CN105753638B - The synthetic method of 2,3,3,3- tetrafluoropropenes - Google Patents
The synthetic method of 2,3,3,3- tetrafluoropropenes Download PDFInfo
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Abstract
The invention discloses a kind of synthetic methods of 2,3,3,3 tetrafluoropropenes, including：A, general formula is CF3‑xClxCF2‑yClyCH2The compound of Cl carries out liquid phase fluorination reaction in the presence of liquid-phase fluorination catalyst, with hydrogen fluoride and obtains 1,2,3 trichlorine, 1,1,2 trifluoro propane, wherein x=2 in compound formula, and 3；Y=1,2, and 3≤x+y≤5；B, 1,2,3 trichlorine, 1,1,2 trifluoro propane carries out gas phase fluorination in the presence of catalysts for gas phase fluorination, with hydrogen fluoride and generates 2,3 dichloro, 1,1,1,2 tetrafluoropropane, 2,3 dichloro, 1,1,1,3 tetrafluoropropane；C, in the presence of dechlorination catalyst, the gas phase dechlorination reaction carried out with hydrogen generates 2,3,3,3 tetrafluoropropenes, 1,3,3,3 tetrafluoropropenes for 2,3 dichloro, 1,1,1,2 tetrafluoropropane, 2,3 dichloro, 1,1,1,3 tetrafluoropropane.Present invention is mainly used for synthesize 2,3,3,3 tetrafluoropropenes.
Description
Technical field
The present invention relates to a kind of synthetic methods of HF hydrocarbon, more particularly to 2,3,3,3- tetrafluoropropene (HFO- of one kind
Synthetic method 1234yf).
Background technology
Compared with chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbon (HFCs), HF hydrocarbon (HFOs) is free of chlorine,
It does not threaten to earth's ozone layer, while there are low greenhouse effects to dive value, have become the weight of hydrofluorocarbons industrial research at present
Point.2,3,3,3- tetrafluoropropenes, i.e. HFO-1234yf, as one kind of HF hydrocarbon, the latent value of ozone depletion is 0, greenhouse effects
Latent value is 4, can be used as refrigerant, extinguishing chemical, heat transfer medium, propellant, foaming agent, foaming agent, gas medium, bactericidal agent and carries
Body, polymer monomer remove granule fluid, carrier gas flow, grinding with polishing agent, replace drier and electric cycle operation fluid,
It is widely used.
WO2009153493 discloses one kind with 1,1,1,2,2,3- hexafluoropropane (HFC-236cb) as raw material, prepares
The method of HFO-1234yf, this method are in hydrogen and catalyst n i-Cr/AlF first3In the presence of, HFC-236cb defluorinates
Hydrogen generates 1,2,3,3,3- pentafluoropropenes (HFO-1225ye), and then HFO-1225ye adds hydrogen to obtain 1,1,1,2,3- pentafluoropropane
(HFC-245eb), finally HFO-1234yf is obtained through dehydrofluorination in the presence of hydrogen again.
US20110190554 disclose it is a kind of with 1,1,2,3,3,3- hexafluoropropene (HFP) for starting material, it is hydrogenated,
The method of dehydrofluorination plus hydrogen, dehydrofluorination four-step reaction synthesis HFO-1234yf.
In above two synthetic method, reaction raw materials are not easy to obtain, and cost is higher, and need to be passed through at least chemistry meter
The hydrogen of amount amount, hydrogenation step often use higher molar ratio, in addition, higher to effectively control the exothermicity of reaction
At a temperature of be passed through excessive hydrogen and can also increase associated safety risk, condition is harsh, is unfavorable for industrialized production.
US2011207975 discloses one kind with 1,1,2,3- tetrachloropropylenes (TCP) or 1,1,1,2,3- pentachloropropanes
(HCC-240db) method for being Material synthesis HFO-1234yf.This method is first in Cr2O3It is anti-first in the presence of catalyst
Progress HF gas phase fluorination TCP or HCC-240db in device is answered, obtains 2- chloro-3,3,3 ,-trifluoropropenes (HCFC-1233xf), so
Afterwards in SbCl5Under effect, liquid-phase fluorination HCFC-1233xf obtains 2- chloro-1,1,1,2-tetrafluoropropanes in the second reactor
(HCFC-244bb), HCFC-244bb dehydrochlorination reactions are finally carried out in third reactor obtain HFO-1234yf.
WO2012099776 is disclosed to be prepared by TCP through HCFC-1233xf, HCFC-244bb with three steps of integration
The method of HFO-1234yf.
WO2009125199 discloses one kind by bis- chloro- 1,1,1- trifluoros propane (HCFC-243db) of 2,3- through HCFC-
The method that 1233xf, HCFC-244bb prepare HFO-1234yf.
