CN105753638A - 2,3,3,3-tetrafluoropropene synthetic method - Google Patents
2,3,3,3-tetrafluoropropene synthetic method Download PDFInfo
- Publication number
- CN105753638A CN105753638A CN201410771684.5A CN201410771684A CN105753638A CN 105753638 A CN105753638 A CN 105753638A CN 201410771684 A CN201410771684 A CN 201410771684A CN 105753638 A CN105753638 A CN 105753638A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- chloro
- synthetic method
- mol ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a 2,3,3,3-tetrafluoropropene synthetic method including the steps: a, in the presence of a liquid phase fluorination catalyst, carrying out a liquid phase fluorination reaction of a compound represented by the general formula of CF3-xClxCF2-yClyCH2Cl with hydrogen fluoride to generate 1,2,3-trichloro-1,1,2-trifluoropropane, wherein in the compound general formula, x=2 or 3, y=1 or 2, and 3<=(x+y)<=5; b, in the presence of a gas phase fluorination catalyst, carrying out a gas phase fluorination reaction of 1,2,3-trichloro-1,1,2-trifluoropropane with hydrogen fluoride to generate 2,3-dichloro-1,1,1,2-tetrafluoropropane and 2,3-dichloro-1,1,1,3-tetrafluoropropane; and c, in the presence of a dechloridation catalyst, carrying out a gas phase dechloridation reaction of 2,3-dichloro-1,1,1,2-tetrafluoropropane and 2,3-dichloro-1,1,1,3-tetrafluoropropane with hydrogen gas to generate 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. The synthetic method is mainly used for synthesis of 2,3,3,3-tetrafluoropropene.
Description
Technical field
The present invention relates to the synthetic method of a kind of HF hydrocarbon, particularly relate to the synthetic method of a kind of 2,3,3,3-tetrafluoropropenes (HFO-1234yf).
Background technology
Compared with Chlorofluorocarbons (CFCs) (CFCs), HCFC (HCFCs), hydrogen fluorohydrocarbon (HFCs), HF hydrocarbon (HFOs) is not chloride, earth's ozone layer is not threatened, there is the latent value of low greenhouse effect simultaneously, become the emphasis of hydrofluorocarbons industrial research at present.2,3,3,3-tetrafluoropropene, i.e. HFO-1234yf, as the one of HF hydrocarbon, the latent value of ozone depletion is 0, greenhouse effect dive value be 4, can as cold-producing medium, extinguishing chemical, heat transfer medium, propellant, foaming agent, foaming agent, gas medium, biocide carrier, polymer monomer, remove granule fluid, carrier gas flow, grinding and polishing agent, replace desiccant and electricity periodic duty fluid, be widely used.
WO2009153493 discloses one with 1,1,1,2,2,3-HFC-236fa (HFC-236cb) for raw material, and the method preparing HFO-1234yf, first the method is at hydrogen and catalyst n i-Cr/AlF3Existence under, HFC-236cb dehydrofluorination generates 1,2,3,3,3-pentafluoropropene (HFO-1225ye), then HFO-1225ye hydrogenation obtains 1,1,1,2,3-pentafluoropropanes (HFC-245eb), finally obtain HFO-1234yf through dehydrofluorination more in the presence of hydrogen.
US20110190554 discloses one with 1,1,2,3,3,3-hexafluoropropene (HFP) for initiation material, the method that hydrogenated, dehydrofluorination, hydrogenation, dehydrofluorination four-step reaction synthesize HFO-1234yf.
In above two synthetic method, reaction raw materials not easily obtains, relatively costly, and need to pass into the hydrogen being at least stoichiometry, hydrogenation step, in order to effectively control the exothermicity of reaction, often adopts higher mol ratio, in addition, passing into excessive hydrogen at a higher temperature and also can increase associated safety risk, condition is harsh, is unfavorable for industrialized production.
US2011207975 discloses the method that one is Material synthesis HFO-1234yf with 1,1,2,3-tetrachloropropylene (TCP) or 1,1,1,2,3-pentachloropropane (HCC-240db).The method is first at Cr2O3Under the existence of catalyst, the first reactor carries out HF gas phase fluorination TCP or HCC-240db, obtain 2-chloro-3,3,3 ,-trifluoropropene (HCFC-1233xf), then at SbCl5Under effect, in the second reactor, liquid-phase fluorination HCFC-1233xf obtains 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), finally carries out HCFC-244bb dehydrochlorination reaction in the 3rd reactor and obtains HFO-1234yf.
WO2012099776 discloses the method being prepared HFO-1234yf by TCP through HCFC-1233xf, HCFC-244bb with three steps integrated.
WO2009125199 discloses a kind of method being prepared HFO-1234yf through HCFC-1233xf, HCFC-244bb by 2,3-bis-chloro-1,1,1-trifluoro propane (HCFC-243db).
