CN106748626A - A kind of preparation of the method and its catalyst of the trifluoro propene of 1 chlorine of synthesis of trans 3,3,3 - Google Patents
A kind of preparation of the method and its catalyst of the trifluoro propene of 1 chlorine of synthesis of trans 3,3,3 Download PDFInfo
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- 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
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Abstract
The present invention provides a kind of preparation of the method and its catalyst of the trifluoro propene of 1 chlorine of synthesis of trans 3,3,3, it is characterised in that：With 1,1,1,3,3 pentachloropropanes are raw material, under composite catalyst effect, the chlorine 3,3 of hydrogen fluoride gas phase fluorination synthesis of trans 1,3 trifluoro propenes, the composite catalyst is made up of component A chrome green major catalyst, B component oxide promoter and C component co-catalysts, and B component is one or more in zinc oxide, cobalt oxide, aluminum oxide, and C components are chemically modified treated activated carbon.The composite catalyst that this patent is provided has specific surface area big, and catalysis activity is high, can with high selectivity (98.2%) under the reaction condition that the application is provided the trifluoro propene of 1 chlorine of synthesis of trans 3,3,3, and catalyst has the advantages that the long-life.
Description
Technical field
The present invention relates to a kind of trans 1- chloro-3,3,3 ,-trifluoropropenes preparation method, more particularly to 1,1,1,3,3- five
Chloropropane is raw material, under composite highly effective catalyst action, vapor phase method synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes.
Background technology
Hydro-chloro fluoroolefin (HCFC) such as the chloro- 3,3,3- trifluoro propenes of 1-（HCFC-1233zd）It is synthesis 1,1,1,3,
3- pentafluoropropanes（HFC-245fa）Important source material.Compare with fluoric ether (HFC), it has relatively low consumption ozone potential
Value (ODP) and chamber effect potential value (GWP), United States Patent (USP) US0098755, US0207788, and US6362383 etc. are open
It is to substitute HFC-245fa, it is contemplated that in foaming agent, one of prime candidate of the aspect such as refrigerant and solvent application.Additionally, it
It is also used as fluorochemical monomer complex functionality macromolecule, and as to introducing CF in organic molecule3The building block raw material of group.
The synthetic method of 1- chloro-3,3,3 ,-trifluoropropenes is broadly divided into liquid-phase fluorination process and gaseous fluoridizing method, and liquid phase method is more
With transition metal chloride SbCl5, SbCl3, TaCl5, NbCl5, MoCl5 TiCl4Deng being catalyst, batch (-type) synthesis, work
The industry three wastes are more, and environmental pollution is big, equipment corrosion is serious, and vapor phase method is easy to continuous production, pollute small, and yield is high, by increasingly
Many fluorine chemical enterprises are used, wherein with 1,1,1,3,3- pentachloropropane (HCC-240fa) is the synthetic route of raw material,
It is method widely used at present.
Take HCC-240fa as the existing document report of reactant synthesis HCFC-1233zd：
United States Patent (USP) US6362383 discloses liquid-phase fluorination HCC-240fa, using Louis acid TiCl4Catalyst, reaction temperature 120
DEG C, reaction pressure 25bar is continuously added to hydrogen chloride gas, the yield 41.5% of product HFC-245fa, HCFC- in course of reaction
The yield 1.5% of 1233zd, the accessory substance of formation is more.United States Patent (USP) US6844475 is disclosed using Louis acid TiCl4Catalysis
Agent, anhydrous HF liquid-phase fluorination HCC-240fa synthesis HCFC-1233zd, 120 DEG C of reaction temperature, reaction pressure 360psi, chromatogram is received
Rate 90%.
Japan Patent JP9194404 is disclosed with Cr2O3/Al2O3It is catalyst, at 150 DEG C ~ 300 DEG C, through 1,1,1,3,
3- pentachloropropanes (HCC-240fa) synthesize HCFC-1233zd with hydrogen fluoride gas phase reaction, and yield is less than 90%, and HCFC-
The yield of 1233zd is reduced with the reduction of reaction temperature.Japan Patent JP10067693 discloses one kind to be fluorinated Al2O3To urge
Agent, in the method that 250 DEG C ~ 400 DEG C gas phase fluorination HCC-240fa synthesize HCFC-1233zd, its yield is 90% ~ 95%, fluorination
Reaction temperature is higher, and catalyst surface knot carbon speed is fast, causes catalyst easily to inactivate.