In the above preparation method, first, Cr is related to2O3, aluminium oxide or fluorided alumina load Cr2O3Equal chromium base
Catalyst, in fact, be also mostly chromium-based catalysts in the application of HFCs industrial productions, and these compounds containing chromium, catalyst, meeting
The alimentary canal and kidney of people are damaged, especially high valence chrome is even more to have strong carcinogenesis, right in the production and use process
Human and environment is unfriendly, can all cause to seriously endanger.Secondly, intermediate HCFC-1233xf and HCFC- have also been all referred to
244bb, but both halogenated hydrocarbons boiling points are close, have azeotrope-like characteristic, and easily form azeotropic mixture with HF, there are difficulties
The problem of to detach, their mixture cannot achieve by standard technology, conventional method and efficiently separate, especially when it
When forming a kind of binary azeotrope or Azeotrope-like ingredient.In addition it has found that and is carrying out HCFC-244bb dehydrochlorination preparations
When HFO-1234yf, wherein HCFO-1233xf, HF impurity contained can seriously affect service life and the production of dehydrochlorination catalyst
Object selectivity, easily leads to the reduction of HFO-1234yf selectivity, the reduction of catalyst activity and the shortening of catalyst life.
Although the presently disclosed method for preparing HFO-1234yf is more, there is such as severe reaction conditions, urge
Agent is unfriendly to environment, reaction intermediate be difficult to separation and caused by energy consumption, cost increase, target product selectivity it is low it is equal not
Foot, therefore, for significantly more efficient preparation method, there are sustained improvements and demand.
Invention content
It is insufficient it is an object of the invention to overcome present in background technology, a kind of intermediate is provided and is easily isolated, is catalyzed
The synthetic method for the 2,3,3,3- tetrafluoropropenes (HFO-1234yf) that agent is environmentally friendly, reaction condition is mild.
The present invention is with formula CF3-xClxCF2-yClyCH2Cl compounds are starting material, through liquid-phase fluorination, gas phase fluorination, dechlorination
Three-step reaction generates 2,3,3,3- tetrafluoropropenes (HFO-1234yf), and reaction process is as follows：
In order to achieve the object of the present invention, provided by the invention 2, the synthetic method of 3,3,3- tetrafluoropropenes, including it is following
Step：
A, in the presence of liquid-phase fluorination catalyst, general formula CF3-xClxCF2-yClyCH2The compound of Cl and hydrogen fluoride into
Row liquid phase fluorination reaction generates 1,2,3- tri- chloro- 1,1,2- trifluoro propane (HCFC-233bc), wherein x=in compound formula
2,3；Y=1,2, and 3≤x+y≤5；Reaction condition is：80 DEG C~160 DEG C of reaction temperature, hydrogen fluoride and CF3-xClxCF2- yClyCH2The molar ratio of Cl is 5~20：1, the dosage of fluorination catalyst is CF3-xClxCF2-yClyCH2The 3% of Cl mass~
50%；
B, 1,2,3- tri- chloro- 1,1,2- trifluoro propane carries out gas phase in the presence of catalysts for gas phase fluorination, with hydrogen fluoride
Fluorination reaction generates bis- chloro- 1,1,1,2- tetrafluoropropanes (HCFC-234bb) of 2,3-, bis- chloro- 1,1,1,3- tetrafluoropropanes of 2,3-
(HCFC-234da)；Reaction condition is：240 DEG C~350 DEG C of reaction temperature；Hydrogen fluoride and tri- chloro- 1,1,2- trifluoropropyls of 1,2,3-
The molar ratio 3~30 of alkane：1, reaction contact time 0.5 second~60 seconds；
C, bis- chloro- 1,1,1,2- tetrafluoropropanes of 2,3-, bis- chloro- 1,1,1,3- tetrafluoropropanes depositing in dechlorination catalyst of 2,3-
Under, the gas phase dechlorination reaction carried out with hydrogen generates 2,3,3,3- tetrafluoropropenes (HFO-1234yf), 1,3,3,3- tetrafluoros third
Alkene (HFO-1234ze)；Reaction condition is：200 DEG C~300 DEG C of reaction temperature, hydrogen and 2,3- bis- chloro- 1,1,1,2- tetrafluoro third
The molar ratio 0~1 of bis- chloro- 1,1,1,3- tetrafluoropropanes total amount of alkane and 2,3-：1,1~60 second time of contact.
Formula CF described in step a3-xClxCF2-yClyCH2Cl compounds are selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl、
Or CF2ClCCl2CH2Cl, suitable reaction raw materials further include CCl certainly3CFClCH2Cl、CFCl2CFClCH2Cl。
Formula CF described in step a3-xClxCF2-yClyCH2Cl compounds are CCl3CCl2CH2Cl。
Liquid-phase fluorination catalyst described in step a is Fe2O3-TaCl5-CF3SO3H composite catalysts, wherein Fe2O3、
TaCl5、CF3SO3The molar ratio of H three is 1:2:5.Suitable catalyst further includes other lewis acids, halogenated transition metal
Object, halogenosulfonic acid or combination thereof, for example, sexavalence molybdenum halides, quinquevalence antimony halide, tetravalent titanium halide, trivalent chromium fluorine
Compound, the fluoride of chrome green；The molar ratio of three can also be 2:2:5 or 2:1:5 or 2:3:5, certain fluoroform
The amount of sulfonic acid can select in a wider scope, and mole can be Fe2O31 to 20 times of mole, preferably 2 to
10 times, consider reaction effect and catalyst service life, more preferable 5 times.