In above-mentioned preparation method, first, relate to Cr2O3, aluminium oxide or fluorided alumina load Cr2O3Deng chromium-based catalysts, in fact, the application of HFCs commercial production mostly also is chromium-based catalysts, and these compounds containing chromium, catalyst, digestive tract and the kidney of people can be caused damage, especially high valence chrome has strong carcinogenesis especially, with in use procedure, human and environment is unfriendly producing, and all can cause serious harm.Secondly, also intermediate HCFC-1233xf and HCFC-244bb has been all referred to, but both halogenated hydrocarbons boiling points are close, there is the characteristic of class azeotropic, and all easy and HF formation azeotropic mixture, there is the problem being difficult to separate, their mixture cannot realize efficiently separating by standard technology, conventional method, particularly when it forms a kind of binary azeotrope or Azeotrope-like composition.In addition have found that when carrying out HCFC-244bb dehydrochlorination and preparing HFO-1234yf, HCFO-1233xf, HF impurity wherein contained can have a strong impact on life-span and the selectivity of product of dehydrochlorination catalyst, be easily caused HFO-1234yf optionally reduce, the shortening of the reduction of catalyst activity and catalyst life.
Although the method preparing HFO-1234yf disclosed at present is more, but there is such as severe reaction conditions, catalyst is unfriendly to environment, reaction intermediate be difficult to separate and cause energy consumption, cost increase, target product selectivity is low waits deficiency, therefore, significantly more efficient preparation method is existed to Continual Improvement and demand.
Summary of the invention
It is an object of the invention to overcome the deficiency existed in background technology, it is provided that the synthetic method of 2,3,3, the 3-tetrafluoropropenes (HFO-1234yf) that a kind of intermediate is easily isolated, catalyst is environmentally friendly, reaction condition is gentle.
The present invention is with formula CF3-xClxCF2-yClyCH2Cl compound is initiation material, generates 2,3,3,3-tetrafluoropropenes (HFO-1234yf) through liquid-phase fluorination, gas phase fluorination, dechlorination three-step reaction, and course of reaction is as follows:
In order to realize the purpose of the present invention, the synthetic method of 2,3,3,3-tetrafluoropropenes provided by the invention, comprise the following steps:
A, under the existence of liquid-phase fluorination catalyst, formula is CF3-xClxCF2-yClyCH2The compound of Cl and fluohydric acid gas carry out liquid phase fluorination reaction and generate 1,2,3-tri-chloro-1,1,2-trifluoro propane (HCFC-233bc), wherein, x=2 in compound formula, 3；Y=1,2, and 3≤x+y≤5；Reaction condition is: reaction temperature 80 DEG C～160 DEG C, fluohydric acid gas and CF3-xClxCF2-yClyCH2The mol ratio of Cl is 5～20:1, and the consumption of fluorination catalyst is CF3-xClxCF2-yClyCH2The 3%～50% of Cl mass；
B, 1,2,3-tri-chloro-1,1,2-trifluoro propane are under the existence of catalysts for gas phase fluorination, with fluohydric acid gas carry out gas phase fluorination generate 2,3-bis-chloro-1,1,1,2-tetrafluoropropane (HCFC-234bb), 2, chloro-1,1,1, the 3-tetrafluoropropane (HCFC-234da) of 3-bis-；Reaction condition is: reaction temperature 240 DEG C～350 DEG C；Mol ratio 3～the 30:1 of fluohydric acid gas and 1,2,3-tri-chloro-1,1,2-trifluoro propane, reaction contact time 0.5 second～60 seconds；
C, 2,3-bis-chloro-1,1,1,2-tetrafluoropropane, 2,3-bis-chloro-1,1,1,3-tetrafluoropropane is under the existence of dechlorination catalyst, and the gas phase dechlorination reaction carried out with hydrogen generates 2,3,3,3-tetrafluoropropenes (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze)；Reaction condition is: reaction temperature 200 DEG C～300 DEG C, the mol ratio 0～1:1 of hydrogen and 2,3-bis-chloro-1,1,1,2-tetrafluoropropane and 2,3-bis-chloro-1,1,1,3-tetrafluoropropane total amounts, 1～60 second time of contact.
Formula CF described in step a3-xClxCF2-yClyCH2Cl compound is selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl or CF2ClCCl2CH2Cl, the reaction raw materials being certainly suitable for also includes CCl3CFClCH2Cl、CFCl2CFClCH2Cl。
Formula CF described in step a3-xClxCF2-yClyCH2Cl compound is CCl3CCl2CH2Cl。
Liquid-phase fluorination catalyst described in step a is Fe2O3-TaCl5-CF3SO3H composite catalyst, wherein Fe2O3、TaCl5、CF3SO3The mol ratio of H three is 1:2:5.The catalyst being suitable for also includes other lewis acid, transition metal halide, halogenosulfonic acid or their combination, for instance sexavalence molybdenum halides, quinquevalence antimony halogenide, tetravalent titanium halide, chromic fluoride, the fluoride of chromic oxide；The molar ratio of three can also be 2:2:5 or 2:1:5 or 2:3:5, and the amount of certain trifluoromethanesulfonic acid is can to select in wider scope, and its mole can be Fe2O31 to 20 times of mole, it is preferable that 2 to 10 times, it is considered to reaction effect and catalyst service life, more preferably 5 times.
