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CN101492342A - Hydrofluorinating 2-chloro-3, 3, 3-trifluoropropene to 2-chloro-1, 1,1, 2-tetrafluoropropane, with catalysts SbCl3, SbCl5, SbF5, TiCl4, SnCl4, Cr2O3and fluorinated Cr2O3 - Google Patents

Hydrofluorinating 2-chloro-3, 3, 3-trifluoropropene to 2-chloro-1, 1,1, 2-tetrafluoropropane, with catalysts SbCl3, SbCl5, SbF5, TiCl4, SnCl4, Cr2O3and fluorinated Cr2O3 Download PDF

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CN101492342A
CN101492342A CNA200910126749XA CN200910126749A CN101492342A CN 101492342 A CN101492342 A CN 101492342A CN A200910126749X A CNA200910126749X A CN A200910126749XA CN 200910126749 A CN200910126749 A CN 200910126749A CN 101492342 A CN101492342 A CN 101492342A
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chloro
trifluoro propene
tetrafluoropropane
catalyzer
sbcl
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D·C·默克
R·C·约翰逊
童雪松
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Honeywell International Inc
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Honeywell International Inc
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Abstract

A process for making 2-chloro-1,1,1,2-tetrafluoropropane, comprising hydrofluorinating 2-chloro-3,3,3-trifluoropropene in the presence of a catalyst selected from the group consisting of: SbCl3, SbCl5, SbF5, TiCl4, SnCl4, Cr2O3 and fluorinated Cr2O3.

Description

Use catalyst S bCl 3, SbCl 5, SbF 5, TiCl 4, SnCl 4, Cr 2O 3With fluoridize Cr 2O 3With 2-chloro-3,3,3-trifluoro propene hydrofluorination is a 2-chloro-1,1,1, the 2-tetrafluoropropane
The cross reference application
The application requires the right of priority of the U.S. Provisional Application No.61/021121 of submission on January 15th, 2008, and the full content of the document is hereby incorporated by.
Technical field
The present invention relates to 2-chloro-1,1,1, the preparation method of 2-tetrafluoropropane.The invention further relates to have high per pass conversion (single-pass conversion level) pass through hydrofluorination 2-chloro-3,3, the 3-trifluoro propene prepares 2-chloro-1,1,1, the method for 2-tetrafluoropropane.
Background technology refrigeration agent and whipping agent 2,3,3,3-tetrafluoeopropene (1234yf) be by 2-chloro-1,1,1,2-tetrafluoropropane (244bb) dehydrochlorination.244bb can be by 2-chloro-3,3, and 3-trifluoro propene (1233xf) is produced.
When 2-chloro-3,3, the 3-trifluoro propene is to 2-chloro-1,1,1, when the transformation efficiency of 2-tetrafluoropropane hangs down, and 2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3, the 3-trifluoro propene all is present in the mixture of product flow.2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3,3-trifluoro propene have similar boiling point and Azeotrope-like characteristic, and this makes them be difficult to separate by for example conventional distillation of standard technique.
A kind of method that solves the low-conversion problem is to increase product to flow to the circulation of reactor, thereby is further transformed.The circulation that increases will need the size of processing unit (plant) and scale to increase the level or the product production of expecting to keep, thereby increase production cost significantly.In addition, the separation difficulty of component in the product flow.
By 2-chloro-3,3, the 3-trifluoro propene prepares 2-chloro-1,1,1 with high per pass conversion level, and the method for 2-tetrafluoropropane will be an ideal.
Summary of the invention
A kind of preparation 2-chloro-1,1,1, the method for 2-tetrafluoropropane, it is included in and is selected from SbCl 3, SbCl 5, SbF 5, TiCl 4, SnCl 4, Cr 2O 3With fluoridize Cr 2O 3The existence of catalyzer under, hydrofluorination 2-chloro-3,3,3-trifluoro propene.
The preferred catalyst chlorine activation of anhydrous hydrogen fluoride and possibility anhydrous (possibly anhydrous).In addition, keep catalyst activation by adding chlorine (or similar oxygenant) continuously or in batches.
