CN102603465B - Preparation method of 2,3,3,3-tetrafluoropropene - Google Patents
Preparation method of 2,3,3,3-tetrafluoropropene Download PDFInfo
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Abstract
The invention provides a preparation method of 2,3,3,3-tetrafluoropropene, which uses 1,1,2,3-tetrachloropropene as a raw material and comprises the following steps: (1) reacting 1,1,2,3-tetrachloropropene with a first fluorinating reagent to produce 1,1,2-trichloro-3-fluoropropene; (2) reacting 1,1,2-trichloro-3-fluoropropene with a second fluorinating reagent to produce 2-chloro-3,3,3-trifluoropropene; (3) reacting 2-chloro-3,3,3-trifluoropropene with a third fluorinating reagent to produce 2-chloro-1,1,1,2-tetrafluoropropane; and (4) carrying out dehydrochlorination reaction of 2-chloro-1,1,1,2-tetrafluoropropane to produce 2,3,3,3-tetrafluoropropene. The preparation method provided by the invention is mainly used for preparing 2,3,3,3-tetrafluoropropene.
Description
Technical field
The present invention relates to the preparation method of a kind of 2,3,3,3-tetrafluoeopropene (HFO-1234yf), relate in particular to a kind of 1,1,2,3-tetrachloro propylene polystep reaction and obtain the preparation method of 2,3,3,3-tetrafluoeopropene.
Background technology
The latent value of ozone depletion of 2,3,3,3-tetrafluoeopropene is zero, and greenhouse gases is lower, is considered to the ideal substitute of HFC-134a.
At present, with 1,1,2,3-tetrachloro propylene and anhydrous hydrogen fluoride, for raw material, synthetic 2,3,3, the 3-tetrafluoeopropene of three-step reaction is that 2,3,3,3-tetrafluoeopropene is reported more synthetic route.This route is under the effect of catalyzer, the first step is carried out fluoridation and is generated 2-chloro-3,3,3-trifluoro propene (HCFO-1233xf), the further hydrogen fluoride addition reaction of second step HCFO-1233xf generates 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), there is dehydrochlorination reaction generation HFO-1234yf in HCFC-244bb then.Because 1,1,2,3-tetrachloro propylene is unstable, when high temperature, easily generate polymkeric substance or de-HCl and generate alkynes.WO2009015317 discloses a kind of preparation method of 2,3,3,3-tetrafluoeopropene, the method, at the raw material 1,1,2 of the first step reaction, is added a small amount of Resorcinol, quadrol, Diisopropylamine etc. in 3-tetrachloro propylene and is improved 1 as stablizer, the stability of 1,2,3-tetrachloro propylene.
Summary of the invention
Technical problem to be solved of the present invention is to overcome the deficiency existing in background technology, provides one to avoid 2,3,3 of 1,1,2,3-tetrachloro propylene autohemagglutination or de-HCl, the preparation method of 3-tetrafluoeopropene.
The preparation method who the invention provides a kind of 2,3,3,3-tetrafluoeopropene, comprises the following steps:
(1) 1,1,2,3-tetrachloro propylene reacts with the first fluorination reagent and generates the chloro-3-fluorine of 1,1,2-tri-propylene;
(2) 1, the chloro-3-fluorine of 1,2-tri-propylene reacts with the second fluorination reagent and generates 2-chloro-3,3,3 ,-trifluoropropene;
(3) 2-chloro-3,3,3 ,-trifluoropropene and the 3rd is fluoridized reagent react generation 2-chloro-1,1,1,2-tetrafluoropropane;
(4) 2-chloro-1,1,1,2-tetrafluoropropane dehydrochlorination reaction generates 2,3,3,3-tetrafluoeopropene.
The step (1) of the inventive method is liquid phase fluorination reaction, 90 DEG C～120 DEG C of temperature of reaction, reaction times 1h～10h, the first fluorination reagent and 1,1, the mol ratio of 2,3-tetrachloro propylene is 1～5: 1, and wherein the first fluorination reagent is that alkaline metal fluoride cpd, basic metal are fluoridized hydrogen salt, tertiary amine hydrofluoride, fluoridize quaternary amine or fluoridized quaternary amine hydrofluoride.