The reaction condition of the liquid phase fluorination reaction described in step a is: reaction temperature 110 DEG C～130 DEG C, fluohydric acid gas and CF3-xClxCF2-yClyCH2The mol ratio of Cl is 10～15:1, Fe in fluorination catalyst2O3With TaCl5Consumption 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 catalyst, wherein, A is the VIIIth race's element, it is preferable that one or more combinations in Ni, Fe, Co, B is High field side injection, namely there is the element that ion electricity price is higher, radius is less, have relatively macroion field intensity, including lanthanide series, Sc and Y, and Th, U, Pb, Zr, Hf, Ti, Nb, Ta, one or more combinations in preferred Zr, Y, La, C is alkali earth metal, it is preferable that the one in Mg, Ca, Ba；The mol ratio of Mn, A, B, C is (0.3～2): (0.6～5): (0.1～1): (2～9), it is preferable that (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 catalyst, and wherein the mol ratio of Mn, Ni, Zr, Ca is 0.6:3:0.4:6；The preparation method of this catalyst includes: reacted with precipitant by the mixed solution of a certain proportion of tri-kinds of metal soluble-salts of Mn, Ni, Zr, pH controls at 7.5-9.5, stir, precipitate, filter and dry, again by mixed to the oxide of a certain amount of Ca, hydroxide or carbonate uniformly, again at 200 DEG C-500 DEG C, no less than three thermogrades when, carry out baking inphases, finally obtain then through fluohydric acid gas activation processing at 200 DEG C-380 DEG C.
The reaction condition of gas phase fluorination described in step b is: reaction temperature 280 DEG C～320 DEG C；Mol ratio 10～the 20:1 of fluohydric acid gas and the chloro-1,1,2-trifluoro propane of 1,2,3-tri-；Reaction contact time 10 seconds～30 seconds.When this gas phase fluorination temperature is too high, by-product HCFC-234da, 1,2-bis-chloro-3,3,3-trifluoro propene (HCFO-1223xd), tetrachloropropylene (TCE), trifluorobichloroethane (HCFC-123) substantially increase, causing that target product HCFC-234bb optionally reduces, when the temperature is too low, reaction conversion ratio will adversely reduce.Especially, when reacting on the temperature higher than 450 DEG C and carrying out, carbide can be produced and adhere to or be deposited on reaction tube wall or filler, block the inside of reactor gradually.For this situation, it is possible to by passing into a certain amount of N2Reaction, thus playing alleviation or eliminating, also can be suspended and pass into oxygen or the air carbide residue to remove in reaction tube in reactor by diluting reaction raw material.
Dechlorination catalyst described in step c is Cu-V-Mg-F catalyst, wherein the mol ratio of Cu, V, Mg three is (2～4): (1～2): (4～7), preferably (3～4): (1～2): (4～6), more preferably 4:1:5, the preparation method of this 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, add the ammonium hydrogencarbonate that mass fraction is 10%, regulate pH to control to be about 9, about 5h, scrubbed rear centrifugation, then dry at 120 DEG C, then at 200 DEG C of-500 DEG C of temperature, no less than three thermogrades when, carry out baking inphases, finally pass sequentially through again fluohydric acid gas, Hydrogen activation process obtain.The preparation method being suitable for this catalyst has infusion process, coprecipitation, blending method, sol-gel process etc..This dechlorination reaction can also be in protonic solvent; the liquid phase dechlorination reaction of HCFC-234bb and HCFC-234db and reducing agent effect; wherein protonic solvent includes methanol, ethanol, acetic acid or ethylene glycol; can certainly be the tert-butyl alcohol, formic acid, acetic anhydride, glycerol or diglycol; other simultaneously common protonic solvent is also applied for this step, such as the polyhydric alcohol that propylene glycol, polyethylene glycol 200 and hydroxyl are not fully protected；Reducing agent is Mg, Al, Zn or Fe, or Ag and Fe bimetallic reduction system, it is also possible to be the compositions of Cu, Ag, the compositions of Ni and Fe, the compositions of Cu and Fe, the compositions of Cu and Al, Pd and Fe, and they combinations
The reaction condition of the gas phase dechlorination reaction described in step c is: reaction temperature 260 DEG C～300 DEG C, the mol ratio 0.3:1 of hydrogen and HCFC-234bb and HCFC-234db total amount, 5～30 seconds times of contact.In this gas phase dechlorination reaction, hydrogen is the key factor affecting this reaction with the mol ratio of HCFC-234bb and HCFC-234da total amount, when passing into excessive hydrogen, although reaction can realize converting completely, but the selectivity of target product substantially reduces, mol ratio preferably 0.1～0.5:1 that hydrogen is suitable with HCFC-234bb and HCFC-234da, more preferably 0.1～0.3:1, hydrogen to pass into trans can be can also be off and on, semi-continuously continuously.
The reaction pressure of step a of the present invention is less on the impact of this fluorination reaction, can select to operate easily pressure according to the material of consersion unit, anticorrosive and pressure degree, preferably, described reactor is to be manufactured by the material of tolerance fluohydric acid gas and the corrosiveness of catalyst, such as Hastelloy (Hastalloy), inconel (Inconel), monel metal (Monel) and be lined with the container of fluoropolymer.
Reaction described in step b of the present invention can carry out in any reactor being suitable for gas phase fluorination.The fluorination reactor type of step b neither be crucial, it is possible to use tubular reactor, fluidized-bed reactor etc..It addition, adiabatic reactor or isothermal reactor also can be used.