Chinese patent CN101028994B using oxidation state more than or equal to 4 high-valency metal antimony, niobium, tantalum, zirconium, vanadium,
Molybdenum etc., impregnated on alumina catalyst support, chrome green, aluminum fluoride or magnesium fluoride, prepare loaded catalyst, 150 DEG C ~ 180
DEG C gas phase fluorination HCC-240 fa, synthesize the high income of HCFC-1233zd up to 98%.Although the process yield has reached industry
Change application requirement, the patented technology without reference to catalyst stability, such as by its industrial applications, these loaded catalysts
There must be high stability, the invention in addition limits its practical application from high-valency metal antimony, niobium, tantalum, zirconium, vanadium, molybdenum etc..
In addition to the above-mentioned report for synthesizing HCFC-1233zd as reactant with HCC-240fa, Chinese patent CN1087189C is public
Open 1 ~ 4 halogenated hydrocarbons of carbon atom with hydrogen fluoride in the gas phase, through catalytic addition and substitution, prepare the halogenated hydrocarbons containing fluorine atom.
Catalyst precarsor is mainly made up of the hydroxide of chromium (III), also containing at least one selected from cobalt, nickel, copper, silver, zinc, cadmium, mercury,
The material of aluminium, gallium, tin and lead element；In the presence of the hydrogen, in 350 DEG C ~ 500 DEG C roastings；Or in inert gas, in 100
DEG C ~ 600 DEG C of thermal bake-outs above-mentioned catalyst precarsors for the treatment of, then in the presence of the hydrogen, after the heat treatment is calcined at the temperature disclosed above
Compound and prepare catalyst；Or any one catalyst prepared by partially fluorinated above-mentioned catalyst.Chinese patent
With 1,1- dichloroethanes for reactant, the open hydrogen fluoride gas phase fluorination that is used for synthesizes 1,1- Difluoroethanes to CN100427207C
Catalyst, including chromium, other Metal Substrates and fluorine, oxygen element composition.Metal Substrate is in Gu, Manganese, zinc, iron, magnesium, aluminium, nickel
One or two elements., to the less pollution of environment, catalysis activity is higher, and good stability, catalyst is used for the chromium-based catalysts
Long lifespan, and activation of catalyst regeneration is easy；1,1- Difluoroethanes are not polymerized in catalytic reaction process；Chromium base
Catalyst contact area is big, and catalysis activity is high, and space-time yield is high, and at 150 DEG C ~ 200 DEG C, pressure does not influence product to reaction temperature
Species, by-product species are less.Additionally, the catalyst is prepared using coprecipitation, process is simple, it is easy to operate.
Method is disclosed in synthesis HCFC-1233zd, and gas phase fluorination system is complicated, using different catalysis
Agent can cause different response paths, therefore, different catalysts its activity and selectivity performance difference, such as catalyst is using high
Valency metal, although catalysis activity is high, the HCFC-1233zd of synthesis is two kinds of mixtures of isomers；And due to catalysis
Agent surface Carbon deposition causes rapid deactivation, and poor catalyst stability, short life is difficult industrialization.HCFC-1233zd has two kinds
Isomers, trans HCFC-1233zd (E) and cis HCFC- 1233zd (Z), the physical property of both isomers is in the presence of poor
It is different, 20 DEG C of the boiling point of pure 1233zd (E), 40 DEG C of the boiling point of pure 1233zd (Z).HCFC-1233zd (E) is with its excellent performance
Consistent accreditation is obtained, it both can be used for high-performance, hard polyaminoester insulating foams and produce as liquid blowing agent, also can use
Make refrigerant, cleaning agent, heat-conduction medium etc., can be used to produce HFC-245fa as raw material again, before development well
Scape.Trans HCFC-1233zd (E) has high thermodynamic stability than cis HCFC-1233zd (Z), in fluorination Cr2O3Catalyst
Under effect, in 300 DEG C of temperature, trans HCFC-1233zd (E) has 10% to be isomerized to cis HCFC- 1233zd (Z), and remaining is
Accessory substance.
A kind of first public side of gas phase fluorination HCC-240fa synthesis of trans isomers HCFC-1233zd (E) of this patent
Method, the method uses a kind of composite catalyst, the advantage is that there is high activity under the conditions of fluorination reaction, and high selectivity is high
Stability.
The content of the invention
The present invention is intended to provide a kind of method of synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes, it uses high activity, Gao Xuan
Selecting property, and high stability catalyst, are suitable for hydrogen fluoride gas phase fluorination HCC-240fa synthesis of trans HCFC-1233zd.
In order to clearly demonstrate the present invention, hydrogen fluoride gas phase fluorination HCC- 240fa, synthesis of trans are represented with below formula
The course of reaction of HCFC-1233zd.