The step (2) of the inventive method is gas phase catalytic fluorination reaction, 150 DEG C～300 DEG C of temperature of reaction, duration of contact 2s～60s, the second fluorination reagent and 1, the mol ratio of the chloro-3-fluorine of 1,2-tri-propylene is 5: 1～20: 1, and wherein the second fluorination reagent is hydrogen fluoride.
The step (3) of the inventive method is liquid-phase catalysis fluoridation, and temperature of reaction is 50 DEG C～120 DEG C, reaction times 0.5h～10h, the 3rd fluorination reagent and 3-fluoro-2, the mol ratio of 3,3-tri chloropropene is 5: 1～20: 1, and wherein the 3rd fluorination reagent is hydrogen fluoride.
The step (4) of the inventive method is gas phase catalysis dehydrochlorination reaction, 350 DEG C～480 DEG C of temperature of reaction, duration of contact 1s～60s.
The described alkaline metal fluoride cpd of step (1) of the inventive method is Sodium Fluoride, Potassium monofluoride or cesium fluoride, it is potassium hydrogen fluoride that basic metal is fluoridized hydrogen salt, hydrogen fluoride caesium or bifluoride hydrogen potassium, tertiary amine hydrogen fluoride salts is triethylamine two hydrofluorides, Tri-n-Propylamine two hydrofluorides, diisopropylethylamine two hydrofluorides, dimethylcyclohexylamine two hydrofluorides, dimethylcyclohexylamine two hydrofluorides, tri-n-amyl amine two hydrofluorides, pyridine one hydrofluoride or pyrazine one hydrofluoride, fluoridizing quaternary amine is tetrabutyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, tetrapropyl Neutral ammonium fluoride, ethyl-trimethyl Neutral ammonium fluoride or benzyl tributyl Neutral ammonium fluoride, quaternary amine hydrofluoride is tetrapropyl Neutral ammonium fluoride two hydrofluorides or tetrabutyl ammonium fluoride two hydrofluorides.
Preferred version of the present invention comprises the following steps:
(1) 1,1,2,3-tetrachloro propylene reacts with triethylamine two hydrofluorides and generates the chloro-3-fluorine of 1,1,2-tri-propylene, 110 DEG C of temperature of reaction, and reaction times 2h, the mol ratio of triethylamine two hydrofluorides and 1,1,2,3-tetrachloro propylene is 3;
(2) 1,1,2-tri-chloro-3-fluorine propylene and HF are at Cr
2o
3catalyzer exists lower reaction to generate 2-chloro-3,3,3 ,-trifluoropropene, 200 DEG C of temperature of reaction, duration of contact 10s, HF and 1,1, the mol ratio of the chloro-3-fluorine of 2-tri-propylene is 15: 1;
(3) 2-chloro-3,3,3 ,-trifluoropropene reacts at SbCl with HF
5catalyzer exists lower reaction to generate 2-chloro-1,1,1,2-tetrafluoropropane, and temperature of reaction is 80 DEG C, reaction times 6h, and HF and 3-are fluoro-2,3, and the mol ratio of 3-tri chloropropene is 15: 1;
(4) 2-chloro-1,1,1,2-tetrafluoropropane is at Cr
2o
3catalyzer exists lower reaction to generate 2,3,3,3-tetrafluoeopropene, 380 DEG C of temperature of reaction, duration of contact 10s.