The pretreatment of the dechlorination catalyst of step c of the present invention can be undertaken by being heated in nitrogen or other inert gas flows by catalyst about 200 DEG C to about 380 DEG C, then processes activation successively then through the fluohydric acid gas stream of nitrogen dilution excessive in a large number, hydrogen stream to obtain high catalyst activity.The regeneration of catalyst can carry out under the following conditions, makes air or with the air of nitrogen dilution at about 100 DEG C to about 380 DEG C, it is preferable that the temperature of about 150 DEG C to about 365 DEG C passes through catalyst, continues about 8 hours to about 3 days, and this depends on the size of reactor.
nullThe invention have the advantages that and provide a kind of method being effectively synthesized HFO-1234yf，There is intermediate be easily isolated，Intermediate Part a product 1,2,3-tri-chloro-1,1,2-trifluoro propane (HCFC-233bc) (bp:95 DEG C～97 DEG C) and intermediate Part b product 2,3-bis-chloro-1,1,1,2-tetrafluoropropane (HCFC-234bb) (bp:53 DEG C～55 DEG C)、2,3-bis-chloro-1,1,1,The boiling point of 2-tetrafluoropropane (HCFC-234da) (bp:58 DEG C～60 DEG C) differs greatly，About 41 DEG C，Very easily separate，Intermediate Part b product HCFC-234bb and HCFC-234da also differs greatly with the boiling point of step c product and target product tetrafluoropropene (bp:-28 DEG C)，About 70 DEG C，It is also easy to separate；Catalysts is not related to containing chromium, antimony containing compounds, and human and environment is friendly；Having reaction condition gentleness, gas-phase reaction temperature is also less than 350 DEG C, it is most important that dechlorination reaction realizes under a small amount of hydrogen existent condition, it is not necessary to the hydrogen of stoichiometry.
Accompanying drawing explanation
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；
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail
Analytical tool: extra large glad GC-930 type gas chromatograph, Agilent company 30mDB-5 (50m × 0.32mm) capillary chromatographic column；ITQ700 (ion trap): Thermofisherscientific, Agilent company GASPRO (60m × 0.25mm) capillary chromatographic column.
Chromatographic condition: initial column temperature 40 DEG C, keeps 5min, rises to 180 DEG C with the heating rate of 10 DEG C/min, keeps 3min；Temperature of vaporization chamber 220 DEG C, split ratio is 50.
Ion trap mass spectrometry condition: filament emission current 70A；Mass scan range 10-350amu；Full scan mode, scanning speed 10 micro scannings/second；Multiplier voltage 1556V；Transmission line temperature 220 DEG C, carrier gas is helium.
Embodiment 1:
To 500mL equipped with magnetic agitation, the Monel autoclave of packed tower and condenser molectron adds iron sesquioxide (3.7g, 0.023mol), tantalic chloride (16.3g, 0.045mol), trifluoromethanesulfonic acid (17.1g, 0.11mol) it is cooled to-20 DEG C, add anhydrous hydrogen fluoride (27.2g, 1.4mol), progressively it is warming up to 40 DEG C, process 2 hours, it is warming up to 60 DEG C again, process 1 hour, it is warming up to 80 DEG C, process 1 hour, finally it is warming up to 100 DEG C, process 3 hours, so far it is disposed, in processing procedure, pressure is controlled by periodic exhaustion HCl by-product.
At room temperature, reaction unit is carried out evacuation process, wherein sucting reaction raw material 1,1,1,2,2,3-chlordene propane (200g, 0.79mol), it is pressed into anhydrous hydrogen fluoride (158g again, 7.9mol), more progressively it is warming up to 120 DEG C, and maintains 10h at this temperature, during heating pressure is controlled by periodic exhaustion HCl by-product, keeps pressure lower than 1000Kpa.By in product withdraw water absorber extremely, then the washing of gained Organic substance is obtained colourless liquid 3 times, through gas chromatographic analysis, be mainly CF2ClCFClCH2Cl(HCFC-233bc)、CF2ClCCl2CH2Cl (HCFC-232ac), reaction result is in Table 1.
Embodiment 2～5:
Embodiment 2～5 synthesizes 1,2,3-tri-chloro-1 according to the method that embodiment 1 is identical, 1,2-trifluoro propane, the difference is that the reaction temperature in embodiment 1 be 120 DEG C, and the reaction temperature in embodiment 2～5 is 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 according to identical in embodiment 1 method synthesis 1,2,3-tri-chloro-1,1,2-trifluoro propane, the difference is that HF and the CCl in embodiment 13CCl2CH2The mol ratio of Cl is 10:1, and both mol ratios in embodiment 6～8 are followed successively by 5:1,15:1,20:1, and reaction result is as shown in table 2.
Table 2
Embodiment 9～13:
Embodiment 9～13 according to identical in embodiment 1 method synthesis 1,2,3-tri-chloro-1,1,2-trifluoro propane, the difference is that total consumption of iron sesquioxide in the catalyst in embodiment 1, tantalic chloride be 20g, n (Fe2O3): n (TaCl5):: n (CF3SO3H) for 1:2:5, and total consumption of iron sesquioxide in the catalyst in embodiment 9～13, tantalic chloride and Fe2O3、TaCl5、CF3SO3The mol ratio of H three is as shown in table 3, and when carrying out catalyst treatment, fluoride hydrogen amount is adjusted accordingly in molar ratio, and reaction result is in Table 3.