The composite catalyst is by component A oxide major catalyst, B component oxide promoter and C component co-catalysis
Agent is constituted, and wherein component A is chrome green, and B component is zinc oxide, cobalt oxide (II), the one kind in aluminum oxide, or two kinds,
Or more than two kinds, C components are chemically modified treated activated carbon.
The component A and B component, its preparation method is：The hydrogen of trivalent chromium, zinc, divalence cobalt and aluminium is prepared with coprecipitation
Oxide is scrubbed, dry, nitrogen atmosphere or hydrogen atmosphere roasting after, obtain component A and B component.
The preparation process of the C components processes activated carbon using the KOH or NaOH of 2M, and 80 DEG C are flowed back 4 hours, are washed out
To neutrality, 120 DEG C dry 12 hours, are then vacuum dried 4 hours.
The component A and B component oxide, with C components, and shaping additive graphite, grind mixed by high-speed grinder
Close, extruded moulding prepares unsupported catalyst.
The composite catalyst wherein component A content 70% ~ 95% (wt), B component content 3% ~ 25% (wt), C component contents
2%~5%(wt)。
The catalyst prepares hydroxide by component A and the slaine of B component through coprecipitation, and wherein slaine refers to
Metal chloride or its nitrate；Using NaOH solution or NH3·H2O is precipitating reagent, through aging, filtration washing, with distilled water
Washing hydroxide precipitation, is 7 ~ 8 to cleaning solution pH.
The drying temperature of the catalyst precursor hydroxide is 50 ~ 80 DEG C, and the time is 48 ~ 144 hours.In hydrogen gas
Atmosphere calcines hydroxide, 350 ~ 460 DEG C of temperature, and the time is 4 hours；Hydroxide, temperature 350 ~ 560 are calcined in a nitrogen atmosphere
DEG C, the time is 4 hours.After calcining hydroxide, it is calcining that content is added in component A and B component oxide, and C components
The aquadag of component A and B component quality 1.0% ~ 3.0% (wt) afterwards, the ground and mixed in high speed Universal pulverizer, the time is 5
~ 10 minutes；Then methocel solution is added wherein, its concentration is 1.0% ~ 5.0% (wt), extruded moulding, room temperature is air-dried.
The hydrogen fluoride gas phase fluorination HCC-240fa processes, composite catalyst is filled into stainless steel reaction pipe, reaction tube
Heating-up temperature is 350 ~ 370 DEG C, and hydrogen fluoride gas are passed through in heating process carries out activation process to catalyst, is produced during being somebody's turn to do
The a large amount of water of life, continuous activation 10 hours, until being generated there is no water in reaction tube, activation is complete, and catalyst obtains optimal fluorine
Content.In processing procedure, hot-spot will cause the specific surface area of catalyst to reduce.In order to prevent this unfavorable phenomenon, adopt
The method purged with high pure nitrogen, dilutes hydrogen fluoride concentration, so that the maximum elevated the temperature due to the generation of heat is not surpassed
Cross 30 DEG C.
The hydrogen fluoride gas phase fluorination HCC-240fa processes, using acid-base titration control HCC-240fa and hydrogen fluoride
Mol ratio, HCC-240fa is very big to product distribution influence with the mol ratio of hydrogen fluoride, and it is anti-that synthesis HCFC-1233zd (E) needs
Thing mol ratio preferred scope is answered 1:10~1:20.
The hydrogen fluoride gas phase fluorination HCC-240fa processes, dehydrochlorination and the step of fluorination reaction one are carried out, reactant with urge
The time of contact of agent has an impact to product distribution, and the selectivity optimal in order to obtain the present invention, the inlet amount of HCC-240fa is excellent
Elect 0.4 ~ 1.0mL/min. as.
The hydrogen fluoride gas phase fluorination HCC-240fa processes, react under normal pressure, and temperature influences the performance of catalyst, directly
The distribution of product is determined, temperature increases, selectivity is reduced, when preferred range is 180 ~ 220 DEG C, reaction is obtained most
Good selectivity.
When prepared by the composite catalyst, heat treatment condition has a significant impact to the performance of catalyst.In nitrogen or hydrogen
Under atmosphere, hydroxide is calcined using different temperatures, X-ray diffraction (XRD) result display gained component A is amorphous and crystallizes
The ratio of chrome green thing phase is different.Increase sintering temperature to 480 DEG C under hydrogen atmosphere, X-ray diffraction (XRD) result shows
Show that component A mainly mutually exists to crystallize chrome green thing, crystal grain is big.Preformed catalyst specific surface area is small.HCC-240fa is anti-
Answer the remaining proportion 9.09% of mixture, the selectivity 45.7% of HCFC-1233zd (E), catalyst life 14.5 hours.