The reaction condition of liquid phase fluorination reaction described in step a is：110 DEG C~130 DEG C of reaction temperature, hydrogen fluoride and CF3- xClxCF2-yClyCH2The molar ratio of Cl is 10~15：1, Fe in fluorination catalyst2O3With TaCl5Dosage and be CF3-xClxCF2- yClyCH2The 10%~15% of Cl mass.
Catalysts for gas phase fluorination described in step b is Mn-A-B-C composite catalysts, wherein A is the VIIIth race's element, preferably
One or more of Ni, Fe, Co are combined, and B is High field side injection, i.e., with ion electricity price is higher, radius is smaller, has
Compared with the element of macroion field strength, including lanthanide series, Sc and Y and Th, U, Pb, Zr, Hf, Ti, Nb, Ta, preferably Zr, Y, La
One or more of combination, C is alkali earth metal, preferably one kind in Mg, Ca, Ba；The molar ratio of Mn, A, B, C
For (0.3~2)：(0.6~5)：(0.1~1)：(2~9), preferably (0.6~1):(2~4):(0.4~1):(4~7).
Catalysts for gas phase fluorination described in step b is Mn-Ni-Zr-Ca composite catalysts, wherein Mn, Ni, Zr, Ca
Molar ratio be 0.6：3：0.4：6；The preparation method of the catalyst includes：Tri- kinds of metals of a certain proportion of Mn, Ni, Zr are solvable
Property salt mixed solution reacted with precipitating reagent, pH controls are in 7.5-9.5, stirring, precipitation, filtering and dry, then by a certain amount of Ca
Oxide, hydroxide or carbonate it is mixed uniformly, then at 200 DEG C -500 DEG C, in no less than three temperature gradients
Under conditions of carry out baking inphases, finally perfluorinated hydrogen activation process at 200 DEG C -380 DEG C obtains again.
The reaction condition of gas phase fluorination described in step b is：280 DEG C~320 DEG C of reaction temperature；Hydrogen fluoride and 1,2,3-
The molar ratio 10~20 of three chloro- 1,1,2- trifluoros propane：1；Reaction contact time 10 seconds~30 seconds.When the gas phase fluorination temperature
When spending high, by-product HCFC-234da, 1,2- bis- chloro- 3,3,3- trifluoro propenes (HCFO-1223xd), tetrachloropropylene (TCE),
Trifluorobichloroethane (HCFC-123) obviously increases, and leads to the reduction of target product HCFC-234bb selectivity, when temperature is too low
When, reaction conversion ratio will be reduced adversely.Especially when reacting on the temperature progress higher than 450 DEG C, it is viscous to will produce carbide
It is attached to or is deposited on reaction tube wall or filler, gradually block the inside of reactor.It, can be by being passed through one for this situation
Quantitative N2Reaction can also be suspended to play alleviation or elimination and be passed through oxygen or sky into reactor by diluting reaction raw material
Gas removes the carbide residue in reaction tube.
Dechlorination catalyst described in step c is Cu-V-Mg-F catalyst, wherein the molar ratio of Cu, V, Mg three be (2~
4)：(1~2)：(4~7), preferably (3~4)：(1~2)：(4~6), more preferable 4:1:5, the preparation method of the catalyst includes：
By a certain percentage, by V2O5It is added to Cu (NO3)2·3H2O and Mg (NO3)2·6H2In the mixed aqueous solution of O, the mass fraction is added to be
10% ammonium hydrogencarbonate, it is about 9, about 5h to adjust pH controls, is centrifuged after washed, then dried at 120 DEG C, then 200
At a temperature of DEG C -500 DEG C, baking inphases are carried out under conditions of no less than three temperature gradients, finally pass sequentially through again hydrogen fluoride,
Hydrogen activation handles to obtain.The preparation method for being suitable for the catalyst has infusion process, coprecipitation, blending method, sol-gel method
Deng.The dechlorination reaction can also be the liquid phase of HCFC-234bb and HCFC-234db and reducing agent effect in protonic solvent
Dechlorination reaction, wherein protonic solvent include methanol, ethyl alcohol, acetic acid or ethylene glycol, naturally it is also possible to for the tert-butyl alcohol, formic acid, second
Acid anhydrides, glycerine or diglycol, while common other protonic solvents are also applied for this step, such as propylene glycol is gathered
The polyalcohol that ethylene glycol 200 and hydroxyl are not fully protected；Reducing agent be Mg, Al, Zn or Fe or Ag and Fe bimetallics also
Substance system can also be the composition of the composition of Cu, Ag, Ni and Fe, the composition of Cu and Fe, Cu and Al, the group of Pd and Fe
It closes object and its they is combined
The reaction condition of gas phase dechlorination reaction described in step c is：260 DEG C~300 DEG C of reaction temperature, hydrogen and HCFC-
The molar ratio 0.3 of 234bb and HCFC-234db total amounts：1,5~30 seconds times of contact.In the gas phase dechlorination reaction hydrogen with
The molar ratio of HCFC-234bb and HCFC-234da total amounts is to influence the key factor of the reaction, when being passed through excessive hydrogen,
Although reaction may be implemented to convert completely, the selectivity of target product is substantially reduced, hydrogen and HCFC-234bb and HCFC-
Molar ratio suitable 234da preferably 0.1~0.5：1, more preferable 0.1~0.3：1, hydrogen be passed through it is trans- can be intermittently,
Can also be semi-continuously continuously.
