, the purity of reaction precipitation particle is improved, effective impurity for removing reaction precipitation particle surface, is finally removed instead by drying
The moisture of particle surface should be precipitated, obtains catalyst precarsor.
(3), catalyst precarsor is added in roasting converter, while is passed through inert gas and protection processing is dried, so
220~280 DEG C are warming up to 10~25 DEG C per hour of heating rate afterwards, then 3~5h of constant temperature, are further continued for being passed through inert gas
In the case of, then with 30~55 DEG C of heating rate 320~450 DEG C are risen to, 8~15h of constant temperature, continue to be passed through inert blowing gas
Sweep, cool to 180 DEG C.
(4), the catalyst precarsor after calcination process is added in first reactor and carries out activation process, and will catalysis
The load of agent precursor is on porous support so as to form beds, while toward being passed through hydrogen fluoride gas, fluorine in first reactor
The speed that is passed through for changing hydrogen be 1.5~3.5g/min, then is passed through inert gas protection is dried and handle, then with per hour 10~
35 DEG C of heating rate is warming up to 200~280 DEG C, is fluorinated 8~10h, then rise to 350~400 with 10~25 DEG C of heating rate
DEG C, continue to be passed through inert gas, cool to 180 DEG C, 4~6h of constant temperature, then the flow of hydrogen fluoride gas is stepped up, reduce
The flow of inert gas, until be passed through hydrogen fluoride gas 4~8h of constant temperature completely, and ensure activation temperature 15~45 DEG C it
Between, so as to which that improves catalyst enlivens performance so that follow-up reaction efficiency is high, reduces the yield of accessory substance, is finally cooled to
Room temperature is standby.
Further, in step (1), metal salt solution is nitrate solution, sulfate liquor, acylate solution or gold
Belong to mixture more than one or both of complex salt solution, precipitating reagent is one kind or two in bases, carbonate or organic acid
The mixture of the kind above.
Further, in step (4), the material of porous carrier is fluoride or oxyfluoride, and fluoride is aluminum fluoride, fluorine
Change mixture more than one or both of sodium, calcirm-fluoride, oxyfluoride is in fluorine alumina, fluorine sodium oxide molybdena, fluorine calcium oxide
One or more kinds of mixtures.
Further, in step (4), the weight ratio of catalyst precarsor and porous carrier is 1：(1~5).
Further, in step (3) and step (4), the speed that is passed through of inert gas is 0.5~1.5L/min, by having
The activity for being passed through speed, effectively improving catalyst of effect control inert gas, obtained catalyst stabilization performance are good.
Further, inert gas is the mixture of one or both in nitrogen, helium.
Compared with prior art, the process of preparing of catalyst is simple, labor intensity is low, finished catalyst by the present invention
Quality is obviously improved, surface property improves significantly, service life effectively extends.Prepared by present invention process simultaneously after
The specific surface area of catalyst, pore volume, aperture all have significant improvement, and the activity of catalyst are greatly improved, follow-up
HFC-134a prepare in can effectively suppress the yield of accessory substance.And by being carried out to catalyst at roasting in the present invention
Reason so that catalyst has stable activity, then by activation process, increase catalyst enlivens performance so that catalyst
Energy is bigger, increase catalyst contact area between raw material in HFC-134a reaction, so as to improve the yield of product and
The generation rate of reaction, the yield and kind of accessory substance are reduced, is easy to the purification of subsequent product.
The invention provides a kind of technical scheme of the preparation method of HFC-134a catalyst, and method is simple, labor intensity
Low, catalyst product quality after preparation is good, active height, so as to effectively reduce the byproduct of reaction growing amount in subsequent reactions,
The equipment of the handling process and operating process are all fairly simple simultaneously, operation automation, the repeatability for the catalyst being prepared
It is good, and the stable performance of catalyst, improve economic benefit.
Embodiment
A kind of preparation method of HFC-134a catalyst of the present invention, comprises the following steps：
(1), metal salt solution and precipitating reagent are added in stillpot and carry out co-precipitation processing, metal salt solution is nitric acid
Mixture more than one or both of salting liquid, sulfate liquor, acylate solution or metal complex salt solution, precipitating reagent
For mixture more than one or both of bases, carbonate or organic acid, and metal salt solution is controlled by measuring pump
With precipitating reagent according to mol ratio (2.1~3.7)：1 is added in stillpot, while the heater in stillpot is opened, to heavy
Shallow lake groove is internally heated processing, and preheating temperature is maintained at 70~100 DEG C, while electric rotating machine drives heating coil and stirring rod
While rotate, not only improve heater the rate of heat addition so that the temperature rise rate in stillpot is consistent, and again right
Mixed material in stillpot is stirred, and is improved the reaction rate of metal salt solution and precipitating reagent, is accelerated catalyst
Speed is prepared, stirs 30~45min, and gradually steps up the pH value in stillpot, until reach the optimal pH value of reaction, followed by
2~5h of continuous reaction, obtains reaction precipitation particle.