The beneficial effects of the present invention are：Under heat treatment condition disclosed in this patent, X-ray diffraction (XRD) result shows
Show that preformed catalyst component A is mainly unbodied chrome green, but wherein contain the good small grains of dispersiveness, crystal grain
Size estimation is between several nanometers；Catalytically active assessment, not yet the component A chrome green thing of decaying catalyst are carried out
Compare with the catalyst not being fluorinated in advance, change unobvious；The component A of decaying catalyst is entirely unbodied three oxidation
Two chromium.These XRD results, and catalyst activity evaluation result points out that big portion is unbodied chrome green, part jointly
Dispersed tiny chrome green crystal grain well, causes catalyst to have high activity and high stability jointly.This patent is provided
Composite catalyst have specific surface area big, catalysis activity is high, can be with high selectivity (98.2%) under conditions of the application offer
The chloro- 3,3,3- trifluoro propenes of synthesis of trans 1-, and catalyst has the advantages that the long-life.
In catalyst preparation process disclosed in this patent, hydroxide, the shaping of gained oxide are calcined under different condition
The specific surface area of composite catalyst is different afterwards, and HCC-240fa conversion ratios are related to the specific surface area of pre- fluorination treatment catalyst, tool
There is the catalyst of high-specific surface area, catalysis activity is higher.The addition of the cocatalyst B component and C components, influence catalyst
Surface nature, they there may be synergy and major catalyst component A between, therefore under fluorination conditions of the invention, it is multiple
Closing catalyst has a number of surface acidity position, promotes the activity and selectivity of catalyst.The composite catalyst have than
Surface area is big, and catalysis activity is high, and selectivity is high, and catalyst has the advantages that the long-life.
Brief description of the drawings
Fig. 1 is the XRD results that still untapped catalyst is prepared in embodiment 11.
Fig. 2 is the XRD results of the catalyst for preparing and not yet having been inactivated using 100 hours in embodiment 11.
Fig. 3 is prepared and XRD results of decaying catalyst in embodiment 11.
Specific embodiment
The present invention is illustrated below by way of specific embodiment, but is not intended to limit the present invention.
Embodiment 1
133.2 grams of chromium chloride hexahydrates, 6.815 grams of zinc chloride, and 24.15 gram of six water alchlor, Cr3+ : Zn2+ : Al3+
= 1 : 0.1 :0.2 (mol), adds 270 milliliters of distillation water dissolves；76 grams of NaOH, add 100 milliliters of distillation water dissolves, with
Afterwards by NaOH solution（19mol/L）It is slowly added dropwise in Cr3+、Zn2+、Al3+Solution in, magnetic agitation, to occur precipitate, stand
24h is aging.Sediment filtration washing after aging, using 2000 milliliters or so of distillation water washing, until solution ph be 7 ~
8；In 60 DEG C of dryings 48 hours, hydroxide was weighed 73.0 grams after drying；In 350 DEG C, N2The lower roasting of protection 4 hours, after roasting
Oxide weighs 54.0 grams；2.5% (wt%) activated carbon, 3% (wt%) aquadag, using height are added in oxide after baking
Fast Universalpulverizer grinding；5% is added in mixture（wt%）Methocel solution, extruded moulding, room temperature air-dry.
The activated carbon KOH or NaOH treatment of 2M, 80 DEG C are flowed back 4 hours, are then washed till neutrality, and 120 DEG C of drying 12 are small
When, then it is vacuum dried 4 hours.
Embodiment 2
Preparation method with embodiment 1, except that in 350 DEG C, N2The lower roasting of protection is changed to H in 4 hours2The lower roasting 4 of protection is small
When.
Embodiment 3
With embodiment 1, except that changing zinc chloride into CoCL2 6H2O, three kinds of consumptions of salt are 133.2 grams to preparation method
Chromium chloride hexahydrate, 23.84 gram of six water cobaltous dichloride, and 12.33 gram of six water alchlor, Cr3+ : Co2+ : Al3+ = 1 :
0.2 : 0.1(mol)。
Embodiment 4
Preparation method with embodiment 3, except that in 350 DEG C, N2The lower roasting of protection is changed to H in 4 hours2The lower roasting 4 of protection is small
When.
Embodiment 5
Preparation method is with embodiment 1, except that replacing chloride with nitrate, and only uses chromic nitrate（III）And nitric acid
Zinc, the consumption of two kinds of salt is respectively：200.1 gram of nine water chromic nitrate（III）, and 4.132 grams of zinc nitrate hexahydrates, Cr3+ : Zn2+ =
36 :1 (mol), sintering temperature is changed into 420 DEG C from 350 DEG C.