Table 3
Embodiment 14～17:
Embodiment 14～17 according to identical in embodiment 1 method synthesis 1,2,3-tri-chloro-1,1,2-trifluoro propane, the difference is that the reaction raw materials in embodiment 1 be CCl3CCl2CH2Cl, and the reaction raw materials in embodiment 14～17 is CFCl2CCl2CH2Cl、CF2ClCCl2CH2Cl、CCl3CFClCH2Cl、CFCl2CFClCH2Cl, 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 aqueous solution, again at 20 DEG C of-40 DEG C of temperature, adding mass fraction when being stirred continuously is 15% ammonia, regulate pH and control 8.0, reaction 8h, filter and dry 2h at 120 DEG C, then by mixed for a certain amount of calcium carbonate uniformly, then at 200 DEG C roasting 1h, 5 DEG C/min rises to 320 DEG C, roasting 2h, 10 DEG C/min rise to 400 DEG C, roasting 4h, finally obtain then through fluohydric acid gas activation processing at 200 DEG C-380 DEG C, about need 36h.
In the nickel pipe fixed-bed tube reactor that internal diameter is 38mm, load 50mlMn-Ni-Zr-Ca composite catalyst, wherein the mol ratio of Mn, Ni, Zr, Ca is 0.6:2:0.4:7, and catalyst is dried, then at 300 DEG C, pass into HF and 1,2, chloro-1,1, the 2-trifluoro propane (HCFC-233bc) of 3-tri-, react under atmospheric pressure (normal pressure), the mol ratio controlling both is 10:1, and time of contact is 30 seconds, and product is after washing, alkali cleaning remove HCl and HF, with gas chromatogram and mass spectral analysis, reaction result is: generating CF3CFClCH2Cl(HCFC-234bb)、CF3While CHClCHFCl (HCFC-234da), also with a small amount of HCFO-1223xd, CF3The by-products such as CCl=CHF occur, result is in Table 5.
By above-mentioned reactant liquor rectification is obtained HCFC-234bb, HCFC-234da, purity respectively 99.2%, 97.9%, through GC-MS,1H-NMR、13C-NMR、19F-NMR characterizes qualification, as Figure 1-4.
Boiling point: 53 DEG C-55 DEG C
Fig. 1 mass spectral results and peak ownership thereof are as follows: m/z184:m/z186:m/z188=9:6:1 (M+), for the isotopic peak ratio containing two chlorine；M/z149:m/z151=3:1 [(M-Cl)+], for the isotope ratio containing a chlorine, m/z165:m/z167:m/z169=9:6:1 [(M-F)+], it is reasonable to lose；M/z69 (CF3+) and m/z114 (C2H2FCl2+) is complementary ion；m/z75(C3HF2+)；M/z49:m/z51=3:1 (CH2Cl+).
Learnt by above analysis: this compound is the chloro-1,1,1,2-tetrafluoropropane of 2,3-bis-.
Fig. 2, Fig. 3, Fig. 4 show that this compound is 2,3-bis-chloro-1,1,1,3-tetrafluoropropane, shown in specific as follows
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 reacts according to synthetic method identical in embodiment 18, the difference is that the reaction temperature in embodiment 18 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, and reaction result is in Table 5.
Table 5
Embodiment 23～26:
Embodiment 23～26 reacts according to synthetic method identical in embodiment 18, the difference is that the mol ratio of HF and the HCFC-233bc in embodiment 18 be 10:1, and both mol ratios in embodiment 24～26 are followed successively by 5:1,15:1,20:1,30:1, reaction result is in Table 6.
Table 6
Embodiment 27～29:
Embodiment 27～29 reacts according to synthetic method identical in embodiment 18, the difference is that the time of contact in embodiment 18 be 30s, and in embodiment 27～29 time of contact be followed successively by 10s, 20s, 60s, reaction result is in Table 7.
Table 7
Embodiment 30～36:
Embodiment 30～36 reacts according to synthetic method identical in embodiment 18, the difference is that the catalyst in embodiment 18 be Mn-Ni-Zr-Ca composite catalyst, 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 is as shown in table 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)2·3H2In the mixed aqueous solution of O, add the ammonium hydrogencarbonate that mass fraction is 10%, regulate pH and control to be about 9, about 5h, scrubbed rear centrifugation, again at 120 DEG C dry, then at 200 DEG C roasting 1h, 5 DEG C/min rises to 320 DEG C, roasting 2h, 5 DEG C/min rises to 450 DEG C, roasting 4h, finally pass sequentially through again excessive fluohydric acid gas, Hydrogen activation process obtain.
In the nickel pipe fixed-bed tube reactor that internal diameter is 38mm, loading 50ml containing above-mentioned Cu-V-Mg-F catalyst, wherein the mol ratio of Cu, V, Mg three is 4:1:5, passes into H at 280 DEG C2After two hours, pass into 2,3-bis-chloro-1,1,1,2-tetrafluoropropane (HCFC-234bb), 2,3-bis-chloro-1,1,1,3-tetrafluoropropane (HCFC-234da) (both weight/mass percentage composition are 96.5%, 3.9%) reacts under atmospheric pressure (normal pressure), and the mol ratio controlling hydrogen and HCFC-234bb and HCFC-234da total amount is 0.3:1, time of contact is 30 seconds, with gas chromatogram, mass spectral analysis reaction result, concurrently there are by-product CF what generate HFO-1234yf, HFO-1234ze3CF=CClH (HCFO-1224yd), CF3CFHCH3(HCFC-254eb), wherein dechlorination reaction conversion ratio is the summation of HCFC-234bb, HCFC-234da conversion ratio, and result is in Table 9.