Hydrofluorination reaction is a gas phase fluorination.The catalyzer that is preferred for gas phase fluorination is the SbCl that is carried on the gac 5Gas phase fluorination is under about 30 ℃～about 200 ℃ of temperature, and preferably approximately carries out for 50 ℃～about 120 ℃.Gas phase fluorination is under about 5psia～about 200psia pressure, and preferably approximately 30psia～approximately 175psia carries out.
Hydrogen fluoride and 2-chloro-3,3, the mol ratio of 3-trifluoro propene are about 1: 1～about 30: 1, preferably approximately 2: 1～about 15: 1.
Perhaps, the hydrofluorination step is a liquid-phase fluorination, and wherein temperature of reaction is about 30-200 ℃, preferably approximately 50-120 ℃; And wherein reaction pressure is about 15-200psia, preferably approximately 50-175psia; And wherein hydrogen fluoride and 2-chloro-3,3, the mol ratio of 3-trifluoro propene is about 1: 1～about 30: 1, preferably approximately 2: 1～about 15: 1.
EmbodimentIn the method for the invention, the catalyzer of selecting for use is used for improving by HF 2-chloro-3,3, and two keys of 3-trifluoro propene carry out addition by 2-chloro-3,3, and the 3-trifluoro propene prepares 2-chloro-1,1,1, the per pass conversion of 2-tetrafluoropropane.Catalyst system therefor is as follows: SbCl 3, SbCl 5, SbF 5, TiCl 4, SnCl 4, Cr 2O 3With fluoridize Cr 2O 3Randomly, 2-chloro-3,3,3-trifluoro propene can contain the HCl that is taken out of by step before in addition.
Hydrofluorination reaction can carry out in gas phase or liquid phase.
In gas-phase hydrofluorination reaction, HF (hydrogen fluoride gas) by catalyst bed by continuously feeding.Of short duration only use the HF incoming flow after, make 2-chloro-3,3, the 3-trifluoro propene was with about 1: 1～about 1: 30, and the ratio of preferably approximately 1: 2～about 1: 15 (2-chloro-3,3,3-trifluoro propene/HF mol ratio) continues charging by catalyst bed.HF and 2-chloro-3,3, carry out under the pressure that is reflected at (50 ℃～about 120 ℃ of preferably approximatelies) and about 5psia～about 200psia (pound/square inch absolute) under about 30 ℃～about 200 ℃ of temperature (preferably approximately 30psia～about 175psia) of 3-trifluoro propene.Catalyzer can be carried on the carrier, and for example on gac, perhaps load or independence do not exist.Except that gac, the useful catalysts carrier comprises: aluminum oxide, fluorided alumina, aluminum fluoride, alkaline earth metal oxide, alkali fluoride earth metals, zinc oxide, zinc fluoride, stannic oxide and Tin tetrafluoride..Before using, catalyzer whether needs with anhydrous hydrogen fluoride HF (hydrogen fluoride gas) and/or Cl 2The state of catalyzer is depended in (chlorine) activation.Need, can be by adding chlorine continuously or in batches or similar oxygenant keeps catalyst activation.
In the liquid phase hydrofluorination reaction, catalyzer joins in the reactor with liquid form, chooses wantonly to activate with HF.Then, the activatory catalyzer is heated to the expected response temperature of about 30 ℃～about 200 ℃ (50 ℃ to about 120 ℃ of preferably approximatelies) and pressure is remained on (preferably approximately 50psia～about 175psia) in about 15psia～about 200psia scope.Of short duration only with the HF charging after, make 2-chloro-3,3, the incoming flow of 3-trifluoro propene is with about 1: 1～about 1: 30, and the ratio of preferably approximately 1: 2～about 1: 15 (2-chloro-3,3,3-trifluoro propene/HF mol ratio) continues charging by catalyzer.Need, can be by adding Cl continuously or in batches 2Or similar oxygenant keeps catalyst activation.
2-chloro-3,3, the 3-trifluoro propene prepares 2-chloro-1,1,1, and the raising of 2-tetrafluoropropane or improved per pass conversion are key characters of the present invention.Hydrofluorination reaction preferably proceeds to and obtains about 70% or higher, preferably approximately 90% or higher and most preferably about 93% or higher transformation efficiency.Transformation efficiency be multiply by 100 and calculates divided by reactant (2-chloro-3,3, the 3-trifluoro propene) mole number that adds in the reactor by reactant (2-chloro-3,3, the 3-trifluoro propene) mole number that consumes.Preferably the selectivity of 2-chloro-1,1,1,2 tetrafluoropropane is reached about 60% or higher and most preferably about 80% or higher.Selectivity is calculated by the mole number of the product that forms (2-chloro-1,1,1, the 2 tetrafluoropropane) mole number divided by the reactant that consumes.
