CN101028993A - Method for producign 1,1,1,3,3-propane pentafluoride - Google Patents
Method for producign 1,1,1,3,3-propane pentafluoride Download PDFInfo
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- CN101028993A CN101028993A CN 200710090539 CN200710090539A CN101028993A CN 101028993 A CN101028993 A CN 101028993A CN 200710090539 CN200710090539 CN 200710090539 CN 200710090539 A CN200710090539 A CN 200710090539A CN 101028993 A CN101028993 A CN 101028993A
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Abstract
A process for preparing 1,1,1,3,3-pentafluoropropane (HFC-245fa) from HF and 1,1,1,3,3-pentachloropropane (HCC-240fa) features the three-step gas-phase catalytic fluorinating reaction between the intermediates 1-Cl-3,3,3- trifluoropropene (HCFC-1233zd) and 1,1,1,3-tertafluoropropene (HFC-1234ze). The HCFC-1233zd, HFC-1234ze and HFC-245fa are respectively prepared in the first, second and third reactors.
Description
Technical field
The present invention relates to a kind of 1,1,1,3, the preparation method of 3-pentafluoropropane (HFC-245fa) relates in particular to a kind of with hydrogen fluoride and 1,1,1,3,3-pentachloropropane (HCC-240fa) is a raw material, through 1-chloro-3,3,3-trifluoro propene (HCFC-1233zd), 1,1,1, three step of 3-tetrafluoeopropene (HFC-1234ze) intermediate gas phase fluorination obtains 1,1,1,3, the preparation method of 3-pentafluoropropane.
Background technology
1,1,1,3, the 3-pentafluoropropane is a kind of fluorinated hydrocarbons compound to atmospheric ozone layer safety, mainly is used as trifluorochloromethane (CFC-11) and 1 at present, 1, the substitute of 1-chloro fluoroethane (HCFC-141b) whipping agent in addition, also is widely used as solvent, propellant, fire-fighting medium and dry etching agent.
At present, with 1,1,1,3, the 3-pentachloropropane is a raw material, obtains the main preparation methods that HFC-245fa is industrial HFC-245fa through fluoridizing.It is raw material with HCC-240fa that U.S. Pat 6018084, US61111500 and Chinese patent CN1206394 disclose a kind of respectively, the method for the synthetic HFC-245fa of two step gas phase catalytic fluorinations.At first, with HCC-240fa gas phase and HF reaction in the presence of fluorination catalyst, mainly contained the mixture of HCFC-1233zd, the first step reaction product is removed after the byproduct hydrogen chloride then, gas phase and HF reaction obtains HFC-245fa in the presence of fluorination catalyst.
Above-mentioned 1,1,1,3, among the 3-pentafluoropropane preparation method, because the boiling point of the raw material HCFC-1233zd (boiling point is 20.8 ℃) of second step reaction and product HFC-245fa (boiling point is 15 ℃) is approaching, can not they be separated by simple distillation, and HCFC-1233zd is not separated with HFC-245fa in the above-mentioned patent and be further described, can't learn and how target product HFC-245fa be separated from the second step reaction product, obtain single purpose product HFC-245fa.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that exists in the background technology, provides not contain HCFC-1233zd in a kind of product, and is segregative 1,1,1,3, the preparation method of 3-pentafluoropropane.
With 1,1,1,3, the 3-pentachloropropane is a raw material, and the principal reaction of the synthetic HFC-245fa of gaseous fluoridizing method is as follows:
HCC-240fa+3HF→HCFC-1233zd+4HCl (1)
In order to realize purpose of the present invention, the present invention adopts three reactors, first reactor mainly carries out the reaction that HF fluoridizes HCC-240fa, under proper reaction conditions, the transformation efficiency of HCC-240fa can reach 100%, be subjected to the influence of HCl dividing potential drop, mainly react (1), primary product is HCFC-1233zd; Second reactor mainly carries out the reaction that HF fluoridizes HCFC-1233zd, and react (2) and (3), reaction product is HFC-1234ze and HFC-245fa.And the HFC-245fa that obtains after the second reactor reaction product separated and unreacted HCFC-1233zd be circulated to second reactor and re-use, and reaction (3) moved, the selectivity of increase HFC-1234ze to the direction of HFC-1234ze; The 3rd reactor mainly reacts (3), obtains purpose product HFC-245fa.Because HFC-1234ze (boiling point is for-19 ℃) differs bigger with the boiling point of HFC-245fa, be easy to from the product stream of the 3rd reactor, separate by distillation HFC-245fa, do not contain HCFC-1233zd among the purpose product HFC-245fa.