Embodiment 38～41:
Embodiment 38～41 is according to synthetic method synthesis 2,3,3 identical in embodiment 37,3-tetrafluoropropene, the difference is that the reaction temperature in embodiment 37 be 260 DEG C, and the reaction temperature in embodiment 38～41 is followed successively by 200 DEG C, 240 DEG C, 260 DEG C, 300 DEG C, and reaction result is as shown in table 9.
Table 9
Embodiment 42～45:
Embodiment 42～45 is according to synthetic method synthesis 2 identical in embodiment 37,3,3,3-tetrafluoropropene, the difference is that in the catalyst in embodiment 37, the mol ratio of Cu, V, Mg three is 4:1:5, and in the catalyst in embodiment 42～45 Cu, V, Mg three mole be 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 is according to synthetic method synthesis 2 identical in embodiment 37,3,3,3-tetrafluoropropene, the difference is that in embodiment 37, the mol ratio of hydrogen and HCFC-234bb, HCFC-234da total amount is 0.3:1, and both mol ratios in embodiment 46～48 are followed successively by 0.1:1,0.5:1,1:1, and reaction result is as shown in table 11.
Table 11
Embodiment 49～52:
Embodiment 49～52 is according to synthetic method synthesis 2,3,3 identical in embodiment 37,3-tetrafluoropropene, institute the difference is that in embodiment 37 time of contact be 30s, and the time of contact in embodiment 49～52 time is 5s, 10s, 20s, 50s, and reaction result is as shown in table 12.
Table 12
Embodiment 53:
Embodiment 53 is according to synthetic method synthesis 2 identical in embodiment 37,3,3,3-tetrafluoropropene, the difference is that the reaction raw materials in embodiment 37 be HCFC-234bb and HCFC-234da compositions (both weight/mass percentage composition are 96.5%, 3.9%), and the reaction raw materials in embodiment 53 is HCFC-234bb, reaction result shows: reaction conversion ratio is 85.2%, selecting response behavior 99.2%.
Embodiment 54:
Embodiment 53 is according to synthetic method synthesis 2 identical in embodiment 37,3,3,3-tetrafluoropropene, the difference is that the reaction raw materials in embodiment 37 be HCFC-234bb and HCFC-234da compositions (both weight/mass percentage composition are 96.5%, 3.9%), and the reaction raw materials in embodiment 53 is HCFC-234da, reaction result shows: reaction conversion ratio is 84.7%, selecting response behavior 99.1%.
The above, it is only the section Example of the present invention, not the present invention is done any pro forma restriction, every any simple amendment above-described embodiment made according to the technical spirit of the present invention, equivalent variations and modification, belong within the scope of technical solution of the present invention.
Claims (10)
1. the synthetic method of a tetrafluoropropene, it is characterised in that comprise the following steps:
A, under the existence of liquid-phase fluorination catalyst, formula is CF3-xClxCF2-yClyCH2The compound of Cl and fluohydric acid gas carry out liquid phase fluorination reaction and generate 1,2,3-tri-chloro-1,1,2-trifluoro propane, wherein, in compound formula x=1,2,3；Y=1,2, and 3≤x+y≤5；Reaction condition is: reaction temperature 80 DEG C～160 DEG C, fluohydric acid gas and CF3-xClxCF2-yClyCH2The mol ratio of Cl is 5～20:1, and the consumption of fluorination catalyst is CF3-xClxCF2-yClyCH2The 3%～50% of Cl mass；
B, 1,2,3-tri-chloro-1,1,2-trifluoro propane, under the existence of catalysts for gas phase fluorination, carry out gas phase fluorination with fluohydric acid gas and generate 2,3-bis-chloro-1,1,1,2-tetrafluoropropane, 2,3-bis-chloro-1,1,1,3-tetrafluoropropane；Reaction condition is: reaction temperature 240 DEG C～350 DEG C；Mol ratio 3～the 30:1 of fluohydric acid gas and 1,2,3-tri-chloro-1,1,2-trifluoro propane, reaction contact time 0.5 second～60 seconds；
C, 2,3-bis-chloro-1,1,1,2-tetrafluoropropane, 2,3-bis-chloro-1,1,1,3-tetrafluoropropane are under the existence of dechlorination catalyst, and the gas phase dechlorination reaction carried out with hydrogen generates 2,3,3,3-tetrafluoropropenes, 1,3,3,3-tetrafluoropropene；Reaction condition is: reaction temperature 200 DEG C～300 DEG C, the mol ratio 0～1:1 of hydrogen and 2,3-bis-chloro-1,1,1,2-tetrafluoropropane and 2,3-bis-chloro-1,1,1,3-tetrafluoropropane total amounts, 1～60 second time of contact.
2. the synthetic method of 2,3,3,3-tetrafluoropropenes according to claim 1, it is characterised in that the formula CF described in step a3-xClxCF2-yClyCH2Cl compound is selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl or CF2ClCCl2CH2Cl。
3. the synthetic method of 2,3,3,3-tetrafluoropropenes according to claim 2, it is characterised in that described formula CF3-xClxCF2-yClyCH2Cl compound is CCl3CCl2CH2Cl。
4. the synthetic method of 2,3,3,3-tetrafluoropropenes according to claim 1, it is characterised in that the liquid-phase fluorination catalyst described in step a is Fe2O3-TaCl5-CF3SO3H composite catalyst, wherein Fe2O3、TaCl5、CF3SO3The mol ratio of H is 1:2:5.