Hydrofluorination reaction preferably carries out in corrosion-resistant reaction vessel.The example of corrosion resistant material is Hastelloy, Nickel, Incoloy, Inconel, Monel and fluoropolymer liner.Container can have fixed or fluidizing catalyst bed, perhaps contains liquid catalyst.If desired, at run duration, can use rare gas element in the reactor, for example nitrogen or argon gas.
Be embodiments of the invention below, but be not limited only to this.Except as otherwise noted, all per-cents and umber are all calculated by weight.
Embodiment
Embodiment 1
Carry out 2-chloro-3,3,3-trifluoro propene (1233xf)+HF → 2-chloro-1,1,1, the gas phase fluorination of 2-tetrafluoropropane (244bb).The fluorination catalyst of this experiment is the 50 weight %SbCl that are immersed on the 50 weight %Calgon PCB gacs 5
The 50 weight %SbCls of several kg load of preparation on activated carbon in the laboratory 5At first make catalyzer cross 10 mesh sieves and remove fine powder.2272.6 grams (perhaps about 2800cc) join in two placed in-line 2-inch gas phase pipe reactors altogether, and it is loaded in the sand-bath with the control heating.
By adding and SbCl 5Mol ratio is at least 5: 1 HF, adds Cl then 2With SbCl 5Mol ratio is at least 3: 1 Cl 2Come deactivated catalyst.At last, make a large amount of excessive HF pass through catalyst bed 2 hours.
Adopt the 2-chloro-3,3 of various steel cylinder dresses, 3-trifluoro propene coarse raw materials reacts as organic charging, thereby produces 2-chloro-1,1,1,2 tetrafluoropropane.Before removing excessive HF, the reactor stream fluid is collected in the distillation tower.In the experiment, obtained 93.5% 2-chloro-3,3,3-trifluoro propene transformation efficiency.With the mole is unit, and maximum has obtained 98.4% 2-chloro-1,1,1,2-tetrafluoropropane selectivity.Reaction continuous service 76.5 hours does not attempt using Cl 2Carry out catalyst regeneration.After going into operation about 65 hours, catalyzer begins to present the sign of inactivation.Experimental data and reaction conditions are shown among following table 1A and the 1B.
Production time (hour) T(℃) P(Mpa) Catalyzer 2-chloro-3,3,3-trifluoro propene input speed (mmol/ min) 2-chloro-3,3,3-trifluoro propene input speed (g/hr) HF input speed (mmol/min) HF input speed (g/hr) HF:2-chloro-3,3,3-trifluoro propene mol ratio Catalyzer (ml) Duration of contact (second)
1-23 72 0.33 SbCl 5/C 120 95.3 185.2 222.3 15.5 2800 99
23-29 72 0.33 SbCl 5/C 18.3 145.2 215.5 258.6 11.8 2800 84
29-42 72 0.33 SbCl 5/C 23.4 186.0 241.9 290.3 10.3 2800 74
42-53 74 0.33 SbCl 5/C 30.2 240.4 275.9 331.1 9.1 2800 64
53-60 76 0.33 SbCl 5/C 39.3 322.1 317.5 381.0 8.1 2800 54
60-65.5 77 0.33 SbCl 5/C 48.1 394.6 400.7 480.8 8.3 2800 43
65.5-73.5 80 0.33 SbCl 5/C 51.1 408.2 404.5 485.4 7.9 2800 42
73.5-76.5 79 0.33 SbCl 5/C 33.9 281.2 355.3 426.4 10.5 2800 49
Table 1B
Figure A20091012674900061
Table 1C
Figure A20091012674900071
Table 1D
Figure A20091012674900072