Embodiment 6
Preparation method with embodiment 5, except that in 420 DEG C, N2The lower roasting of protection is changed to H in 4 hours2The lower roasting 4 of protection is small
When.
Embodiment 7
Preparation method is with embodiment 5, except that addition C Composition Actives charcoal is changed into 5.0% (wt%) from 2.5% (wt%).
Embodiment 8
Preparation method is with embodiment 5, except that sintering temperature is changed into 130 DEG C, two hours from 420 DEG C；420 DEG C, four hours,
H2Atmosphere.
Embodiment 9
Preparation method is with embodiment 5, except that sintering temperature is changed into 560 DEG C from 420 DEG C.
Embodiment 10
Preparation method with embodiment 5, except that by NaOH（16mol/L）Solution becomes NH3·H2O（7.5mol/L）.
Embodiment 11
Preparation method with embodiment 9, except that in 460 DEG C, N2The lower roasting of protection is changed to H in 4 hours2The lower roasting 4 of protection is small
When.
The specific surface area of extruded moulding catalyst, 188.3 m2/g, aperture, 5.28nm, pore volume, 0.249 cm3/g；It is attached
Fig. 1 is its XRD diffraction patterns, and the XRD shows the diffraction pattern of the chrome green of crystallization, the width ratio of its half maximum peak
The width of monocrystalline chrome green, 2 θ are the peak of graphite 25.2 in figure, and 2 θ of the diffraction maximum of the chrome green of crystallization are 44.4
, and overlap of peaks at 34.4 and 36.2,63.2 and 65.0.Catalyst was not yet inactivated using 100 hours, the fluorination catalyst
Specific surface area, 447.5 m2/g, aperture, 2.46 nm, pore volume, 0.276 cm3/g, accompanying drawing 2 is its XRD diffraction patterns,
Compare no significant change with accompanying drawing 1.The specific surface area of inactivation rear catalyst, 18.2 m2/g, aperture, 3.65 nm, pore volume,
0.017 cm3/g, accompanying drawing 3 is its XRD diffraction patterns, and component A is amorphous three oxidation during the figure shows decaying catalyst
Two chromium.
Comparative catalyst preparation example 12-17, prepares loaded catalyst, spherical gamma-Al2O3Carrier：F, 3.0-5.0 mm,
Specific surface area >=300 m2/ g, pore volume >=0.40 mL/g, the g/mL of bulk density 0.73 ± 0.03.Tooth form γ-Al2O3Carry
Body：F, 2.68 mm, specific surface area 167.8m2/ g, the mL/g of pore volume 0.82, the g/mL of bulk density 0.47.Supported active
Before component, 130ᵒC, is separately dried spherical gamma-Al2O3With tooth form γ-Al2O3, 24 hours.
Embodiment 12
5.1 grams of chromium chloride hexahydrates, are dissolved in 25 milliliters of distilled water, and this solution is used as maceration extract；21.5 grams of spherical gammas-
Al2O3Carrier adds maceration extract, dries, 70ᵒC, 72 hours.
Embodiment 13
Preparation method with embodiment 12, using spherical gamma-Al2O3It is carrier, 2.1 grams of zinc dichloride and 5.1 gram of six water trichlorine
Change the chromium aqueous solution as maceration extract.
Embodiment 14
Preparation method with embodiment 12, using spherical gamma-Al2O3It is carrier, 4.2 grams of zinc dichloride and 5.1 gram of six water trichlorine
Change the chromium aqueous solution as maceration extract.
Embodiment 15
Preparation method with embodiment 12, using 21.5 grams of tooth form γ-Al2O3It is carrier, 2.55 grams of chromium trichloride aqueous solution conducts
Maceration extract.
Embodiment 16
Preparation method with embodiment 12, using 21.5 grams of tooth form γ-Al2O3It is carrier, 1.05 grams of zinc dichlorides and 2.55 gram three
Chromium chloride solution is used as maceration extract.
Embodiment 17
Preparation method with embodiment 12, using 21.5 grams of tooth form γ-Al2O3It is carrier, 2.1 grams of zinc dichlorides and 2.55 grams of trichlorines
Change the chromium aqueous solution as maceration extract.
Embodiment 18
Embodiment 1-11 prepares the active testing of catalyst.