5. the synthetic method of 2,3,3,3-tetrafluoropropenes according to claim 1 or 4, it is characterised in that the reaction condition of described liquid phase fluorination reaction is: reaction temperature 110 DEG C～130 DEG C, fluohydric acid gas and CF3-xClxCF2-yClyCH2The mol ratio of Cl is 10～15:1, Fe in fluorination catalyst2O3With TaCl5Consumption and be CF3-xClxCF2-yClyCH2The 10%～15% of Cl mass.
6. according to claim 12,3,3, the synthetic method of 3-tetrafluoropropene, it is characterized in that, the catalysts for gas phase fluorination described in step b is Mn-A-B-C composite catalyst, wherein, A is group VIII element, one or more combinations in Ni, Fe, Co, B is High field side injection, one or more combinations in Zr, Y, La, C is alkali earth metal, the one in Mg, Ca, Ba；The mol ratio of Mn, A, B, C is (0.3～2): (0.6～5): (0.1～1): (2～9).
7. the synthetic method of 2,3,3,3-tetrafluoropropenes according to claim 6, it is characterised in that described catalysts for gas phase fluorination is Mn-Ni-Zr-Ca composite catalyst, wherein the mol ratio of Mn, Ni, Zr, Ca is 0.6:3:0.4:6；The preparation method of this catalyst includes: reacted with precipitant by the mixed solution of tri-kinds of metal soluble-salts of Mn, Ni, Zr in proportion, pH controls at 7.5-9.5, stir, precipitate, filter and dry, again by mixed to the oxide of Ca, hydroxide or carbonate uniformly, again at 200 DEG C-500 DEG C, no less than three thermogrades when, carry out baking inphases, finally obtain then through fluohydric acid gas activation processing at 200 DEG C-380 DEG C.
8. the synthetic method of 2,3,3,3-tetrafluoropropenes according to claim 1, it is characterised in that the reaction condition of gas phase fluorination described in step b is: reaction temperature 280 DEG C～320 DEG C；Mol ratio 10～the 20:1 of fluohydric acid gas and the chloro-1,1,2-trifluoro propane of 1,2,3-tri-；Reaction contact time 10 seconds～30 seconds.
9. according to claim 12,3,3, the synthetic method of 3-tetrafluoropropene, it is characterized in that, the dechlorination catalyst described in step c is Cu-V-Mg-F catalyst, and wherein the mol ratio of Cu, V, Mg three is (2～4): (1～2): (4～7)；The preparation method of this catalyst includes: in proportion by V2O5It is added to Cu (NO3)2·3H2O and Mg (NO3)2·6H2In the mixed aqueous solution of O, add the ammonium hydrogencarbonate that mass fraction is 10%, regulate pH to control to be about 9, about 5h, scrubbed rear centrifugation, then dry at 120 DEG C, then at 200 DEG C of-500 DEG C of temperature, no less than three thermogrades when, carry out baking inphases, finally pass sequentially through again fluohydric acid gas, Hydrogen activation process obtain.
10. 2,3,3 according to claim 1 or 9, the synthetic method of 3-tetrafluoropropene, it is characterised in that the reaction condition of described gas phase dechlorination reaction is: reaction temperature 260 DEG C～300 DEG C, hydrogen and 2,3-bis-chloro-1,1,1,2-tetrafluoropropane and 2,3-bis-chloro-1,1, the mol ratio 0.3:1 of 1,3-tetrafluoropropane total amount, 5～30 seconds times of contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410771684.5A CN105753638B (en) | 2014-12-13 | 2014-12-13 | The synthetic method of 2,3,3,3- tetrafluoropropenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410771684.5A CN105753638B (en) | 2014-12-13 | 2014-12-13 | The synthetic method of 2,3,3,3- tetrafluoropropenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105753638A true CN105753638A (en) | 2016-07-13 |
| CN105753638B CN105753638B (en) | 2018-08-31 |
Family
ID=56336423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410771684.5A Active CN105753638B (en) | 2014-12-13 | 2014-12-13 | The synthetic method of 2,3,3,3- tetrafluoropropenes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105753638B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018155069A1 (en) * | 2017-02-24 | 2018-08-30 | セントラル硝子株式会社 | Method for producing 1,2,2,2-tetrafluoroethyl difluoromethyl ether (desflurane) |
| CN111757863A (en) * | 2018-03-07 | 2020-10-09 | 阿科玛法国公司 | Production process of 2-chloro-3, 3, 3-trifluoropropene |
| CN114127036A (en) * | 2019-07-03 | 2022-03-01 | 科慕埃弗西有限公司 | Compositions and methods for synthesizing 2, 3-dichloro-1, 1, 1, 2-tetrafluoropropane and 2, 3, 3, 3-tetrafluoropropene |
| US20220119327A1 (en) * | 2019-07-01 | 2022-04-21 | Daikin Industries, Ltd. | Alkane production method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665405A (en) * | 2008-07-31 | 2010-03-10 | 霍尼韦尔国际公司 | Method for producing 2,3,3,3-tetrafluoropropene |
| WO2012061022A2 (en) * | 2010-11-02 | 2012-05-10 | E. I. Du Pont De Nemours And Company | Use of copper-nickel catalyst for dehalogenation of chlorofluorocompounds |