The reaction pressure of step a of the present invention influences the fluorination reaction smaller, material that can be according to consersion unit, anti-corruption
Erosion and pressure-resistant degree select convenient operating pressure, it is preferable that the reactor is by tolerance hydrogen fluoride and catalyst
The material manufacture of corrosiveness, for example, Hastelloy (Hastalloy), inconel (Inconel), monel metal
(Monel) and it is lined with fluoropolymer-containing container.
Reaction described in step b of the present invention can carry out in any reactor for being suitable for gas phase fluorination.Step b
Fluorination reactor type nor key, tubular reactor, fluidized-bed reactor etc. can be used.In addition, adiabatic reactor
Or isothermal reactor also can be used.
The pretreatment of the dechlorination catalyst of step c of the present invention can by by catalyst in nitrogen or other inert gas flows
In be heated to about 200 DEG C to about 380 DEG C to carry out, then pass through again the diluted hydrogen fluoride stream of a large amount of excessive nitrogen, hydrogen stream according to
Secondary processing activation is to obtain high catalyst activity.The regeneration of catalyst can carry out under the following conditions, make air or use nitrogen
For diluted air at about 100 DEG C to about 380 DEG C, preferably from about 150 DEG C to about 365 DEG C of temperature lasts about 8 hours by catalyst
To about 3 days, this depended on the size of reactor.
Advantage of the present invention：A kind of method being effectively synthesized HFO-1234yf is provided, is easily isolated with intermediate, it is intermediate
Tri- chloro- 1,1,2- trifluoros propane (HCFC-233bc) (bp of body step a products 1,2,3-：95 DEG C~97 DEG C) and intermediate Part b
Bis- chloro- 1,1,1,2- tetrafluoropropanes (HCFC-234bb) (bp of product 2,3-：53 DEG C~55 DEG C), bis- chloro- 1,1,1,2- tetra- of 2,3-
Fluoro-propane (HCFC-234da) (bp：58 DEG C~60 DEG C) boiling point differ greatly, about 41 DEG C, easily detach, intermediate Part b products
HCFC-234bb and HCFC-234da also with step c products, that is, target product tetrafluoropropene (bp：- 28 DEG C) boiling point differ greatly,
It about 70 DEG C, is also easy to detach；Catalysts are not related to containing chromium, antimony containing compounds, to human and environment close friend；With reaction condition
Mildly, gas phase reaction temperature is also no more than 350 DEG C, it is most important that dechlorination reaction is realized under the conditions of being existing for a small amount of hydrogen
, do not need the hydrogen of stoichiometry.
Description of the drawings
Fig. 1 is product CF3CFClCH2The GC-MS collection of illustrative plates of Cl；
Fig. 2~4 are product CF3CHClCHFCl's1H-NMR、13C-NMR、19F-NMR collection of illustrative plates；
Specific implementation mode
Below by specific embodiment, invention is further described in detail
Analytical instrument：The glad GC-930 types gas chromatograph in sea, agilent company 30m DB-5 (50m × 0.32mm) capillary
Chromatographic column；ITQ 700 (ion trap)：Thermofisher scientific, agilent company GASPRO (60m × 0.25mm)
Capillary chromatographic column.
Chromatographic condition：40 DEG C of initial column temperature keeps 5min, rises to 180 DEG C with the heating rate of 10 DEG C/min, keeps
3min；220 DEG C of temperature of vaporization chamber, split ratio 50.
Ion trap mass spectrometry condition：Filament emission current 70A；Mass scan range 10-350amu；Full scan mode, scanning
10 micro scannings of speed/second；Multiplier voltage 1556V；220 DEG C of transmission line temperature, carrier gas is helium.