The catalyst filling for taking 10 ~ 20g embodiments 1-11 preparations enters 304 stainless steel reaction pipes, diamond heating, temperature
350 ~ 370 DEG C, hydrogen fluoride gas are passed through in heating process carries out activation process to catalyst, to improve follow-up fluorination effect.It is living
During change, a large amount of water, continuous activation 10 hours are produced, until being generated there is no water in reaction tube, activated complete.Subsequent HCC-
Reaction tube is passed through after 240fa and hydrogen fluoride vaporization, in the presence of catalyst, fluorination reaction occurs.In course of reaction, using acid
Alkali titration controls the mol ratio of HCC-240fa and hydrogen fluoride.Fluorination reaction under normal pressure, reaction temperature is 200 DEG C, HCC-
240fa is 1 with the mol ratio of hydrogen fluoride:10, HCC-240fa inlet amount is 0.6mL/min..Analyzed using GC-MS and GC
Reaction result, the G/C content change of judgment criteria main detection HCFC-1233zd (E) of catalyst life, when G/C content declines
Reach more than 10%, it is believed that catalyst is inactivated.Activity evaluation is listed in table 1.
Embodiment 19
Preparation method is with embodiment 11, except that fluorination reaction under normal pressure, reaction temperature is changed into 225 DEG C, reaction from 200 DEG C
The results are shown in Table 1.
Embodiment 20
Preparation method is with embodiment 11, except that fluorination reaction under normal pressure, reaction temperature is changed into 250 DEG C, reaction from 200 DEG C
The results are shown in Table 1.
Embodiment 21
Preparation method is with embodiment 11, except that fluorination reaction under normal pressure, reaction temperature is changed into 275 DEG C, reaction from 200 DEG C
The results are shown in Table 1.
Embodiment 22
Preparation method is with embodiment 11, except that fluorination reaction under normal pressure, reaction temperature is changed into 300 DEG C, reaction from 200 DEG C
The results are shown in Table 1.
The gas phase fluorination HCC-240fa of table 1. synthesizes the result of unsupported catalyst in HCFC-1233zd (E).
The comparative catalyst's activity rating of embodiment 23.
Embodiment 12-17 prepares the active testing of catalyst.
160g catalyst activity charcoals are added in quartz glass tube (1.5 m × 30 mm), using " charging suitable for reading, lower mouth goes out
The mode of material ", and to ensure the smooth of product discharge, nitrogen purging is passed through in course of reaction, the flow of nitrogen is 10mL/
Min., at 190 ~ 200 DEG C, product is collected in ice salt bath cooling for reaction temperature control, and in the whole stage of reaction, GC analysis tracking is anti-
Should.
HCC-240fa 3.0Kg are put into altogether, and feed rate is 30mL/h., is tightly held by activated carbon unreacted HCC-240fa
It is 0.32Kg, theoretical deserved product 2.23Kg is actual to collect the tetrachloropropylene 2.0Kg of product 1,1,3,3-, reaction yield
89.6%, 1,1,3,3- tetrachloropropylene G/C content ﹥ 94%.
Take 10 ~ 20g embodiments 12-17 and prepare catalyst filling and enter 304 stainless steel reaction pipes, diamond heating, temperature is
350 ~ 370 DEG C, hydrogen fluoride gas are passed through in heating process carries out activation process to catalyst.In activation process, a large amount of water are produced,
Continuous activation 10 hours, until being generated there is no water in reaction tube, activation is complete.It is passed through instead after tetrachloropropylene and hydrogen fluoride vaporization
Ying Guan, in course of reaction, using acid-base titration control tetrachloropropylene and the mol ratio of hydrogen fluoride.Fluorination reaction under normal pressure, instead
It is 200 DEG C to answer temperature, and tetrachloropropylene is 1 with the mol ratio of hydrogen fluoride:10, the inlet amount of tetrachloropropylene is 0.6mL/min..
Using GC-MS and GC analytical reactions results, the G/C content of judgment criteria main detection HCFC-1233zd (E) of catalyst life
Change, reaches more than 10%, it is believed that catalyst is inactivated when G/C content declines.Activity evaluation is listed in table 2.
The gas phase fluorination tetrachloropropylene of table 2. synthesizes the result of loaded catalyst in HCFC-1233zd (E).
Embodiment 24
15 times of amplification fluorinated reactive evaluation tests of single tube are carried out using 304 stainless-steel pipes.Tube inner diameter is 30mm, and length is
90cm.Weigh 300g embodiments 11 and prepare catalyst, be uniformly filled into reaction tube, it effectively loads length for 50cm.Using plus
The torrid zone is heated to reaction tube, and heating-up temperature is 350 DEG C, and hydrogen fluoride gas are passed through in heating process to be carried out at activation to catalyst
Reason.In activation process, a large amount of water, continuous activation 10 hours are produced, until being generated there is no water in reaction tube, activated complete.