Alkaline metal fluoride cpd in the step (1) of the inventive method is Sodium Fluoride, Potassium monofluoride or cesium fluoride; It is sodium bifluoride, potassium hydrogen fluoride, hydrogen fluoride caesium or bifluoride hydrogen potassium that basic metal is fluoridized hydrogen salt.Tertiary amine hydrogen fluoride salts general formula in step (1) is: tertiary amine nHF, and 0 < n≤4.0 in formula, tertiary amine is that molecular formula is R
1r
2r
3the open chain amine of N, R in formula
1～R
3be C
1～C
10alkyl, or for containing-N=or
the cyclammonium of group and 4～9 carbon atoms, comprise triethylamine, Tri-n-Propylamine, diisopropylethylamine, tri-n-butylamine, tri-n-amyl amine, dimethylcyclohexylamine, pyridine, 2-picoline, 2,4,6-trimethylpyridine, pyrimidine, pyrazine, N-methyl piperidine, N-methyl Pyrrolidine etc., but be not limited to above lifted compound.Preferred tertiary amine is triethylamine, Tri-n-Propylamine, diisopropylethylamine, tri-n-amyl amine, pyridine or 2-picoline.N in tertiary amine hydrogen fluoride salts general formula tertiary amine nHF is very large to fluoridation activity influence.In the time that n is bigger than normal, the nucleophilic fluorination ability of tertiary amine nHF is lower, and in certain scope, n is less, and the nucleophilic fluorination ability of tertiary amine nHF is just higher, and in the time that n is less than normal, the alkalescence of tertiary amine nHF is bigger than normal, and reaction preference declines to some extent.The preferred n of the present invention is 1.0≤n≤3.0.The quaternary amine of fluoridizing in step (1) is tetrabutyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, ethyl-trimethyl Neutral ammonium fluoride or benzyl tributyl Neutral ammonium fluoride; Quaternary amine hydrofluoride is tetrapropyl Neutral ammonium fluoride two hydrofluorides, tetrabutyl ammonium fluoride two hydrofluorides.In the time that the first fluorination reagent is selected alkaline metal fluoride cpd, step (1) is carried out under polyol solvent exists, and wherein polyvalent alcohol is ethylene glycol, 1,2-PD, 1, ammediol, 2,3-butanediol, glycol ether, Triethylene glycol, tetraethylene-glycol or glycerol.By controlling solvent adding amount, the amount concentration that makes 1,1,2,3-tetrachloro propylene is 1.0mol/L～15.0mol/L, preferably 1.0mol/L.
In the step (2) of the inventive method, 1,1,2-tri-chloro-3-fluorine propylene and anhydrous hydrogen fluoride generate 2-3 in gas phase fluorination, the mixture of 3,3-tri chloropropene and HCl.Reaction is preferably carried out under catalysts for gas phase fluorination exists, can select any catalysts for gas phase fluorination well known in the prior art, including, but not limited to oxide compound, oxyhydroxide, halogenide, oxyhalogenide, inorganic salt and their mixture of chromium, aluminium, cobalt, nickel, iron, zinc and magnesium.Be applicable to catalyzer of the present invention and comprise Cr
2o
3, FeCl
3/ C, Cr
2o
3/ AlF
3, Cr
2o
3/ MgF
2, Cr
2o
3/ Al
2o
3, Cr
2o
3/ C, NiCl
2/ AlF
3, CoCl
2/ AlF
3, ZnCl
2/ Cr
2o
3/ AlF
3, Cr
2o
3/ CaF
2, FeCl
3/ CaF
2or their mixture etc.Reaction conditions is preferred: 180 DEG C～220 DEG C of temperature of reaction, 5 seconds～10 seconds duration of contact, the mol ratio of HF and the chloro-3-fluorine of 1,1,2-tri-propylene is 10: 1～15: 1.Reaction can be carried out in any reactor that is suitable for gas phase fluorination, in the reactor of preferentially manufacturing at the material (as Hastalloy, Inconel, Monel) hydrogen fluoride to corrosion-resistant effect, carries out.
In the step (3) of the inventive method, HCFO-1233xf and HF are at the synthetic HCFC-244bb of liquid-phase fluorination.Reaction is preferably carried out under liquid-phase fluorination catalyst exists, any liquid-phase fluorination catalyst well known in the prior art be can select, Lewis acid, transition metal halide, transition metal oxide, IVb family metal halide, Vb family metal halide, fluosulfonic acid or their mixture comprised.The preferred SbCl of liquid-phase fluorination catalyst
5, SbCl
3, SnCl
4, TaCl
5, TiCl
4, NbCl
5, MoCl
6, FeCl
5or their fluorinated species or mixture.Most preferably SbCl
5.Step (2) can adopt interrupter method, also can be continuous processing.The residence time in reaction times and continuous processing in interrupter method is depended on temperature of reaction, reaction mass mole proportioning.Generally, the reaction times in interrupter method is 0.5h～10h; The residence time in continuous processing is 10min～30min.