Embodiment 1：
Di-iron trioxide is added to Monel autoclaves of the 500mL equipped with magnetic agitation, packed tower and condenser assembly
(3.7g, 0.023mol), tantalic chloride (16.3g, 0.045mol), trifluoromethanesulfonic acid (17.1g, 0.11mol) are cooled to -20
DEG C, anhydrous hydrogen fluoride (27.2g, 1.4mol) is added, is gradually warming up to 40 DEG C, is handled 2 hours, then be warming up to 60 DEG C, processing 1
Hour, 80 DEG C are warming up to, is handled 1 hour, is finally warming up to 100 DEG C, is handled 3 hours, is so far disposed, is pressed in processing procedure
Power is controlled by periodically discharging HCl by-products.
At room temperature, reaction unit is subjected to vacuumize process, thereto sucting reaction raw material 1,1,1,2,2,3- chlordene
Propane (200g, 0.79mol), then it is pressed into anhydrous hydrogen fluoride (158g, 7.9mol), then 120 DEG C are gradually warming up to, and in this temperature
Lower maintenance 10h, during heating pressure controlled by periodically discharging HCl by-products, keep pressure be less than 1000Kpa.It will production
In the water absorber that object is emitted into, then gained organic matter is washed 3 times and obtains colourless liquid, through gas chromatographic analysis, predominantly
CF2ClCFClCH2Cl(HCFC-233bc)、CF2ClCCl2CH2Cl (HCFC-232ac), reaction result is shown in Table 1.
Embodiment 2~5：
Embodiment 2~5 synthesizes 1,2,3- tri- chloro- 1 according to 1 identical method of embodiment, and 1,2- trifluoro propane is different
Be reaction temperature in embodiment 1 be 120 DEG C, and the reaction temperature in embodiment 2~5 be followed successively by 80 DEG C, 110 DEG C, 130 DEG C,
160 DEG C, reaction result is as shown in table 1.
Table 1
Embodiment 6~8：
Embodiment 6~8 is different according to identical method synthesis 1,2,3- tri- chloro- 1,1,2- trifluoro propane, institute in embodiment 1
Be HF and CCl in embodiment 13CCl2CH2The molar ratio of Cl is 10:1, and the two molar ratio in embodiment 6~8 is successively
It is 5:1、15:1、20:1, reaction result is as shown in table 2.
Table 2
Embodiment 9~13：
Embodiment 9~13 is according to identical method synthesis 1,2,3- tri- chloro- 1 in embodiment 1, and 1,2- trifluoro propane, institute is not
Be di-iron trioxide in catalyst in embodiment 1, tantalic chloride total dosage be 20g, n (Fe2O3)：n(TaCl5)：:n
(CF3SO3H it is) 1：2：5, and di-iron trioxide, total dosage of tantalic chloride and Fe in the catalyst in embodiment 9~132O3、
TaCl5、CF3SO3The molar ratio of H three is as shown in table 3, and when progress catalyst treatment, and fluorination hydrogen amount is made accordingly to adjust in molar ratio
Whole, reaction result is shown in Table 3.
Table 3
Embodiment 14~17：
Embodiment 14~17 is according to identical method synthesis 1,2,3- tri- chloro- 1 in embodiment 1, and 1,2- trifluoro propane, institute is not
Be reaction raw materials in embodiment 1 be CCl3CCl2CH2Cl, and the reaction raw materials in embodiment 14~17 are
CFCl2CCl2CH2Cl、CF2ClCCl2CH2Cl、CCl3CFClCH2Cl、CFCl2CFClCH2Cl is shown in Table 4.
Table 4
Embodiment 18：
The preparation of catalyst：By a certain percentage, a certain amount of manganese acetate, nickel nitrate, zirconium chloride are mixed into 2mol/L water
Solution, then it is 15% ammonium hydroxide that mass fraction, which is added, at a temperature of 20 DEG C -40 DEG C, under conditions of being stirred continuously, and adjusts pH controls and exists
8.0,8h, filtering and the dry 2h at 120 DEG C are reacted, then a certain amount of calcium carbonate is mixed uniformly, then roasted at 200 DEG C
Burn 1h, 5 DEG C/min rises to 320 DEG C, roasts 2h, and 10 DEG C/min rises to 400 DEG C, roasts 4h, finally again perfluorinated hydrogen 200 DEG C-
Activation process obtains at 380 DEG C, about needs 36h.
In the nickel tube fixed-bed tube reactor that internal diameter is 38mm, 50ml Mn-Ni-Zr-Ca composite catalysts are packed into,
Wherein the mol ratio of Mn, Ni, Zr, Ca are 0.6:2:0.4:7, and catalyst is dried and then at 300 DEG C, is passed through
Both HF and 1,2,3- tri- chloro- 1,1,2- trifluoro propane (HCFC-233bc), is reacted under atmospheric pressure (normal pressure), control
Molar ratio is 10:1, time of contact is 30 seconds, and reaction product is after washing, alkali cleaning remove HCl and HF, with gas-chromatography and mass spectrum
Analysis, reaction result are：Generating CF3CFClCH2Cl(HCFC-234bb)、CF3While CHClCHFCl (HCFC-234da),
Also with a small amount of HCFO-1223xd, CF3The by-products such as CCl=CHF occur, and the results are shown in Table 5.