Embodiment 2
2-chloro-3,3,3-trifluoro propene (1233xf)+HF → 2-chloro-1,1,1, the liquid phase fluorination reaction of 2-tetrafluoropropane (244bb).The fluorination catalyst of this experiment is SbCl 5
To the packed column that is equipped with 2 inches ID (internal diameter) and the Teflon of condenser TM(Teflon is E.I.duPont de Nemours﹠amp to the liner Liquid-phase reactor; The trade mark of Co) adds about 6100 gram SbCl in 5Reactor is 2.75 inches ID * 36 inch L (length).At first in reactor, add a large amount of excessive Cl 2To guarantee that catalyzer is in the pentavalent attitude.Reactor is heated to about 85 ℃-87 ℃.At first begin charging HF.After adding 1.3lbs (pound) HF, beginning charging 2-chloro-3,3,3-trifluoro propene.2-chloro-3,3, the purity of 3-trifluoro propene raw material is approximately 98GC area % (gas-chromatography).Therapy lasted operation 71 hours.For current operation, run duration approximately added chlorine in per 4 hours to keep catalyst activity in batches.Run duration HF and 2-chloro-3,3, the charging of 3-trifluoro propene changes.Initial operating stage, the average 0.495lbs/hr of HF charging, 2-chloro-3,3, the average 0.408lbs/hr of 3-trifluoro propene (chlorine weight accounts for 5.4% in the organism) thus make HF/2-chloro-3,3,3-trifluoro propene ratio reaches 7.9/1, the residence time is 135 seconds.The operation mid-term, the average 0.843lbs/hr of HF charging (Pounds Per Hour), 2-chloro-3,3, the average 0.66lbs/hr of 3-trifluoro propene (chlorine weight accounts for 3.3% in the organism) thus make HF/2-chloro-3,3,3-trifluoro propene ratio reaches 8.33/1, the residence time is 80 seconds.Move latter stage, speed is accelerated.The average 1.42lbs/hr of HF charging during this period of time, 2-chloro-3,3, the average 1.24lbs/hr of 3-trifluoro propene (chlorine weight accounts for 2% in the organism) thus make HF/2-chloro-3,3,3-trifluoro propene ratio reaches 7.5/1, the residence time is 47 seconds.The reaction later stage, unreacted 2-chloro-3,3, the 3-trifluoro propene increases gradually, and this may be Cl 2The result that level is lower or the residence time is short.
In the experiment in the reactor temperature range be that 78-91 ℃ and pressure range are 85psig-115psig (pound per square inch).Collection organic coarse raw material in service is used gas chromatographic analysis, and the GC analytical results is as follows.
When using gas chromatographic analysis, organic phase shows below:
GC area %
1,1,1,2,2-pentafluoropropane=11.80
2-chloro-1,1,1,2-tetrafluoropropane=82.87
2-chloro-3,3,3-trifluoro propene=1.14
2-chloro-1,1,1,3,3-pentafluoropropane=0.52
2,3-two chloro-3,3-difluoro propylene=0.20
1,2-two chloro-3,3,3-trifluoro propene=2.44
Following table 2 comprises 2-chloro-3,3,3-trifluoro propene transformation efficiency and product selectivity data:
Table 2
(transformation efficiency and selectivity all are unit with the mole)