Fluorination process is passed through reaction tube with embodiment 18 after HCC-240fa and hydrogen fluoride vaporization, in course of reaction, uses
It is 1 with the mol ratio of hydrogen fluoride that acid-base titration controls HCC-240fa:10, HCC-240fa inlet amount be 0.6 mL/
Min., it is fluorinated under normal pressure, reaction temperature is 200 DEG C.Crude product is collected using two-stage cooling device after fluorination, and one-level cooling refrigerant is
Mixture of ice and water, temperature is 0 DEG C, and two grades of cooling refrigerants are the mixture of ethylene glycol and water, and ice maker refrigeration, temperature is -25 DEG C of left sides
It is right.After two-stage cooling is collected, another plus primary activity charcoal adsorbs the mixture of HCC-245fa and HCFC-1233zd (E).In catalysis
There is fluorination reaction in the presence of agent, primary product is HCFC-1233zd (E) and a small amount of HCC-245fa.
It wherein continuous 3 hours is timing node mass balance to choose：Total feed is 164.0g, and two-stage cooling device is received altogether
Collect crude product 95.9g, charcoal absorption weightening 2.9g, obtain crude product total amount 98.8g, always feed intake 164.0g, and theory obtains product
Amount 120.3g, reaction yield is 82.1%.The crude product GC analysis results that wherein two-stage cooling device is obtained：HCC-240fa contents：
0.62%, HCFC-1233zd (E) content：91.2%, HCC-245fa content：1.7%, difluoro dichloropropylene content：4.1%.Material
The main cause being lost：Using the method for high pure nitrogen purging in whole experiment process, dilute hydrogen fluoride concentration to drop
Lower security risk, part crude product is blown away by high pure nitrogen.
In catalyst preparation process disclosed in this patent, hydroxide, the shaping of gained oxide are calcined under different condition
The specific surface area of composite catalyst is different afterwards, and HCC-240fa conversion ratios are related to the specific surface area of pre- fluorination treatment catalyst, tool
There is the catalyst of high-specific surface area, catalysis activity is higher, be 188.3 m2/g such as not yet using the specific surface area of catalyst, urge
Agent is used 100 hours, is not yet inactivated, and specific surface area is 447.5 m2/g, HCC-240fa remaining ratios in the reactive mixture
Example is 0.68%.
The addition of the cocatalyst B component and C components, influences the surface nature of catalyst, and they are with major catalyst A groups
Synergy is there may be between part, therefore under fluorination conditions of the invention, composite catalyst has a number of surface
Acidic site, promotes the activity and selectivity of catalyst.The addition of B component oxide in composite catalyst, hence it is evident that lifting catalysis is lived
Property and stability, and purpose product HCFC-1233zd (E) selectivity, such as plus zinc oxide, reactant HCC-240fa is anti-
It is selectively 76.8% for 0.95%, HCFC-1233zd (E) to answer the remaining proportion of mixture, after adding zinc oxide, HCC-240fa
0.12%, HCFC-1233zd (E) is reduced in the remaining proportion of reactant mixture selectively bring up to 82.3%；B component cobalt oxide
(II) addition, improves catalyst stability.The addition of C components in composite catalyst, significantly lifts purpose product HCFC-
The selectivity of HCFC-1233zd (E) in the selectivity of 1233zd, particularly its two kinds of isomers, C Composition Active charcoals are by 2.5%
(wt%) it is changed into 5.0% (wt%), the selectivity of HCFC-1233zd (E) is improved to 89.2% by 61.3%.
The composite catalyst has specific surface area big, and catalysis activity is high, and selectivity is high, and catalyst has the long-life etc. excellent
Point.
Claims (10)
1. a kind of method of synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes, it is characterised in that：With 1,1,1,3,3- pentachloro-s third
Alkane is raw material, and under composite catalyst effect, hydrogen fluoride gas phase fluorination synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes are described multiple
Catalyst is closed to be made up of component A oxide major catalyst, B component oxide promoter and C component co-catalysts.
2. the method for a kind of synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes according to claim 1, it is characterised in that：Institute
State the component A oxide major catalyst that composite catalyst is by 70% ~ 95%, 3% ~ 25% B component oxide promoter, and 2% ~
5%C components co-catalyst is constituted.
3. the method for a kind of synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes according to claim 1 and 2, it is characterised in that：
Described component A is chrome green, and described B component is one or more in zinc oxide, cobalt oxide, aluminum oxide, described
C components be chemically modified treated activated carbon.
4. the composite catalyst in the synthesis of trans 1- chloro-3,3,3 ,-trifluoropropene methods described in claim 1 or 2 is prepared, its
It is characterised by：The hydroxide of trivalent chromium, zinc, divalence cobalt and aluminium is prepared with coprecipitation first, then scrubbed, dry, nitrogen
Obtain the composite oxides of component A and B component after gas atmosphere or hydrogen atmosphere roasting, then with C component ground and mixeds, extrusion into
Type, prepares unsupported catalyst.
