CN110496615A - A kind of preparation method of catalysts for gas phase fluorination - Google Patents
A kind of preparation method of catalysts for gas phase fluorination Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012938 design process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011438 discrete method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and chromium
-
- 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
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of catalysts for gas phase fluorination, it include: to first pass through to prepare fluorination catalyst, have many advantages, such as that specific surface area is high, stability is strong, active component not easily runs off, the service life is long using the fluorination catalyst that method of the invention is prepared, replace gas phase fluorination suitable for fluorine chlorine, is especially suitable for being catalyzed the preparation of R134a and R125 product.
Description
Technical field
The present invention relates to a kind of catalysts for gas phase fluorination and its preparation method and application, and in particular to one kind is for halogenated
The catalyst of the gas phase fluorination of hydrocarbon and hydrogen fluoride, in particular for being catalyzed the catalyst and its system that prepare R134 and R125
Preparation Method.
Background technique
In fluorine chemical field, since the Ozone Depletion Potential (ODP) of hydrogen fluorohydrocarbon (HFCs) is 0, global warming potential
Value (GWP) is smaller, and refrigeration performance is similar to fluorochlorohydrocarbon (CFCs), is the ideal substitute of CFCs, is widely used in large-scale quotient
Industry refrigerant, foaming agent, extinguishing chemical etc..Gas phase exchange chloride for fluoride is the key reaction of selective synthesis fluorochemical,
Since its is simple and easy to do, economical and practical, have many advantages, such as that pollution is few easy to operate, the industry that oneself is widely used in hydrofluorocarbon is raw
During production.Common gas phase fluorination is such as:
CF3CH2Cl+HF→CF3CH2F(HFC-134a)+HCl
CCl2=Cl2+5HF→CF3CHF2(HFC-125)+5HCl
Since the exchange reaction of two kinds of halogen ions of F and Cl is thermodynamically obstructed, effective catalyst is generally required to reduce
The activation energy of reaction is accelerated the positive of reaction and is carried out, reduces backward reaction, improve reaction rate.The choosing of catalysts for gas phase fluorination
It selects and research is of great significance.The bulk catalyst of gas phase fluorination is generally chromium-based catalysts.So far, improve
The method of catalyst performance is usually to add assistant metal, non-metal assistant is added or changes the structure of catalyst.
One of Co, Mn, Zn, Fe, Mg, Al, Ni are added in the catalyst as Chinese patent CN1931431A is disclosed
Or two kinds of elements.
For another example Chinese patent CN105727929 discloses a kind of fluorination catalyst of bigger serface, contains Cr, Al, Mg
With the 4th kind of metallic element, the 4th kind of metallic element is selected from one of Ga, Cd and Co, two or three.
For another example CN101214447A discloses a kind of Naluminum fluoride base fluorating catalyst and preparation method thereof, which exists
Ammonium aluminum fluoride class compound is added in preparation process, increases specific surface area and the aperture of catalyst.Fluorination catalyst is by for many years
Although development has very big progress, still remains catalyst and be easy carbon distribution, the short problem of catalyst life causes to produce
Byproduct in process object increases, and needs regenerated catalyst of frequently stopping, and makes that increased production cost, while catalyst activity and selection
Property needs to be further increased.Especially refrigerant product R during the preparation process, by-product is selectively excessively high, catalyst activity
The problems such as lower and easy carbon distribution, is serious, is badly in need of developing a kind of catalyst production haveing excellent performance, being suitble to catalysis to prepare refrigerant
Product.
Summary of the invention
In view of the above-mentioned problems, the present invention is in catalyst formulation design process, in conjunction with gas phase fluorine mechanism of catalytic reaction (fluorine
Chlorine exchange reaction), it is contemplated that in addition the synergistic effect of influence and various metals auxiliary agent of the various metal promoters to the reaction exists
Expanding agent is added in the combination formula to change catalyst pore structure, while by the debunching action of repeated ultrasonic bring, being obtained
Catalytic active component high degree of dispersion, activity is high, it is not easy to product and service life long fluorination catalyst.