(2), the reaction precipitation particle that step (1) reaction obtains is continued to precipitate 1~1.5h of aging in stillpot, made
The particle growth that must be produced, form the pure coarse crystal of even particle size so that reaction precipitation grain structure gradually becomes surely
Determine structure, then reaction precipitation particle is separated out of stillpot, enter and carrying out washing treatment, reaction precipitation particle are carried out in sink
Upper spray boom group and lower spray boom group spray out cleaning solution while entering in sink, and reaction precipitation particle is washed
Processing, the purity of reaction precipitation particle is improved, effective impurity for removing reaction precipitation particle surface, is finally removed instead by drying
The moisture of particle surface should be precipitated, obtains catalyst precarsor.
(3), catalyst precarsor is added in roasting converter, while is passed through inert gas and protection processing is dried, so
220~280 DEG C are warming up to 10~25 DEG C per hour of heating rate afterwards, then 3~5h of constant temperature, are further continued for being passed through inert gas
In the case of, then with 30~55 DEG C of heating rate 320~450 DEG C are risen to, 8~15h of constant temperature, continue to be passed through inert blowing gas
Sweep, cool to 180 DEG C.
(4), the catalyst precarsor after calcination process is added in first reactor and carries out activation process, and will catalysis
The load of agent precursor is on porous support so as to form beds, and the material of porous carrier is fluoride or oxyfluoride, fluorine
Compound is mixture more than one or both of aluminum fluoride, sodium fluoride, calcirm-fluoride, and oxyfluoride is fluorine alumina, fluorine oxygen
The weight ratio of mixture more than one or both of change sodium, fluorine calcium oxide, catalyst precarsor and porous carrier is 1：(1~
5), while toward hydrogen fluoride gas is passed through in first reactor, the speed that is passed through of hydrogen fluoride is 1.5~3.5g/min, then is passed through lazy
Property gas be dried protection processing, the speed that is passed through of inert gas be 0.5~1.5L/min, inert gas be nitrogen, helium
The mixture of middle one or both, by effectively controlling the activity for being passed through speed, effectively improving catalyst of inert gas, it is made
Catalyst stabilization performance it is good, be then warming up to 200~280 DEG C with 10~35 DEG C per hour of heating rate, fluorination 8~
10h, then 350~400 DEG C are risen to 10~25 DEG C of heating rate, continue to be passed through inert gas, cool to 180 DEG C, it is permanent
4~6h of temperature, then the flow of hydrogen fluoride gas is stepped up, the flow of inert gas is reduced, until being passed through hydrogen fluoride gas completely
4~8h of constant temperature, and ensure activation temperature between 15~45 DEG C, so as to which that improves catalyst enlivens performance so that follow-up
Reaction efficiency is high, reduces the yield of accessory substance, it is standby to be finally cooled to room temperature.
Compared with prior art, the process of preparing of catalyst is simple, labor intensity is low, finished catalyst by the present invention
Quality is obviously improved, surface property improves significantly, service life effectively extends.Prepared by present invention process simultaneously after
The specific surface area of catalyst, pore volume, aperture all have significant improvement, and the activity of catalyst are greatly improved, follow-up
HFC-134a prepare in can effectively suppress the yield of accessory substance.And by being carried out to catalyst at roasting in the present invention
Reason so that catalyst has stable activity, then by activation process, increase catalyst enlivens performance so that catalyst
Energy is bigger, increase catalyst contact area between raw material in HFC-134a reaction, so as to improve the yield of product and
The generation rate of reaction, the yield and kind of accessory substance are reduced, is easy to the purification of subsequent product.
The invention provides a kind of technical scheme of the preparation method of HFC-134a catalyst, and method is simple, labor intensity
Low, catalyst product quality after preparation is good, active height, so as to effectively reduce the byproduct of reaction growing amount in subsequent reactions,
The equipment of the handling process and operating process are all fairly simple simultaneously, operation automation, the repeatability for the catalyst being prepared
It is good, and the stable performance of catalyst, improve economic benefit.
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technique effect, made ground simple change, equivalent substitution or modification etc., all cover
Among protection scope of the present invention.