In the step (4) of the inventive method, the de-HCl of HCFC-244bb gas phase generates target product HFO-1234yf.Reaction is preferably carried out under dehydrochlorination catalyzer exists, and can select any dehydrochlorination catalyzer well known in the prior art, comprises metal halide, halo metal oxide, metal or metal alloy, gac or their mixture.In the time using metal halide or metal oxide for catalyzer, preferably monovalence, divalence or trivalent metal halogenide, oxide compound and their combination, more have the monovalence selected and bivalent metal halide or their mixture, as Cr
3+, Fe
3+, Mg
2+, Ca
2+, Ni
2+, Zn
2+, Li
+, K
+, Cs
+or Na
+halogenide.In the time using metal, metal alloy or their mixture for catalyzer, comprise Fe, Co, Ni, Cr, Mn, Pd, Pt, Cu or their alloys and mixts.Catalyzer can use carrier, also can not use carrier.Preferred catalyzer is gac, iron, CsCl/CaF
2, CsCl/MgF
2, CsCl/C, FeCl
3/ C etc.For the extending catalyst life-span, step (4) preferably nitrogen.Helium, argon gas, CO
2, the diluent gas such as HF carries out under existing, preferably HF.HF, as diluent gas, can suppress the de-HF reaction of HCFC-244bb, improves the selectivity of target product HFO-1234yf.
The present invention does not do further restriction to the reaction pressure of step (1)～(4), and working pressure is selected according to the working pressure of reaction product separation system.
Reaction process of the present invention can represent with following equation:
(1)：CCl
2＝CClCH
2Cl+MF·HF→CCl
2＝CClCH
2F+KCl·HF
(TCP) (HCFO-1231)
(2)：CCl
2＝CClCH
2F+HF→CH
2＝CClCF
3+HCl
(HCFO-1231) (HCFO-1233xf)
(3)：CF
3CCl＝CH
2+HF→CF
3CClFCH
3
(HCFO-1233xf) (HCFC-244bb)
(4)：CF
3CClFCH
3→CF
3CF＝CH
2+HCl
(HCFC-244bb) (HFO-1234yf)
Compared with prior art, the present invention is first by 1,1, and 2,3-tetrachloro propylene is converted into metastable intermediate 1,1, the chloro-3-fluorine of 2-tri-propylene, and it is 1 years old, the transformation efficiency of 1,2,3-tetrachloro propylene reaches 98%, selectivity reaches 93%, and then carries out gas phase fluorination synthetic intermediate 1,1, the chloro-3-fluorine of 2-tri-propylene, thus effectively avoid 1,1,2,3-tetrachloro propylene autohemagglutination or de-HCl, without adding Resorcinol, quadrol or Diisopropylamine stablizer; And method in documents is by the raw material 1,1,2 in the first step reaction, in 3-tetrachloro propylene, needs to add a small amount of Resorcinol, quadrol, Diisopropylamine etc. and improve 1,1,2 as stablizer, the stability of 3-tetrachloro propylene.
Embodiment
Followingly the present invention is described in further detail in conjunction with the embodiments, but does not limit the scope of the invention.
Embodiment 1
1,1,2,3-tetrachloro propylene reacts with Potassium monofluoride and generates the chloro-3-fluorine of 1,1,2-tri-propylene.In the dry there-necked flask of the 50mL that magnetic agitation, thermometer, condensing works are housed, add successively 5.0g 1,1,2,3-tetrachloro propylene (0.028mol), 30mL glycol ether, open and stir, be heated to after 110 DEG C, in reaction solution, add 8.1g Potassium monofluoride (0.069mol), react 1 hour, reaction solution is cooled to room temperature and filters, and filtrate decompression distillation obtains 1,1, the chloro-3-fluorine of 2-tri-propylene, 1,1,2,3-tetrachloro propylene conversion 96.4%, the selectivity 92.2% of the chloro-3-fluorine of 1,1,2-tri-propylene.