| CN102603465A (en) * | 2012-02-20 | 2012-07-25 | 西安近代化学研究所 | Preparation method of 2,3,3,3-tetrafluoropropene |
| WO2013085787A1 (en) * | 2011-12-07 | 2013-06-13 | Honeywell International Inc. | Process for cis-1chloro-3,3,3-trifluoropropene |
| CN103508840A (en) * | 2013-09-28 | 2014-01-15 | 西安近代化学研究所 | Preparation method of 2, 3, 3, 3-tetrafluoropropene |
-
2014
- 2014-12-13 CN CN201410771684.5A patent/CN105753638B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665405A (en) * | 2008-07-31 | 2010-03-10 | 霍尼韦尔国际公司 | Method for producing 2,3,3,3-tetrafluoropropene |
| WO2012061022A2 (en) * | 2010-11-02 | 2012-05-10 | E. I. Du Pont De Nemours And Company | Use of copper-nickel catalyst for dehalogenation of chlorofluorocompounds |
| WO2013085787A1 (en) * | 2011-12-07 | 2013-06-13 | Honeywell International Inc. | Process for cis-1chloro-3,3,3-trifluoropropene |
| CN102603465A (en) * | 2012-02-20 | 2012-07-25 | 西安近代化学研究所 | Preparation method of 2,3,3,3-tetrafluoropropene |
| CN103508840A (en) * | 2013-09-28 | 2014-01-15 | 西安近代化学研究所 | Preparation method of 2, 3, 3, 3-tetrafluoropropene |
Non-Patent Citations (1)
| Title |
|---|
| E.W.KAISER ET AL.: "Relative Rate Study of the Kinetics, Mechanism, and Thermodynamics of the Reaction of Chlorine Atoms with CF3CF=CH2 (HFO-1234yf) in 650-950 Torr of N2 or N2/O2Diluent at 296-462 K", 《THE JOURNAL OF PHYSICAL CHEMISTRY A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018155069A1 (en) * | 2017-02-24 | 2018-08-30 | セントラル硝子株式会社 | Method for producing 1,2,2,2-tetrafluoroethyl difluoromethyl ether (desflurane) |
| CN111757863A (en) * | 2018-03-07 | 2020-10-09 | 阿科玛法国公司 | Production process of 2-chloro-3, 3, 3-trifluoropropene |
| US20220119327A1 (en) * | 2019-07-01 | 2022-04-21 | Daikin Industries, Ltd. | Alkane production method |
| CN114127036A (en) * | 2019-07-03 | 2022-03-01 | 科慕埃弗西有限公司 | Compositions and methods for synthesizing 2, 3-dichloro-1, 1, 1, 2-tetrafluoropropane and 2, 3, 3, 3-tetrafluoropropene |
| JP7536076B2 (en) | 2019-07-03 | 2024-08-19 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Compositions and methods for the synthesis of 2,3-dichloro-1,1,1,2-tetrafluoropropane and 2,3,3,3-tetrafluoropropene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105753638B (en) | 2018-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103946192B (en) | For the method manufacturing HF hydrocarbon | |
| CN101801894B (en) | Preparation of halogen and hydrogen containing alkenes over metal fluoride catalysts | |
| KR101595196B1 (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| KR102052141B1 (en) | Process for producing 2,3,3,3-tetrafluoropropene | |
| CN103508840B (en) | Preparation method of 2, 3, 3, 3-tetrafluoropropene | |
| US9862661B2 (en) | Process for the preparation of 2, 3, 3, 3-tetrafluoropropene | |
| CN102947256A (en) | Method for producing tetrafluoropropenes | |
| US9873649B2 (en) | Process for the joint preparation of 1, 3, 3, 3-tetrafluoropropene and 2, 3, 3, 3-tetrafluoropropene | |
| MX2012011894A (en) | Process for the manufacture of tetrafluoroolefins. | |
| CN105753637B (en) | The preparation method of the trans trifluoro propene of 1,2 dichloro 3,3,3 | |
| US8889924B2 (en) | Process for the production of 1,3,3,3-tetrafluoropropene | |
| CN109503315A (en) | The preparation method of tetrafluoropropene | |
| CN104169245A (en) | Process for producing 2,3,3,3-tetrafluoropropene | |
| US20080207963A1 (en) | Preparation of composition containing chromium, oxygen, and either silver or palladium, and their use as catalysts and catalyst precursors | |
| CN105753638A (en) | 2,3,3,3-tetrafluoropropene synthetic method | |
| MX2014004249A (en) | Process for producing 2,3,3,3-tetrafluoropropene. | |
| CN105753640A (en) | Preparation method of 1,3,3,3-tetrafluoropropene | |
| CN112811973B (en) | Preparation method of E-1,3,3, 3-tetrafluoropropene | |
| CN115215722B (en) | Co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene | |
| CN103524293B (en) | Method for preparing 2,3-dichlone-1,1,1,2-tetrachlorofluoropropane | |
| CN105753639A (en) | Preparation method of 2,3,3,3-tetrafluoropropene | |
| WO2021003207A2 (en) | Compositions and methods for synthesis of 2,3-dichloro-1,1,1,2-tetrafluoropropane and 2,3,3,3-tetrafluoropropene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190705 Address after: 255300 Hengdao 979, Zhoucun District, Zibo City, Shandong Province Patentee after: Shandong Huaan Modern Environmental Protection Technology Co., Ltd. Address before: 710065 168 zhangeight East Road, Yanta District, Xi'an, Shaanxi Patentee before: Xi'an Inst. of Modern Chemistry |