Hour 1,1,1,2, the 2-pentafluoropropane 2-chloro-1,1,1, the 2-tetrafluoropropane 2-chloro-3,3, the 3-trifluoro propene 2-chloro-1,1,1,3, the 3-pentafluoropropane 1,2-two chloro-3,3,3-trifluoro propene Other ℃
Elapsed time Selectivity Selectivity Transformation efficiency Selectivity Selectivity Selectivity Temperature
2 64.8 24.2 99.3 0.0 0.0 11.1 87.1
3 68.2 24.2 99.2 0.9 4.8 1.9 90.5
4 67.5 24.3 99.8 0.6 3.6 3.9 90.2
5 64.6 30.0 99.9 1.2 3.1 1.1 90.4
6 67.4 27.2 99.8 1.2 3.1 1.0 85.7
8 82.8 15.6 99.7 0.4 0.8 0.5 78.9
9 78.5 20.2 99.9 0.3 0.6 0.4 78.9
10 65.4 32.3 99.6 0.6 1.0 0.6 83.2
11 61.8 35.8 99.0 0.6 1.0 0.7 78.5
12 64.8 33.7 99.3 0.5 0.6 0.4 79.6
13.5 61.6 37.0 99.8 0.5 0.5 0.4 80.9
14 62.1 36.5 99.7 0.5 0.5 0.5 81.3
15 61.9 36.8 99.6 0.5 0.4 0.4 78.9
16 29.1 68.3 99.5 1.3 0.6 0.7 86.9
17 30.5 67.3 98.6 1.2 0.5 0.5 88.5
18 24.4 73.0 98.8 1.5 0.6 0.5 84.5
19 31.0 66.1 98.3 1.6 0.7 0.5 87.5
20 28.7 66.8 99.8 2.5 1.2 0.9 84.5
21 33.8 62.9 99.7 1.8 0.9 0.6 86.9
22 51.6 46.6 99.5 0.9 0.5 0.5 86.6
23 54.3 45.1 99.7 0.2 0.1 0.2 85.6
24 28.3 70.1 99.5 0.8 0.4 0.4 86.9
25 23.0 74.8 99.0 1.1 0.6 0.5 86.4
26 16.0 76.2 98.3 3.6 2.8 1.3 86.3
27 20.8 73.2 98.3 2.7 2.1 1.2 85.5
28 12.0 78.3 99.0 3.2 2.7 3.8 87
29 11.9 79.8 98.7 2.1 2.0 4.2 87.9
30 11.0 80.8 98.6 2.1 2.0 4.2 87.1
31 13.9 81.7 98.2 0.8 1.0 2.6 86.2
32 10.2 86.6 99.3 0.4 0.7 2.2 85.9
33 9.4 87.9 98.8 0.2 1.4 1.0 85.5
34 12.6 85.8 98.5 0.1 0.7 0.8 85.4
35 15.1 83.6 98.1 0.1 0.5 0.7 85.3
36 4.3 92.3 98.2 0.1 2.2 1.1 85.2
37 4.7 92.3 97.9 0.1 1.8 1.2 84.9
38 4.8 92.7 97.9 0.1 1.5 1.0 85.4
39.5 8.6 89.5 97.8 0.0 0.1 1.8 85.1
41.7 17.1 81.4 98.1 0.0 0.6 0.9 85
42.7 14.0 85.7 97.8 0.0 0.1 0.3 83.6
44.7 20.4 79.1 98.1 0.0 0.0 0.4 80.6
46 6.0 92.5 98.3 0.0 0.9 0.5 84.2
47.5 6.1 91.1 99.7 0.0 1.5 1.3 86.2
48 6.2 91.5 99.9 0.0 1.3 1.0 87.1
49 10.6 86.8 98.9 0.0 1.7 1.9 86.9
50 7.2 91.0 98.1 0.0 1.1 0.7 86.6
51 10.9 88.4 97.7 0.0 0.3 0.4 86.7
52 13.9 82.9 98.7 0.0 2.3 0.9 89.3
53 12.7 86.0 97.9 0.0 0.6 0.8 87.5
54 9.5 89.4 97.7 0.0 0.5 0.6 88
55 6.6 92.2 98.3 0.0 0.6 0.7 87.1
56 6.8 89.6 98.1 0.0 2.7 1.0 87.4
57 7.5 91.1 97.6 0.0 0.7 0.7 87.7
58.1 5.4 91.6 99.8 0.1 1.4 1.6 87.6
60 6.2 92.7 98.8 0.0 0.2 0.9 87.8
61 5.6 93.5 100.0 0.0 0.1 0.7 87.8
62 7.6 89.3 99.6 0.0 2.0 1.0 87.7
63 7.8 89.1 97.9 0.1 2.3 0.7 87.9
64 9.0 90.2 99.3 0.0 0.3 0.5 87.7
65.3 0.0 99.4 96.9 0.0 0.2 0.3 88
66 5.2 91.7 99.7 0.1 2.0 1.0 87.2
69 3.3 96.2 96.1 0.1 0.2 0.3 88
70 3.0 95.1 95.3 0.1 1.3 0.5 87.9
71 2.8 95.4 96.8 0.0 0.4 1.4 88.5
Embodiment 3
Embodiment 3 uses the device identical with embodiment 2
To with embodiment 2 in add about 5615 gram SbCl in the identical reactor 5Reactor is heated to about 85 ℃-87 ℃.Charging HF at first.After adding about 1.5lbs HF, beginning charging 2-chloro-3,3,3-trifluoro propene.2-chloro-3,3, the purity of 3-trifluoro propene raw material is approximately 97.3GC area %.Therapy lasted operation 71 hours.For current operation, run duration needs approximately to add in per 4 hours chlorine to keep catalyst activity in batches.