Embodiment 2～4
Similar to the operation of embodiment 1, difference is reaction conditions difference, and reaction result is as shown in table 1.
Table 1
Embodiment 5～9
Similar to the operation of embodiment 1, difference is that the solvent of embodiment 5～9 is ethylene glycol, reaction times 4h, and the mol ratio of KF and 1,1,2,3-tetrachloro propylene is respectively 1: 1, and 1.5: 1,2: 1,2.5: 1,5: 1, reaction result was as shown in table 2.
Table 2
Embodiment 10
Similar to the operation of embodiment 8, difference is that fluorination reagent is KFHF, 1,1,2,3-tetrachloro propylene conversion 85.4%, 1,1, the selectivity 95.0% of the chloro-3-fluorine of 2-tri-propylene.
Embodiment 11
In the dry there-necked flask of the 50mL that magnetic agitation, thermometer, condensing works are housed, add successively fluorination reagent triethylamine 2HF (10.8g, 0.084mol), add subsequently 1,1,2,3-tetrachloro propylene (5.0g, 0.028mol), nucleophilic fluorination reagent and 1,1,2, the mol ratio of 3-tetrachloro propylene is 3, reacts 1 at 110 DEG C 2 hours, 1,2,3-tetrachloro propylene conversion is 90%, the chloro-3-fluorine of 1,1,2-tri-Propylene Selectivity is 95%.
Embodiment 12～15
Similar to the operation of embodiment 11, difference is nucleophilic fluorination reagent difference, and reaction result is as shown in table 3.
Table 3
Embodiment 16～19
In being the fixed-bed tube reactor of ∮ 38mm, caliber packs 60ml Cr into
2o
3catalyzer, HF and 1,1, the chloro-3-fluorine of 2-tri-propylene is preheated to after temperature of reaction, then enters reactor and under suitable reaction conditions, carry out gas phase fluorination, after reaction 20h, reaction product is analyzed by gas-chromatography, and analytical procedure is area normalization method, and reaction result is shown in Table 4.
Table 4
Embodiment 20
The operational condition identical with embodiment 17, carries out longevity test, moves continuously 300h rear catalyst and has no obvious inactivation, and reaction result is shown in Table 5.
Under identical reaction conditions, carry out 1,1,2, the simultaneous test of the synthetic 2-chloro-3,3,3 ,-trifluoropropene of 3-tetrachloro propylene gas phase fluorination, moved after 20 hours, the transformation efficiency of 1,1,2,3-tetrachloro propylene is 100%, the selectivity of 2-chloro-3,3,3 ,-trifluoropropene is 96%, moves after 100 hours, it is 80% that the transformation efficiency of 1,1,2,3-tetrachloro propylene drops to, the selectivity of 2-chloro-3,3,3 ,-trifluoropropene drops to 85%.
Embodiment 21～24
2-chloro-3,3,3 ,-trifluoropropene carries out with synthetic the reacting in the 2L stainless steel autoclave of being furnished with stirring, distillation tower of 2-chloro-1,1,1,2-tetrafluoropropane of HF liquid-phase fluorination, and catalyzer is selected SbCl
5.To adding successively in reactor 3-fluoro-2,3,3-tri chloropropene, SbCl
5and hydrogen fluoride, under suitable reaction conditions, react, reaction product is in washing, the dry cold-trap that is collected in-40 DEG C, after reaction finishes, the product of collecting in gas chromatographic analysis cold-trap, calculate transformation efficiency and selectivity, analytical procedure is area normalization method, and the reaction result under differential responses condition is in table 6.
Table 5
Table 6
Embodiment 25～28
In being the fixed-bed tube reactor of ∮ 38mm, caliber packs 60ml Cr into
2o
3catalyzer, 2-chloro-1,1,1,2-tetrafluoropropane is preheated to after temperature of reaction, then enters reactor and under suitable reaction conditions, carry out the de-HCl reaction of gas phase, after reaction 5h, reaction product is analyzed by gas-chromatography, and analytical procedure is area normalization method, and the reaction result under differential responses condition is in table 7.