Above-mentioned in order to reach, the present invention provides a kind of preparation methods of catalysts for gas phase fluorination, including walk as follows
It is rapid:
(1) ammonium salt stirring and dissolving is formed into mixed solution in the in the mixed solvent of ethylene glycol and ethyl alcohol；To mixed solution
Middle that the metal oxide with catalytic activity is added, ultrasonic disperse obtains mixed liquor, and it is anti-that mixed solution is transferred to polytetrafluoroethylene (PTFE)
It answers in kettle, carries out water hydro-thermal reaction
(2) it is cooled to room temperature after hydro-thermal reaction, stirs while the soft template that mass ratio is 2%-~4% is added
Aqueous solution and KI solution adjust pH, ultrasonic intermittent stirring rear for several times；Then it separates, wash, is dry, being calcined after addition expanding agent
Obtain fluorination catalyst.
The present invention is modified to fluorination catalyst using the discrete method of ultrasonic wave, so that fluorination catalyst is with higher
Catalytic activity and stability.Discrete ultrasonic wave is a kind of new method for improving catalyst ability, can use remodeling catalysis
Agent composed structure improves the yield of fluorinated hydrocarbons to be conducive to its playing a role in fluorine catalysis reaction.
Preferably, the chromic salts of the in the mixed solvent of step (1) is chromium chloride or chromic nitrate, more preferably easily to obtain
Chromium chloride, additional amount by chromium ion concentration be 0.02~0.12mol/L in terms of be added.
Preferably, the volume ratio of the in the mixed solvent ethylene glycol and ethyl alcohol of ethylene glycol and ethyl alcohol are as follows: V ethylene glycol: V ethyl alcohol
=1:2.
Metallic element in the metal oxide of addition are as follows: in Al, In, Ni, La, Co, Mg, Ce, Fe, Mn, Cu, Y and Ga
One kind；In some embodiments, Cr and metal element A l, In, Ni, La, Co, Mg, Ce, Fe, Mn, Cu, Y and Ga are a kind of
A variety of total mass ratios is 10~90；After metal oxide is added, 30~60min of ultrasound.
Preferably, 150~160 DEG C of hydrothermal temperature, the time 3~6 hours, it is further preferred that 160 DEG C are reacted 5 hours.It is soft
The ratio of template solution influences the content in catalyst, other compositions relative amount is also influenced, thus to fluorination catalyst effect
There is certain influence；Preferably, the soft template solution person's of choosing cetyl trimethylammonium bromide in step (2), additional amount is with ten
Six alkyl trimethyl ammonium bromides and chromium chloride molar ratio are (15~100): 100 meters；Further preferably (50~100): 100,
Most preferably 50%.
The additional amount of KI, i.e. ratio influence the content in catalyst, other compositions relative amount are also influenced, thus to fluorine
Changing catalytic effect has certain influence.
Preferably, in step (2) KI solution additional amount by KI and chromium chloride molar ratio for (25~100): in terms of 100；Into one
Step is preferably (50~100): 100, most preferably 75%.KI concentration is 0.3~0.5mol/L, preferably 0.4mol/L.
Preferably, in step (2) ultrasound twice, each 60min.One is stirred at interval of 10min stirring rod after ultrasound
It is secondary, it stirs 10~12 times.
Preferably, in step (2), adjusting pH is 3~5.
Preferably, twice, each 60min, interval 10min are stirred primary ultrasound with stirring rod.
Preferably, in step (2), with water and ethanol washing 3 times.
In preparation method provided by the invention, expanding agent can be added to change the pore structure and specific surface area of catalyst,
The expanding agent is ammonium salt, and specific existence form is inorganic or organic acid salt.
Preferably, the ammonium salt is (NH4)2CO3、NH4NO3, at least one of ammonium citrate and ammonium tartrate.
Preferably, the mass ratio of the Cr salt and other metal oxide quality sums and expanding agent is 1:0.1~1.More
Mass ratio for the preferably described Cr salt and other metal oxide quality sums and expanding agent is 1:0.1~0.5.
In preparation method provided by the invention, the roasting is carried out in inert gas, and the temperature of the roasting is
300~400 DEG C.In some embodiments, the temperature of roasting is 300~350 DEG C；In other embodiments, roasting
Temperature is 320~350 DEG C.
In preparation method provided by the invention, the time of the roasting is 2~6h.Roasting in some embodiments
Time is 3h, 4h or 5h.
Fluorination catalyst provided by the invention replaces gas phase fluorination suitable for fluorine chlorine, is especially suitable for R125
With the preparation of R134a, and when preparing R134a, by-product control effect is more excellent.