This experiment operation number (operation #) is 36b.Transformation efficiency is higher than 98% rapidly, and other stage of operation keeps above-mentioned state (through closing Friday).Keeping catalyst charge weekend is hot state, and (being called operation #37 now) proceeded in experiment on Monday, and whole week is all observed the similar high conversion of knowing clearly.At operation #36b with next collect about 123 pounds of anacidity 2-chloro-1,1,1 altogether, 2-tetrafluoropropane crude product among the operation #37 in a week.Chlorine adds in the data that indegree is recorded in the operation #37 in the appendix, therefrom as can be seen, adds 1 in the sample behind the chlorine at every turn, and 2-two chloro-3,3,3-tri chloropropene (general about one hour) at once significantly increase, and reduce then.
Reactor temperature range is 78 ℃-86 ℃ in the experiment, and pressure range is 70psig-105psig.Collection organic coarse raw material in service is used gas chromatographic analysis, and the GC analytical results is as follows.
By the 2-chloro-1,1,1 that operation #36b and #37 collect, 2-tetrafluoropropane crude product has following GC and analyzes:
Area %
1,1,1,2,2-pentafluoropropane=4.48
2-chloro-1,1,1,2-tetrafluoropropane=91.59
2-chloro-3,3,3-trifluoro propene=2.10
2-chloro-1,1,1,3,3-pentafluoropropane=0.21
2,3-two chloro-3,3-difluoro propylene=0.17
1,2-two chloro-3,3,3-trifluoro propene=1.13
Following table 3A and 3B have listed 2-chloro-3,3,3-trifluoro propene transformation efficiency and product selectivity data.
Table 3A
(operation #36b is the transformation efficiency and the selectivity of unit with the mole)
Hour elapsed time Airbag # Temperature (℃) 1,1,1,2,2-pentafluoropropane selectivity 2-chloro-1,1,1,2-tetrafluoropropane selectivity 2-chloro-3,3,3-trifluoro propene transformation efficiency % 2-chloro-1,1,1,3,3-pentafluoropropane selectivity 2,3-two chloro-3,3-difluoro propylene selectivity 1,2-two chloro-3,3,3-trifluoro propene selectivity
35.3 36-b3 84.1 0.64 0.26 98.69 0.01 0.02 0.06
36.3 36-b4 85 0.43 0.54 98.70 0.01 0.00 0.01
37.3 36-b5 85.2 0.55 0.41 98.94 0.01 0.01 0.02
38.6 36-b6 85.6 0.44 0.51 98.71 0.01 0.00 0.02
39.2 36-b7 83.6 0.30 0.63 97.77 0.01 0.01 0.03
39.7 36-b8 85.5 0.25 0.70 97.26 0.01 0.01 0.02
40.8 36-b9 86.9 0.36 0.59 98.08 0.01 0.00 0.03
41.6 36-b10 83 0.55 0.44 98.94 0.00 0.00 0.01
42.4 36-b11 85.9 0.40 0.58 98.40 0.00 0.00 0.01
43.4 36-b12 85.3 0.37 0.61 98.42 0.00 0.00 0.00
44.75 36-b13 83.1 0.29 0.70 98.37 0.00 0.01 0.01
45.5 36-b14 80 0.23 0.76 98.44 0.00 0.00 0.00
46.5 36-b15 81.7 0.21 0.76 98.40 0.00 0.00 0.01
47.5 36-b16 81.3 0.19 0.79 98.21 0.00 0.00 0.01
Table 3B
(operation #37 is the transformation efficiency and the selectivity of unit with the mole)
Figure A20091012674900131
Figure A20091012674900141
Figure A20091012674900151
Figure A20091012674900161
The description that should be appreciated that the front only is to exemplary illustration of the present invention.Do not breaking away under the open situation of the present invention, those skilled in the art can make various replacements and change.Therefore, the present invention is intended to comprise that all fall into all these type of replacements, change and variation in the accessory claim scope.