Table 7
Embodiment 29
The operational condition identical with embodiment 25, difference is to add HF as diluent gas, HF and 2-chloro-1, the mol ratio of 1,1,2-tetrafluoropropane is 20: 1,2-chloro-1,1,1, the transformation efficiency 68.8%, 2,3 of 2-tetrafluoropropane, the selectivity 65.7% of 3,3-tetrafluoeopropene, 2-chloro-3, the selectivity 31.2% of 3,3-trifluoro propene.
Claims (3)
1. one kind 2,3,3, the preparation method of 3-tetrafluoeopropene, comprises the following steps:
(1) 1,1,2,3-tetrachloro propylene reacts with the first fluorination reagent and generates the chloro-3-fluorine of 1,1,2-tri-propylene, described reaction is liquid phase fluorination reaction, 90 DEG C～120 DEG C of temperature of reaction, reaction times 1h～10h, the first fluorination reagent and 1,1, the mol ratio of 2,3-tetrachloro propylene is 1～5: 1, and wherein the first fluorination reagent is that alkaline metal fluoride cpd, basic metal are fluoridized hydrogen salt, tertiary amine hydrofluoride, fluoridize quaternary amine or fluoridized quaternary amine hydrofluoride;
(2) 1, the chloro-3-fluorine of 1,2-tri-propylene reacts with the second fluorination reagent and generates 2-chloro-3,3,3-trifluoro propene, described reaction is gas phase catalytic fluorination reaction, 150 DEG C～300 DEG C of temperature of reaction, duration of contact 2s～60s, the second fluorination reagent and 1, the mol ratio of the chloro-3-fluorine of 1,2-tri-propylene is 5: 1～20: 1, and wherein the second fluorination reagent is hydrogen fluoride;
(3) 2-chloro-3,3,3 ,-trifluoropropene and the 3rd is fluoridized reagent react generation 2-chloro-1,1,1,2-tetrafluoropropane, described reaction is liquid-phase catalysis fluoridation, temperature of reaction is 50 DEG C～120 DEG C, reaction times 0.5h～10h, the 3rd fluorination reagent and 3-fluoro-2,3, the mol ratio of 3-tri chloropropene is 5: 1～20: 1, and wherein the 3rd fluorination reagent is hydrogen fluoride;
(4) 2-chloro-1,1,1,2-tetrafluoropropane dehydrochlorination reaction generates 2,3,3,3-tetrafluoeopropene, and described reaction is gas phase catalysis dehydrochlorination reaction, 350 DEG C～480 DEG C of temperature of reaction, duration of contact 1s～60s.
2. according to claim 12, 3, 3, the preparation method of 3-tetrafluoeopropene, it is characterized in that the described alkaline metal fluoride cpd of step (1) is Sodium Fluoride, Potassium monofluoride or cesium fluoride, it is potassium hydrogen fluoride that basic metal is fluoridized hydrogen salt, hydrogen fluoride caesium or bifluoride hydrogen potassium, tertiary amine hydrofluoride is triethylamine two hydrofluorides, Tri-n-Propylamine two hydrofluorides, diisopropylethylamine two hydrofluorides, dimethylcyclohexylamine two hydrofluorides, dimethylcyclohexylamine two hydrofluorides, tri-n-amyl amine two hydrofluorides, pyridine one hydrofluoride or pyrazine one hydrofluoride, fluoridizing quaternary amine is tetrabutyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, tetrapropyl Neutral ammonium fluoride, ethyl-trimethyl Neutral ammonium fluoride or benzyl tributyl Neutral ammonium fluoride, fluoridizing quaternary amine hydrofluoride is tetrapropyl Neutral ammonium fluoride two hydrofluorides or tetrabutyl ammonium fluoride two hydrofluorides.