Drying mode used by some embodiments of the invention is drying drying.It should be pointed out that can achieve identical
The drying means of effect further includes but is not limited to drying, vacuum drying, freeze-drying, pneumatic conveying drying, microwave drying, infrared ray
Dry and dielectric dry etc..Drying time is 1-6h.
It is for convenience, and to provide general meaning to the scope of the present invention.This description should be read to include
One or at least one, and the odd number also includes plural number, unless it is obvious that it is meant otherwise.
Unless otherwise defined, the otherwise meaning of all scientific and technical terminologies used herein and of the art common
As technical staff is generally understood.Although similar or equivalent method and material with approach described herein and material
It can be used in the implementation or test of embodiment of the present invention, but suitable method and material be described below.It is mentioned above
All publications, patent application, patent and other bibliography are incorporated herein in a manner of being cited in full text, except non-quoted has
Body paragraph.If conflict occurs, it is subject to this specification and its included definition.In addition, material, method and embodiment are only
Illustrative, it is no intended to it is limited.
The beneficial effects of the present invention are:
(1) in catalyst formulation design process of the invention, Determination of multiple metal elements is added on the basis of chromium base, is passed through
The formula combination of metallic element in catalyst is adjusted, catalyst active center is changed, is made using the collaboration of other metallic elements
With the catalyst of synthesis catalytic activity with higher is conducive to the yield for improving target product, thus in industrialized production
Energy consumption, save the cost can be largely reduced in the process.
(2) present invention adds expanding agent ammonium salt in catalyst preparation process, and catalyst precursor is in roasting, ammonium salt
Class compound is thermally decomposed to generate volatile matter so that the specific surface area of catalyst increases, the size of pore volume and average pore size and
It is more evenly distributed, changes catalyst pore structure, be conducive to the progress of exchange chloride for fluoride.
(3) activity composition when reducing catalyst load by ultrasonic technology in catalyst preparation process of the invention
Cluster effect, to improve the service efficiency and service life of fluorine catalyst.
(4) when catalyst of the invention is applied to synthesis R134a gas phase fluorination, by-product can greatly be reduced
The selectivity of R134 solves the problems, such as that industrial target product R134a is difficult to separate with its isomer R134, improves and produces
Quality, while reducing energy consumption.
Specific embodiment
Comparative example 1 (coprecipitation)
10gCrCl is weighed respectively3·6H2O, 3.75g Al (NO3)3·9H2O and 1.36gZnCl2In molten 500mL water, obtain
To mixing salt solution, which is mixed with ammonium hydroxide to pH value of solution=9 and is precipitated, throws filter cake after filtering washing
Enter baking oven in 120 DEG C of dry 6h, is then transferred to roaster, 350 DEG C of high-temperature roasting 4h in N2 atmosphere, the sample powder after roasting
It is broken sieving and be added graphite be uniformly mixed, compression molding obtains catalyst precursor.Then above-mentioned catalyst precursor is packed into anti-
It answers in device, the mixed gas for being passed through nitrogen and HF is fluorinated at 350 DEG C, and chromium-based fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 289.83m2/g, be averaged hole
Diameter is 6.01nm.
Comparative example 2
(1) by 10gCrCl3·6H2The ethylene glycol for being dissolved in 500mL of O and in the mixed solvent (the V ethylene glycol: V of ethyl alcohol
Ethyl alcohol=1:2) and 40min is stirred, form solution；
(2) rotor is taken out, 1.02gAl is added into solution2O3, 0.81gZnO, stir 30 minutes, mixed solution is shifted
Into ptfe autoclave, 160 DEG C keep the temperature 5 hours；
(3) after being cooled to room temperature, rotation stirring, is added 0.72 gram of cetyl trimethylammonium bromide (CTAB) and KI is molten
0.51 gram of KI (is dissolved in 5mL water) by liquid, and adjusting pH with HNO3 is 3, is stirred 120 minutes with stirring rod, deionized water is used after separation
Three times with ethanol washing.
(4) it after plunging the sample into 120 DEG C of baking oven dry 6h, adds 15g (NH4)2CO3And it is transferred to roaster, in N2 atmosphere
In 330 DEG C of high-temperature roasting 4h, obtain fluorination catalyst after roasting.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 300.48 ㎡/g, be averaged hole
Diameter is 5.444nm.