Claims (10)

1. one kind prepares 2-chloro-1,1,1, the method for 2-tetrafluoropropane, and it is included in and is selected from SbCl 3, SbCl 5, SbF 5, TiCl 4, SnCl 4, Cr 2O 3With fluoridize Cr 2O 3Catalyzer have down hydrofluorination 2-chloro-3,3,3-trifluoro propene.
2. the method for claim 1, wherein said catalyzer are block or carrier loaded form.
3. method as claimed in claim 2, wherein said carrier are at least a carriers that is selected from carbon, aluminum oxide, fluorided alumina, aluminum fluoride, alkaline earth metal oxide, alkali fluoride earth metals, zinc oxide, zinc fluoride, stannic oxide and Tin tetrafluoride..
4. the method for claim 1, wherein said catalyzer are used anhydrous hydrogen fluoride, anhydrous chlorine or chlorine activation.
5. the method for claim 1, wherein the 2-chloro-3,3, and the 3-trifluoro propene further comprises HCl.
6. method as claimed in claim 4, wherein said catalyzer is by adding the activation of anhydrous chlorine or chlorine continuously or in batches.
7. the method for claim 1, wherein said hydrofluorination is gas phase fluorination or liquid-phase fluorination.
8. method as claimed in claim 7, wherein said fluoridation are carried out under the pressure of the 200psia of about 5psia～approximately under about 30 ℃～about 200 ℃ temperature.
9. method as claimed in claim 4, wherein hydrogen fluoride and 2-chloro-3,3, the mol ratio of 3-trifluoro propene is about 1: 1～about 30: 1.
10. method as claimed in claim 9, wherein hydrogen fluoride and 2-chloro-3,3, the mol ratio of 3-trifluoro propene is about 2: 1～about 15: 1.
CNA200910126749XA 2008-01-15 2009-01-14 Hydrofluorinating 2-chloro-3, 3, 3-trifluoropropene to 2-chloro-1, 1,1, 2-tetrafluoropropane, with catalysts SbCl3, SbCl5, SbF5, TiCl4, SnCl4, Cr2O3and fluorinated Cr2O3 Pending CN101492342A (en)

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US2112108P 2008-01-15 2008-01-15
US61/021121 2008-01-15
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Cited By (13)

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Publication number Priority date Publication date Assignee Title
CN101913984A (en) * 2010-09-07 2010-12-15 西安近代化学研究所 Method for preparing 2-chlor-1,1,1,2-tetrafluoropropane by gas phase fluorination
CN103449962A (en) * 2013-08-15 2013-12-18 巨化集团技术中心 Synthesis method of 2-chloro-1,1,1,2-tetrafluoropropane
CN104072333A (en) * 2014-05-21 2014-10-01 巨化集团技术中心 Preparation method for 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene
CN104140354A (en) * 2014-08-07 2014-11-12 西安近代化学研究所 Method for preparing HCFC-244bb
CN104140355A (en) * 2014-08-07 2014-11-12 西安近代化学研究所 Method for synthesizing 2-chloro-1,1,1,2-tetrafluoropropane
CN105037080A (en) * 2010-06-28 2015-11-11 霍尼韦尔国际公司 Method for prolonging a catalyst's life during hydrofluorination
CN105289669A (en) * 2015-11-11 2016-02-03 西安近代化学研究所 Liquid-phase fluorination catalyst and application
WO2016019718A1 (en) * 2014-08-07 2016-02-11 西安近代化学研究所 Method for preparing 2-chloro-1,1,1,2-tetrafluoropropane
CN106278804A (en) * 2010-11-16 2017-01-04 霍尼韦尔国际公司 The method producing 2,3,3,3 tetrafluoropropenes and the method purifying 2 chlorine 1,1,1,2 tetrafluoropropane
CN107235822A (en) * 2010-04-29 2017-10-10 霍尼韦尔国际公司 The method for preparing tetrafluoropropene
CN107649167A (en) * 2017-10-26 2018-02-02 金华职业技术学院 CO oxidation catalysts and preparation method thereof under a kind of steam and carbon dioxide atmosphere