Claims (6)
1. a kind of preparation method of HFC-134a catalyst, it is characterised in that comprise the following steps：
(1), metal salt solution and precipitating reagent are added in stillpot and carry out co-precipitation processing, and gold is controlled by measuring pump
Belong to salting liquid and precipitating reagent according to mol ratio (2.1~3.7)：1 is added in stillpot, while the heater in stillpot is opened
Open, processing is internally heated to stillpot, preheating temperature is maintained at 70~100 DEG C, while electric rotating machine drives heating coil
Being rotated while with stirring rod, not only improve the rate of heat addition of heater so that the temperature rise rate in stillpot is consistent,
And the mixed material in stillpot is stirred again, the reaction rate of metal salt solution and precipitating reagent is improved, is accelerated
The preparation speed of catalyst, 30~45min is stirred, and gradually step up the pH value in stillpot, until reaching the optimal of reaction
PH value, 2~5h of reaction is further continued for, obtains reaction precipitation particle.
(2), the reaction precipitation particle that step (1) reaction obtains is continued to precipitate 1~1.5h of aging in stillpot so that production
Particle growth, form the pure coarse crystal of even particle size so that reaction precipitation grain structure gradually becomes rock-steady structure,
Reaction precipitation particle is separated out of stillpot again, enters and carrying out washing treatment is carried out in sink, reaction precipitation particle enters
Upper spray boom group and lower spray boom group spray out cleaning solution while in sink, and carrying out washing treatment is carried out to reaction precipitation particle,
The purity of reaction precipitation particle is improved, effective impurity for removing reaction precipitation particle surface, finally reacts heavy by drying to remove
The moisture of shallow lake particle surface, obtains catalyst precarsor.
(3), by catalyst precarsor be added to roasting converter in, while be passed through inert gas be dried protection processing, then with
10~25 DEG C of heating rate is warming up to 220~280 DEG C per hour, then 3~5h of constant temperature, is further continued for being passed through the feelings of inert gas
Under condition, then with 30~55 DEG C of heating rate 320~450 DEG C, 8~15h of constant temperature are risen to, continue to be passed through inert gas purge, it is cold
But 180 DEG C are cooled to.
(4), the catalyst precarsor after calcination process is added in first reactor and carries out activation process, and by before catalyst
Body load is on porous support so as to form beds, while toward being passed through hydrogen fluoride gas, hydrogen fluoride in first reactor
The speed that is passed through be 1.5~3.5g/min, then be passed through inert gas be dried protection processing, then with 10~35 DEG C per hour
Heating rate be warming up to 200~280 DEG C, be fluorinated 8~10h, then 350~400 DEG C are risen to 10~25 DEG C of heating rate, after
It is continuous to be passed through inert gas, cool to 180 DEG C, 4~6h of constant temperature, then the flow of hydrogen fluoride gas is stepped up, reduce inertia
The flow of gas, until being passed through hydrogen fluoride gas 4~8h of constant temperature completely, and activation temperature is ensured between 15~45 DEG C, from
And improve the performance of enlivening of catalyst so that follow-up reaction efficiency is high, reduces the yield of accessory substance, it is standby to be finally cooled to room temperature
With.
A kind of 2. preparation method of HFC-134a catalyst according to claim 1, it is characterised in that：In the step
(1) in, the metal salt solution is one in nitrate solution, sulfate liquor, acylate solution or metal complex salt solution
Kind or two or more mixtures, the precipitating reagent are mixing more than one or both of bases, carbonate or organic acid
Thing.
A kind of 3. preparation method of HFC-134a catalyst according to claim 1, it is characterised in that：In the step
(4) in, the material of the porous carrier is fluoride or oxyfluoride, and the fluoride is in aluminum fluoride, sodium fluoride, calcirm-fluoride
One or more kinds of mixtures, the oxyfluoride be fluorine alumina, fluorine sodium oxide molybdena, one kind in fluorine calcium oxide or two
The mixture of the kind above.
A kind of 4. preparation method of HFC-134a catalyst according to claim 1, it is characterised in that：In the step
(4) in, the weight ratio of the catalyst precarsor and the porous carrier is 1：(1~5).
A kind of 5. preparation method of HFC-134a catalyst according to claim 1, it is characterised in that：In the step
(3) and in step (4), the speed that is passed through of the inert gas is 0.5~1.5L/min, by effectively controlling inert gas
Speed is passed through, effectively improves the activity of catalyst, obtained catalyst stabilization performance is good.
A kind of 6. preparation method of HFC-134a catalyst according to claim 5, it is characterised in that：The inert gas
For the mixture of one or both in nitrogen, helium.
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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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| 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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