3. according to claim 1 and 22,3,3, the preparation method of 3-tetrafluoeopropene, comprises the following steps:
(1) 1,1,2,3-tetrachloro propylene reacts with triethylamine two hydrofluorides and generates the chloro-3-fluorine of 1,1,2-tri-propylene, 110 DEG C of temperature of reaction, and reaction times 2h, the mol ratio of triethylamine two hydrofluorides and 1,1,2,3-tetrachloro propylene is 3;
(2) 1,1,2-tri-chloro-3-fluorine propylene and HF are at Cr
2o
3catalyzer exists lower reaction to generate 2-chloro-3,3,3 ,-trifluoropropene, 200 DEG C of temperature of reaction, duration of contact 10s, HF and 1,1, the mol ratio of the chloro-3-fluorine of 2-tri-propylene is 15: 1;
(3) 2-chloro-3,3,3 ,-trifluoropropene reacts at SbCl with HF
5catalyzer exists lower reaction to generate 2-chloro-1,1,1,2-tetrafluoropropane, and temperature of reaction is 80 DEG C, reaction times 6h, and HF and 3-are fluoro-2,3, and the mol ratio of 3-tri chloropropene is 15: 1;
(4) 2-chloro-1,1,1,2-tetrafluoropropane is at Cr
2o
3catalyzer exists lower reaction to generate 2,3,3,3-tetrafluoeopropene, 380 DEG C of temperature of reaction, duration of contact 10s.
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| CN103420782B (en) * | 2013-07-12 | 2015-05-13 | 西安近代化学研究所 | Method for preparing fluorinated alkene by performing dehydrochlorination on chlorofluorocarbon under action of catalyst |
| CN105753642B (en) * | 2014-12-13 | 2018-06-08 | 西安近代化学研究所 | The preparation method of coproduction 1,3,3,3- tetrafluoropropenes and 2,3,3,3- tetrafluoropropenes |
| CN105753638B (en) * | 2014-12-13 | 2018-08-31 | 西安近代化学研究所 | The synthetic method of 2,3,3,3- tetrafluoropropenes |
| CN105753639B (en) * | 2014-12-13 | 2018-07-31 | 西安近代化学研究所 | A kind of preparation method of 2,3,3,3- tetrafluoropropenes |
| CN106608881A (en) * | 2015-11-15 | 2017-05-03 | 宁夏际华环境安全科技有限公司 | Production process for fluorine reagent |
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| CN110013853B (en) | 2019-05-08 | 2021-10-01 | 西安近代化学研究所 | Catalyst for preparing 2,3,3, 3-tetrafluoropropene through gas-phase hydrodechlorination |
| CN112500259B (en) * | 2020-12-14 | 2023-09-22 | 常熟三爱富中昊化工新材料有限公司 | Process for the preparation of heptafluoropropane |
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| CN101597209A (en) * | 2008-03-20 | 2009-12-09 | 霍尼韦尔国际公司 | Be used to prepare 2,3,3, the integrated process of 3-tetrafluoeopropene |
| WO2011077191A1 (en) * | 2009-12-23 | 2011-06-30 | Arkema France | Catalytic gas phase fluorination of 1230xa to 1234yf |
| CN102351637A (en) * | 2011-08-31 | 2012-02-15 | 浙江师范大学 | Method for preparing 2,3,3,3-tetrafluoropropene |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597209A (en) * | 2008-03-20 | 2009-12-09 | 霍尼韦尔国际公司 | Be used to prepare 2,3,3, the integrated process of 3-tetrafluoeopropene |
| WO2011077191A1 (en) * | 2009-12-23 | 2011-06-30 | Arkema France | Catalytic gas phase fluorination of 1230xa to 1234yf |
| CN102351637A (en) * | 2011-08-31 | 2012-02-15 | 浙江师范大学 | Method for preparing 2,3,3,3-tetrafluoropropene |
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Effective date of registration: 20160519 Address after: 255300 Zhoucun City, Shandong province constant access road, No. 979, Patentee after: Shandong Huaan Modern Environmental Protection Technology Co., Ltd. Address before: 710065 Shaanxi province Xi'an Yanta District Zhang eight road No. 168 Patentee before: Xi'an Inst. of Modern Chemistry |