5. the composite catalyst in the synthesis of trans 1- chloro-3,3,3 ,-trifluoropropene methods described in claim 1 or 2 is prepared, its
It is characterised by：When preparing composite catalyst, catalyst precursor hydroxide, NaOH solution or NH are prepared with coprecipitation3·
H2O is precipitating reagent.
6. the composite catalyst prepared in synthesis of trans 1- chloro-3,3,3 ,-trifluoropropene methods according to claim 5, its
It is characterised by：It is soluble chloride or its nitrate to prepare the slaine used by catalyst precursor hydroxide.
7. the composite catalyst prepared in synthesis of trans 1- chloro-3,3,3 ,-trifluoropropene methods according to claims 6,
It is characterized in that：The drying temperature of catalyst precursor hydroxide is 50 ~ 80 DEG C, and the time is 48 ~ 144 hours, in hydrogen gas
Atmosphere calcines hydroxide, 350 ~ 460 DEG C of temperature, and the time is 4 hours；Hydroxide, temperature 350 ~ 560 are calcined in a nitrogen atmosphere
DEG C, the time is 4 hours.
8. the composite catalyst prepared in synthesis of trans 1- chloro-3,3,3 ,-trifluoropropene methods according to claims 7,
It is characterized in that：After calcining hydroxide, A after content is added in component A and B component oxide, and C components for calcining
The aquadag of component and B component quality 1.0% ~ 3.0%, the ground and mixed in high speed Universal pulverizer, the time is 5 ~ 10 minutes；
Then methocel solution is added wherein, its concentration is 1.0% ~ 5.0% (wt), extruded moulding, room temperature is air-dried.
9. the one kind according to claims 1 prepares trans 1- chloro-3,3,3 ,-trifluoropropenes method, it is characterised in that：Institute
The composite catalyst stated is filled into stainless steel reaction pipe when activating, reaction tube heating-up temperature is 350 ~ 370 DEG C, is led in heating process
Enter hydrogen fluoride gas carries out pre-activate treatment to catalyst, continuous activation 10 hours.
10. the method for a kind of synthesis of trans 1- chloro-3,3,3 ,-trifluoropropenes according to claim 1, it is characterised in that：Fluorine
Change hydrogen and 1,1,1,3,3- pentachloropropane reacts at ambient pressure, reaction temperature is 180 ~ 220 DEG C, 1,1,1,3,3- pentachloropropane and
The mol ratio of hydrogen fluoride is 1:10~1:The inlet amount of 20,1,1,1,3,3- pentachloropropanes is 0.4 ~ 1.0mL/min.
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| CN108057435A (en) * | 2017-11-10 | 2018-05-22 | 乳源东阳光氟有限公司 | A kind of preparation method of catalysts for gas phase fluorination |
| CN111848331A (en) * | 2020-08-19 | 2020-10-30 | 中国科学院兰州化学物理研究所 | Method for synthesizing 2-chloro-3, 3, 3-trifluoropropene through gas phase fluorination |
| CN112979410A (en) * | 2019-12-13 | 2021-06-18 | 浙江省化工研究院有限公司 | Method for improving catalyst stability in HFC-23 resource utilization |
| CN115646480A (en) * | 2022-12-12 | 2023-01-31 | 山东东岳化工有限公司 | Catalyst for preparing 1-chloro-3, 3-trifluoropropene and preparation method and application thereof |
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| CN108383679A (en) * | 2018-04-13 | 2018-08-10 | 淄博飞源化工有限公司 | A kind of co-production of anti-form-1-chloro- 3,3,3- trifluoro propenes and 2,3,3,3- tetrafluoropropenes |
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| CN103880590A (en) * | 2012-12-19 | 2014-06-25 | 中化蓝天集团有限公司 | Process for preparing 1,3,3,3-tetrafluoropropene |
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| CN108057435A (en) * | 2017-11-10 | 2018-05-22 | 乳源东阳光氟有限公司 | A kind of preparation method of catalysts for gas phase fluorination |
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| CN112979410B (en) * | 2019-12-13 | 2022-06-28 | 浙江省化工研究院有限公司 | Method for improving catalyst stability in HFC-23 resource utilization |
| CN111848331A (en) * | 2020-08-19 | 2020-10-30 | 中国科学院兰州化学物理研究所 | Method for synthesizing 2-chloro-3, 3, 3-trifluoropropene through gas phase fluorination |
| CN115646480A (en) * | 2022-12-12 | 2023-01-31 | 山东东岳化工有限公司 | Catalyst for preparing 1-chloro-3, 3-trifluoropropene and preparation method and application thereof |
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