Embodiment 1
(1) by 10gCrCl3·6H2The ethylene glycol for being dissolved in 500mL of O and in the mixed solvent (the V ethylene glycol: V of ethyl alcohol
Ethyl alcohol=1:2) and 40min is stirred, form solution；
(2) rotor is taken out, 1.02gAl is added into solution2O3, 0.81gZnO is 30 minutes ultrasonic, and mixed solution is shifted
Into ptfe autoclave, 160 DEG C keep the temperature 5 hours；
(3) after being cooled to room temperature, rotation stirring, is added 0.72 gram of cetyl trimethylammonium bromide (CTAB) and KI is molten
0.51 gram of KI (is dissolved in 5mL water) by liquid, and adjusting pH with HNO3 is 3, and twice, each 60min is spaced 10min stirring rod to ultrasound
Stirring 1 time.After separation, three times with water and ethanol washing.
(4) it after plunging the sample into 120 DEG C of baking oven dry 4h, adds 24g (NH4)2CO3And it is transferred to roaster, in 2 atmosphere of N
In 330 DEG C of high-temperature roasting 4h, obtain fluorination catalyst after roasting.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 430.67 ㎡/g, be averaged hole
Diameter is 7.11nm.
Embodiment 2
(1) by 10gCrCl3·6H2The ethylene glycol for being dissolved in 500ml of O and in the mixed solvent (the V ethylene glycol: V of ethyl alcohol
Ethyl alcohol=1:2) and 40min is stirred, form solution；
(2) rotor is taken out, 1.02gAl is added into solution2O3, 3gMgO is 30 minutes ultrasonic, and mixed solution is transferred to
In ptfe autoclave, 160 DEG C keep the temperature 5 hours；
(3) after being cooled to room temperature, rotation stirring, is added 0.72 gram of cetyl trimethylammonium bromide (CTAB) and KI is molten
0.51 gram of KI (is dissolved in 5mL water) by liquid, and adjusting pH with HNO3 is 3, and twice, each 60min is spaced 10min stirring rod to ultrasound
Stirring 1 time.After separation, three times with water and ethanol washing
(4) it after plunging the sample into 120 DEG C of baking oven dry 8h, adds 10g (NH4)2CO3And it is transferred to roaster, in 2 atmosphere of N
In 330 DEG C of high-temperature roasting 4h, obtain fluorination catalyst after roasting.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 429.67 ㎡/g, be averaged hole
Diameter is 7.01nm.
Embodiment 3
(1) by 10gCrCl3·6H2The ethylene glycol for being dissolved in 500mL of O and in the mixed solvent (the V ethylene glycol: V of ethyl alcohol
Ethyl alcohol=1:2) and 40min is stirred, form solution；
(2) rotor is taken out, 1.02gAl is added into solution2O3, 5.45mgCoO, ultrasound 30 minutes, by mixed solution turn
It moves on in ptfe autoclave, 160 DEG C keep the temperature 5 hours；
(3) after being cooled to room temperature, rotation stirring, is added 0.72 gram of cetyl trimethylammonium bromide (CTAB) and KI is molten
0.51 gram of KI (is dissolved in 5mL water) by liquid, and adjusting pH with HNO3 is 3, and twice, each 60min is spaced 10min stirring rod to ultrasound
Stirring 1 time.After separation, three times with water and ethanol washing
(4) it after plunging the sample into 120 DEG C of baking oven dry 6h, adds 10g (NH4)2CO3And it is transferred to roaster, in N2 atmosphere
In 330 DEG C of high-temperature roasting 4h, obtain fluorination catalyst after roasting.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 405.36 ㎡/g, be averaged hole
Diameter is 6.84nm.
Embodiment 4
(1) by 10gCrCl3·6H2The ethylene glycol for being dissolved in 500mL of O and in the mixed solvent (the V ethylene glycol: V of ethyl alcohol
Ethyl alcohol=1:2) and 40min is stirred, form solution；
(2) rotor is taken out, 1.02mgAl is added into solution2O3, 4.8mgGa2O3, ultrasound 30 minutes, by mixed solution
It is transferred in ptfe autoclave, 160 DEG C keep the temperature 5 hours；
(3) after being cooled to room temperature, rotation stirring, is added 0.72 gram of cetyl trimethylammonium bromide (CTAB) and KI is molten
0.51 gram of KI (is dissolved in 5mL water) by liquid, and adjusting pH with HNO3 is 3, and twice, each 60min is spaced 10min stirring rod to ultrasound
Stirring 1 time.After separation, three times with water and ethanol washing.