By the way that above-mentioned reaction solution rectifying is obtained HCFC-234bb, HCFC-234da, purity is respectively 99.2%,
97.9%, through GC-MS,1H-NMR、13C-NMR、19F-NMR characterization identifications, as shown in Figs 1-4.
Boiling point：53℃-55℃
Fig. 1 mass spectral results and its peak ownership are as follows：m/z 184:m/z 186:M/z 188=9:6:1 (M+), to contain two
The isotopic peak ratio of a chlorine；m/z 149:M/z 151=3:1 [(M-Cl)+], for containing there are one the isotope ratio of chlorine, m/z
165:m/z167:M/z 169=9:6:1 [(M-F)+], it is reasonable to lose；M/z 69 (CF3+) and m/z 114 (C2H2FCl2+) are
Complementary ion；m/z 75(C3HF2+)；m/z 49:M/z 51=3:1(CH2Cl+).
It is learnt by analyzing above：The compound is bis- chloro- 1,1,1,2- tetrafluoropropanes of 2,3-.
Fig. 2, Fig. 3, Fig. 4 show that the compound is 2,3- bis- chloro- 1, and 1,1,3- tetrafluoropropane is specific as follows shown
1H-NMR(500MHz,CDCl3)δ4.08(m,3JH-F=11.5Hz, 1H), 3.99 (m,4JH-F=0.5Hz,3JH-F=
13Hz,1H)。
13C-NMR(500MHz,CDCl3)δ120.31(qd,1JC-F=1134.5Hz,2JC-F=122.5Hz, 1C), 104.71
(dq,1JC-F=1021Hz,2JC-F=145Hz, 1C), 44.99 (d, JC-F=99.5Hz, 1C).
19F-NMR(500MHz,CDCl3) δ -128.98 (s, 1F), -80.08 (s, 3F).
Embodiment 19~22：
Embodiment 19~22 is reacted according to identical synthetic method in embodiment 18, except that in embodiment 18
Reaction temperature be 300 DEG C, and the reaction temperature in embodiment 19~22 is followed successively by 240 DEG C, 280 DEG C, 320 DEG C, 350 DEG C, instead
5 should be the results are shown in Table.
Table 5
Embodiment 23~26：
Embodiment 23~26 is reacted according to identical synthetic method in embodiment 18, except that in embodiment 18
HF and HCFC-233bc molar ratio be 10:1, and the two molar ratio in embodiment 24~26 is followed successively by 5:1、15:1、20:
1、30:1, reaction result is shown in Table 6.
Table 6
Embodiment 27~29：
Embodiment 27~29 is reacted according to identical synthetic method in embodiment 18, except that in embodiment 18
Time of contact be 30s, and in embodiment 27~29 time of contact be followed successively by 10s, 20s, 60s, reaction result is shown in Table 7.
Table 7
Embodiment 30~36：
Embodiment 30~36 is reacted according to identical synthetic method in embodiment 18, except that in embodiment 18
Catalyst be Mn-Ni-Zr-Ca composite catalysts, and the catalyst in embodiment 30~36 is followed successively by Mn-Ni-La-Ca, Mn-
Fe-Zr-Mg, Mn-Fe-La-Mg, Mn-Co-Y-Ca, Mn-Co-Y-Ba, Mn-Ni-Y-Ca, Mn-Fe-Y-Ca, reaction result such as table
Shown in 8.
Table 8
Embodiment 37：
The preparation of catalyst：By a certain percentage, by V2O5It is added to Mg (NO3)2·6H2O and Cu (NO3)2·3H2The mixing water of O
In solution, it is 10% ammonium hydrogencarbonate to add mass fraction, and it is about 9, about 5h to adjust pH controls, is centrifuged after washed, then
It is dried at 120 DEG C, then roasts 1h at 200 DEG C, 5 DEG C/min rises to 320 DEG C, roasts 2h, and 5 DEG C/min rises to 450 DEG C, roasting
4h finally passes sequentially through excessive hydrogen fluoride again, Hydrogen activation handles to obtain.
In the nickel tube fixed-bed tube reactor that internal diameter is 38mm, it is packed into 50ml and contains above-mentioned Cu-V-Mg-F catalyst,
The molar ratio of middle Cu, V, Mg three is 4：1：5, it is passed through H at 280 DEG C2, after two hours, it is passed through 2,3- bis- chloro- 1,1,1,2- tetra-
(mass percentage of the two is for fluoro-propane (HCFC-234bb), bis- chloro- 1,1,1,3- tetrafluoropropanes (HCFC-234da) of 2,3-
96.5%, 3.9%) it under atmospheric pressure (normal pressure) is reacted, control hydrogen and HCFC-234bb and HCFC-234da total amounts
Molar ratio is 0.3:1, time of contact is 30 seconds, with gas-chromatography, mass spectral analysis reaction result, generate HFO-1234yf,
While HFO-1234ze, there are by-product CF3CF=CClH (HCFO-1224yd), CF3CFHCH3(HCFC-254eb), wherein
Dechlorination reaction conversion ratio is the summation of HCFC-234bb, HCFC-234da conversion ratio, the results are shown in Table 9.