CN110407661A (en) * 2018-04-28 2019-11-05 浙江蓝天环保高科技股份有限公司 The method for transformation of by-product trifluoro-ethylene in a kind of chlorotrifluoroethylene production process
CN113966320A (en) * 2019-06-04 2022-01-21 科慕埃弗西有限公司 2-chloro-3, 3, 3-trifluoropropene (1233xf) compositions and methods for making and using the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007079431A2 (en) * 2006-01-03 2007-07-12 Honeywell International Inc. Method for producing fluorinated organic compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007079431A2 (en) * 2006-01-03 2007-07-12 Honeywell International Inc. Method for producing fluorinated organic compounds

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CN107235822B (en) * 2010-04-29 2024-05-17 霍尼韦尔国际公司 Process for preparing tetrafluoropropene
CN107235822A (en) * 2010-04-29 2017-10-10 霍尼韦尔国际公司 The method for preparing tetrafluoropropene
CN105037080B (en) * 2010-06-28 2018-11-30 霍尼韦尔国际公司 Extend the method for the catalyst life during hydrofluorination
CN105037080A (en) * 2010-06-28 2015-11-11 霍尼韦尔国际公司 Method for prolonging a catalyst's life during hydrofluorination
CN101913984B (en) * 2010-09-07 2013-03-13 西安近代化学研究所 Method for preparing 2-chlor-1,1,1,2-tetrafluoropropane by gas phase fluorination
CN101913984A (en) * 2010-09-07 2010-12-15 西安近代化学研究所 Method for preparing 2-chlor-1,1,1,2-tetrafluoropropane by gas phase fluorination
CN106278804A (en) * 2010-11-16 2017-01-04 霍尼韦尔国际公司 The method producing 2,3,3,3 tetrafluoropropenes and the method purifying 2 chlorine 1,1,1,2 tetrafluoropropane
CN106278803A (en) * 2010-11-16 2017-01-04 霍尼韦尔国际公司 The method producing 2,3,3,3 tetrafluoropropenes and the method purifying 2 chlorine 1,1,1,2 tetrafluoropropane
CN103449962A (en) * 2013-08-15 2013-12-18 巨化集团技术中心 Synthesis method of 2-chloro-1,1,1,2-tetrafluoropropane
CN103449962B (en) * 2013-08-15 2015-06-17 巨化集团技术中心 Synthesis method of 2-chloro-1,1,1,2-tetrafluoropropane
CN104072333A (en) * 2014-05-21 2014-10-01 巨化集团技术中心 Preparation method for 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene
CN104072333B (en) * 2014-05-21 2016-04-13 巨化集团技术中心 A kind of 2-chloro-1,1, Isosorbide-5-Nitrae, the preparation method of 4,4-hexafluoro-2-butylene
CN104140355B (en) * 2014-08-07 2016-03-02 西安近代化学研究所 A kind of method of synthesizing 2-chloro-1,1,1,2-tetrafluoropropane
WO2016019718A1 (en) * 2014-08-07 2016-02-11 西安近代化学研究所 Method for preparing 2-chloro-1,1,1,2-tetrafluoropropane
CN104140355A (en) * 2014-08-07 2014-11-12 西安近代化学研究所 Method for synthesizing 2-chloro-1,1,1,2-tetrafluoropropane
CN104140354A (en) * 2014-08-07 2014-11-12 西安近代化学研究所 Method for preparing HCFC-244bb
CN105289669A (en) * 2015-11-11 2016-02-03 西安近代化学研究所 Liquid-phase fluorination catalyst and application
CN107649167A (en) * 2017-10-26 2018-02-02 金华职业技术学院 CO oxidation catalysts and preparation method thereof under a kind of steam and carbon dioxide atmosphere
CN110407661A (en) * 2018-04-28 2019-11-05 浙江蓝天环保高科技股份有限公司 The method for transformation of by-product trifluoro-ethylene in a kind of chlorotrifluoroethylene production process
CN110407661B (en) * 2018-04-28 2022-07-08 浙江蓝天环保高科技股份有限公司 Method for converting by-product trifluoroethylene in production process of chlorotrifluoroethylene
CN113966320A (en) * 2019-06-04 2022-01-21 科慕埃弗西有限公司 2-chloro-3, 3, 3-trifluoropropene (1233xf) compositions and methods for making and using the same

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