(4) it after plunging the sample into 120 DEG C of baking oven dry 6h, adds 10g (NH4)2CO3, and it is transferred to roaster, in N2 atmosphere
In 330 DEG C of high-temperature roasting 4h, obtain fluorination catalyst after roasting.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 421.6 ㎡/g, average pore size
For 6.98nm.
Embodiment 5 (1) is by 10gCrCl3·6H2The ethylene glycol for being dissolved in 500mL of O and in the mixed solvent (the V second of ethyl alcohol
Glycol: V ethyl alcohol=1:2) and 40min is stirred, form solution；
(2) rotor is taken out, 1.02gAl is added into solution2O3, 4.55gFe2O3, it is 30 minutes ultrasonic, mixed liquor is shifted
Into ptfe autoclave, 160 DEG C keep the temperature 5 hours；
(3) after being cooled to room temperature, rotation stirring, is added 0.72 gram of cetyl trimethylammonium bromide (CTAB) and KI is molten
0.51 gram of KI (is dissolved in 5mL water) by liquid, and adjusting pH with HNO3 is 3, and twice, each 60min is spaced 10min stirring rod to ultrasound
Stirring 1 time.After separation, three times with water and ethanol washing
(4) it after plunging the sample into 120 DEG C of baking oven dry 6h, adds 10g (NH4) 2CO 3 and is transferred to roaster, in N2 gas
330 DEG C of high-temperature roasting 4h in atmosphere, obtain fluorination catalyst after roasting.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 418.7m2/g, average pore size
For 7.09nm.
Fluorination catalyst prepared by comparative example 1, comparative example 2, Examples 1 to 5 is used to synthesize commenting for R134a respectively
Valence experiment, evaluation condition are as follows: being packed into 100mL fluorination catalyst in self-control fixed bed, reaction temperature control is 310~350
℃.R133a and HF are passed through in reactor, the flow of R133a is 24g/h, and HF flow is 60g/h.R133a and HF are after mixing
Into reactor reaction, product gas washing, alkali cleaning use gas chromatographic analysis after removing HCl and HF.The conversion ratio of R133a and
R134a is selectively shown in Table 1.
Evaluation experimental result of 1 catalysts for gas phase fluorination of table to R134a
By data in 1 it is found that compared with comparative example 1, the fluorination catalyst catalysis reaction provided by embodiment 1 is,
R134a conversion ratio has been increased to 98.49% by 95.33%, and the conversion ratio of by-product R134 is had decreased to by 2.325%
0.647%.Show that the catalytic efficiency of the fluorination catalyst prepared by this method is higher, it is more preferable to the control effect of byproduct.
Claims (8)
1. a kind of preparation method of catalysts for gas phase fluorination, which comprises the steps of:
(1) then the metal oxygen with catalytic activity is added in the in the mixed solvent of ethylene glycol and ethyl alcohol in chromic salts stirring and dissolving
Compound, ultrasonic disperse obtain mixed liquor, and mixed solution is transferred to polytetrafluoroethylene (PTFE) and carries out hydro-thermal reaction；
(2) it is cooled to room temperature after hydro-thermal reaction, stirs while the soft template aqueous solution that mass ratio is 2%-~4% is added
With KI solution, pH, ultrasonic intermittent stirring rear for several times are adjusted；Then it separates, wash, is dry, calcining to obtain fluorination after addition expanding agent
Catalyst.
2. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that in the metal oxide
Metallic element are as follows: at least one of Al, In, Ni, La, Co, Mg, Ce, Fe, Mn, Cu, Y and Ga.
3. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that the mixing of step (1) is molten
Chromic salts described in agent be chromium chloride or chromic nitrate, additional amount by chromium ion concentration be 0.02~0.12mol/L in terms of be added.
4. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that in step (1): the gold
Belong to oxide addition by metal oxide resultant and chromic salts mass ratio for (2.5~50): in terms of 100.
5. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that soft described in step (2)
Template solution is cetyl trimethylammonium bromide (CTAB), one of polyvinylpyrrolidone (PVP).
6. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that ultrasound two in step (2)
It is secondary, 30~60min every time.
7. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that the expanding agent is selected from
(NH4)2CO3 、NH4NO3, at least one of ammonium citrate and ammonium tartrate.
8. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that in the step (2)
Roasting is carried out in inert gas, 300-450 DEG C of maturing temperature, time 2-8h.
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