Embodiment 38~41：
Embodiment 38~41 synthesizes 2,3,3,3- tetrafluoropropenes according to identical synthetic method in embodiment 37, different
Be reaction temperature in embodiment 37 be 260 DEG C, and the reaction temperature in embodiment 38~41 be followed successively by 200 DEG C, 240 DEG C, 260
DEG C, 300 DEG C, reaction result is as shown in table 9.
Table 9
Embodiment 42~45：
Embodiment 42~45 synthesizes 2,3,3,3- tetrafluoropropenes according to identical synthetic method in embodiment 37, different
It is in the catalyst in embodiment 37, the molar ratio of Cu, V, Mg three are 4：1：5, and in the catalyst in embodiment 42~45
Cu, V, Mg three's mole is followed successively by 2：1：7、3：1：6、3：2：5、4：2：4, reaction result is as shown in table 10.
Table 10
Embodiment 46~48：
Embodiment 46~48 synthesizes 2,3,3,3- tetrafluoropropenes according to identical synthetic method in embodiment 37, different
It is in embodiment 37, the molar ratio of hydrogen and HCFC-234bb, HCFC-234da total amount is 0.3:1, and embodiment 46~48
In the two molar ratio be followed successively by 0.1:1、0.5:1、1:1, reaction result is as shown in table 11.
Table 11
Embodiment 49~52：
Embodiment 49~52 synthesizes 2,3,3,3- tetrafluoropropenes according to identical synthetic method in embodiment 37, different
Be in embodiment 37 time of contact be 30s, and time of contact in embodiment 49~52 time is 5s, 10s, 20s, 50s, reaction knot
Fruit is as shown in table 12.
Table 12
Embodiment 53：
Embodiment 53 synthesizes 2,3,3,3- tetrafluoropropenes according to identical synthetic method in embodiment 37, except that real
Apply the reaction raw materials in example 37 be HCFC-234bb and HCFC-234da compositions (mass percentage of the two be 96.5%,
3.9%) reaction raw materials, and in embodiment 53 are HCFC-234bb, and reaction result is shown：Reaction conversion ratio is 85.2%, instead
Answer housing choice behavior 99.2%.
Embodiment 54：
Embodiment 53 synthesizes 2,3,3,3- tetrafluoropropenes according to identical synthetic method in embodiment 37, except that real
Apply the reaction raw materials in example 37 be HCFC-234bb and HCFC-234da compositions (mass percentage of the two be 96.5%,
3.9%) reaction raw materials, and in embodiment 53 are HCFC-234da, and reaction result is shown：Reaction conversion ratio is 84.7%, instead
Answer housing choice behavior 99.1%.
The above is only the section Example of the present invention, not does limitation in any form to the present invention, all
It is any simple modification made according to the technical essence of the invention to above-described embodiment, equivalent variations and modification, belongs to this
Within the scope of inventive technique scheme.
Claims (7)
1. the synthetic method of 2,3,3,3- tetrafluoropropene of one kind, which is characterized in that include the following steps：
A, in the presence of liquid-phase fluorination catalyst, general formula CF3-xClxCF2-yClyCH2The compound of Cl carries out liquid with hydrogen fluoride
Phase fluorination reaction generates 1,2,3- tri- chloro- 1,1,2- trifluoro propane, wherein x=1 in compound formula, 2,3；Y=1,2, and 3
≤x+y≤5；
The liquid-phase fluorination catalyst is Fe2O3-TaCl5-CF3SO3H composite catalysts, wherein Fe2O3、TaCl5、CF3SO3H's rubs
You are than being 1:2:5；Liquid phase fluorination reaction condition is：80 DEG C~160 DEG C of reaction temperature, hydrogen fluoride and CF3-xClxCF2-yClyCH2Cl
Molar ratio be 5~20：1, Fe in liquid-phase fluorination catalyst2O3With TaCl5Dosage and be CF3-xClxCF2-yClyCH2Cl mass
10%~15%；
B, 1,2,3- tri- chloro- 1,1,2- trifluoro propane carries out gas phase fluorination in the presence of catalysts for gas phase fluorination, with hydrogen fluoride
Reaction generates bis- chloro- 1,1,1,2- tetrafluoropropanes of 2,3-, bis- chloro- 1,1,1,3- tetrafluoropropanes of 2,3-；
The catalysts for gas phase fluorination is Mn-A-B-C composite catalysts, wherein A is the VIIIth race's element, is selected from Ni, Fe, Co
One or more of combination, B is High field side injection, and selected from one or more of Zr, Y, La combination, C is alkali
Earth metal element, one kind in Mg, Ca, Ba；The molar ratio of Mn, A, B, C are (0.3~2)：(0.6~5)：(0.1~1)：
(2~9)；Gas phase fluorination condition is：240 DEG C~350 DEG C of reaction temperature；Hydrogen fluoride and tri- chloro- 1,1,2- trifluoros of 1,2,3-
The molar ratio 3~30 of propane：1, reaction contact time 0.5 second~60 seconds；
C, bis- chloro- 1,1,1,2- tetrafluoropropanes of 2,3-, bis- chloro- 1,1,1,3- tetrafluoropropanes of 2,3- dechlorination catalyst presence
Under, the gas phase dechlorination reaction carried out with hydrogen generates 2,3,3,3- tetrafluoropropenes, 1,3,3,3- tetrafluoropropenes；
The dechlorination catalyst is Cu-V-Mg-F catalyst, and wherein the molar ratio of Cu, V, Mg three are (2~4)：(1~2)：(4
~7)；The preparation method of the catalyst includes：In proportion by V2O5It is added to Cu (NO3)2·3H2O and Mg (NO3)2·6H2The mixing of O
In aqueous solution, it is 10% ammonium hydrogen carbonate to add mass fraction, and it is about 9, about 5h to adjust pH controls, is centrifuged after washed, then
It is dried at 120 DEG C, then at a temperature of 200 DEG C -500 DEG C, baking inphases is carried out under conditions of no less than three temperature gradients,
Hydrogen fluoride is finally passed sequentially through again, Hydrogen activation handles to obtain；Gas phase dechlorination reaction condition is：Reaction temperature 200 DEG C~300
DEG C, hydrogen and 2,3- bis- chloro- 1,1,1,2- tetrafluoropropane and 2,3- bis- chloro- 1, the molar ratio 0.1 of 1,1,3- tetrafluoropropane total amount
~1：1,5~50 seconds times of contact.
2. according to claim 12, the synthetic method of 3,3,3- tetrafluoropropenes, which is characterized in that the formula described in step a
CF3-xClxCF2-yClyCH2Cl compounds are selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl or CF2ClCCl2CH2Cl。
3. according to claim 22, the synthetic method of 3,3,3- tetrafluoropropenes, which is characterized in that the formula CF3- xClxCF2-yClyCH2Cl compounds are CCl3CCl2CH2Cl。
4. according to claim 12, the synthetic method of 3,3,3- tetrafluoropropenes, which is characterized in that the liquid described in step a
Phase fluorination reaction condition is：110 DEG C~130 DEG C of reaction temperature, hydrogen fluoride and CF3-xClxCF2-yClyCH2The molar ratio of Cl is 10
~15：1, Fe in liquid-phase fluorination catalyst2O3With TaCl5Dosage and be CF3-xClxCF2-yClyCH2The 10% of Cl mass.
5. according to claim 12, the synthetic method of 3,3,3- tetrafluoropropenes, which is characterized in that the gas described in step b
Phase fluorination catalysts are Mn-Ni-Zr-Ca composite catalysts, and wherein the molar ratio of Mn, Ni, Zr, Ca are 0.6：3：0.4：6；
The preparation method of the catalyst includes：It is in proportion that the mixed solution of tri- kinds of metal soluble-salts of Mn, Ni, Zr and precipitating reagent is anti-
Answer, pH controls are in 7.5-9.5, stirring, precipitation, filtering and dry, then by the oxide of Ca, hydroxide or carbonate and its mix
It closes uniformly, then at 200 DEG C -500 DEG C, baking inphases is carried out under conditions of no less than three temperature gradients, finally again through fluorine
Change hydrogen activation process at 200 DEG C -380 DEG C to obtain.
6. according to claim 12, the synthetic method of 3,3,3- tetrafluoropropenes, which is characterized in that gas phase described in step b
The reaction condition of fluorination reaction is：280 DEG C~320 DEG C of reaction temperature；Hydrogen fluoride and tri- chloro- 1,1,2- trifluoros propane of 1,2,3-
Molar ratio 10~20：1；Reaction contact time 10 seconds~30 seconds.
7. according to claim 12, the synthetic method of 3,3,3- tetrafluoropropenes, which is characterized in that the gas described in step c
The reaction condition of phase dechlorination reaction is：260 DEG C~300 DEG C of reaction temperature, hydrogen and 2,3- bis- chloro- 1,1,1,2- tetrafluoropropane and
The molar ratio 0.3 of bis- chloro- 1,1,1,3- tetrafluoropropanes total amounts of 2,3-：1,5~30 seconds times of contact.
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| FR3078698B1 (en) * | 2018-03-07 | 2020-02-21 | Arkema France | PROCESS FOR PRODUCTION OF 2-CHLORO-3,3,3-TRIFLUOROPROPENE |
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