The invention provides a kind of 1,1,1,3, the preparation method of 3-pentafluoropropane, with hydrogen fluoride and 1,1,1,3, the 3-pentachloropropane is a raw material, may further comprise the steps:
A. hydrogen fluoride, 1,1,1,3, the 3-pentachloropropane enters first reactor, reacts in the presence of fluorination catalyst, reaction conditions is: the mol ratio 5～20 of reaction pressure 0MPa～1.0MPa, HF and HCC-240fa, 2 seconds～30 seconds duration of contact, 150 ℃～350 ℃ of temperature of reaction, comprise the 1-chloro-3,3 that reaction generates, 3-trifluoro propene, hydrogenchloride and unreacted hydrogen fluoride in the product stream;
B.1-chloro-3,3, and 3-trifluoro propene and hydrogen fluoride enter second reactor, react in the presence of fluorination catalyst, reaction conditions is: the mol ratio 3～15 of reaction pressure 0MPa～1.0MPa, HF and HCFC-1233zd and HFC-245fa total amount, 5 seconds～30 seconds duration of contact, 250 ℃～380 ℃ of temperature of reaction comprise 1 of generation in the product stream, 1,1,3-tetrafluoeopropene, 1,1,1,3,3-pentafluoropropane, hydrogenchloride and unreacted hydrogen fluoride and 1-chloro-3,3, the 3-trifluoro propene;
C. hydrogen fluoride and 1,1,1, the 3-tetrafluoeopropene enters the 3rd reactor, issues angry phase catalytic fluorination reaction in the existence of catalyzer, and reaction conditions is: the mol ratio 1～5 of reaction pressure 0MPa～2.0MPa, HF and HFC-1234ze, 2 seconds～20 seconds duration of contact, 50 ℃～250 ℃ of temperature of reaction, comprise 1 of reaction generation in the product stream, 1,1,3,3-pentafluoropropane and unreacted hydrogen fluoride, 1,1,1, the 3-tetrafluoeopropene;
D. the product that obtains of step a, b flows to into first distillation tower and separates, and tower still component is 1,1,1,3,3-pentafluoropropane, 1-chloro-3,3, and 3-trifluoro propene, 1,1,1,3-tetrafluoeopropene and hydrogen fluoride, the cat head component is a hydrogenchloride, discharges reactive system;
E. the tower still component of steps d first distillation tower enters second column and separates, and tower still component is 1,1,1,3,3-pentafluoropropane, 1-chloro-3,3,3-trifluoro propene and hydrogen fluoride, the cat head component is 1,1,1, the 3-tetrafluoeopropene, 1,1,1, the 3-tetrafluoeopropene enters the 3rd reactor and reacts;
F. the step e tower still component that obtains second column enters first phase separator, phase separation temperature is-20 ℃～30 ℃, be rich in hydrofluoric inorganic first reactor and second reactor of being circulated to respectively mutually, be rich in 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3, the organic phase of 3-trifluoro propene is circulated to second reactor and re-uses;
G. the product that obtains of step f flows to into the 3rd distillation tower and separates, and tower still component is 1,1,1,3,3-pentafluoropropane and hydrogen fluoride, and the cat head component is 1,1,1, the 3-tetrafluoeopropene, 1,1,1, the 3-tetrafluoeopropene enters the 3rd reactor and reacts;
H. the tower still component of the 3rd distillation tower that obtains of step g enters second phase separator, and phase separation temperature is-20 ℃～30 ℃, is rich in to be circulated to the 3rd reactor hydrofluoric inorganic the branch mutually, be rich in 1,1,1,3, the 3-pentafluoropropane enters after-treatment system, after operations such as deacidification, rectifying, obtain target product 1,1,1,3, the 3-pentafluoropropane.
The reaction conditions of the present invention's first reactor is preferably: reaction pressure 0.3～0.6MPa, hydrogen fluoride and 1,1,1,3, the mol ratio 10～15 of 3-pentachloropropane; 5 seconds～10 seconds duration of contact; 200 ℃～250 ℃ of temperature of reaction; The reaction conditions of second reactor is preferably: reaction pressure 0.3MPa～0.6MPa; Hydrogen fluoride and 1-chloro-3,3,3-trifluoro propene and 1,1,1,3, the mol ratio 6～10 of 3-pentafluoropropane total amount; 10 seconds～15 seconds duration of contact; 300 ℃～350 ℃ of temperature of reaction, the reaction conditions of the 3rd reactor is preferably: reaction pressure 0.6MPa～1.0MPa; Hydrogen fluoride and 1,1,1, the mol ratio 1～3 of 3-tetrafluoeopropene; 5 seconds～10 seconds duration of contact; 100 ℃～150 ℃ of temperature of reaction.
Among the present invention, the reaction product of first reactor and second reactor enters first distillation tower separates, and its cat head component is HCl, discharges reactive system; Its tower still component HF, HCFC-1233zd, HFC-1234ze enter second column with HFC-245fa and further separate.The cat head component of second column is HFC-1234ze, enters the 3rd reactor and reacts, and the tower still component of second column is HF, HCFC-1233zd and HFC-245fa, enters first phase separator and separates.Hydrofluoric inorganic first reactor and second reactor of being circulated to respectively mutually is rich on the first phase separator upper strata, and lower floor is rich in 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3, and the organic phase of 3-trifluoro propene is circulated to second reactor and re-uses.The reaction product of the 3rd reactor enters the 3rd distillation tower separates, and its cat head component is HFC-1234ze, is circulated to the 3rd reactor and re-uses; Its tower still component is HF and HFC-245fa, enters second phase separator and separates.The second phase separator upper strata is rich in and is circulated to the 3rd reactor hydrofluoric inorganic the branch mutually, and lower floor is rich in 1,1,1,3, and the 3-pentafluoropropane enters after-treatment system, obtains target product 1,1,1,3, the 3-pentafluoropropane after operations such as deacidification, rectifying.
The present invention can suitably select according to the working pressure of the level of equipment, general facilities, reactive system and the isolating composition of desire etc. to the operational condition of distillation tower without limits.Working pressure is 0.1MPa～1.0MPa, preferred 0.3MPa～0.6MPa.Generally speaking, for easy and simple to handle, the working pressure of distillation tower is consistent with reactive system.Tower top temperature and tower still temperature are by working pressure and material component decision thereof.
Among the present invention, fresh HF raw material can preferably enter reactive system from first reactor and the 3rd reactor by the 3rd reactor, first reactor or/and second reactor enters reactive system.
The present invention to the catalyzer in the fluoridation without limits, any known fluorination catalyst all is applicable to the present invention, for example: chromic oxide, chromium fluoride, fluorizated chromic oxide, aluminum fluoride, fluorizated aluminum oxide, be carried on chromic oxide on gac, aluminum fluoride, the magnesium fluoride, contain chromic oxide and the activated carbon supported SbCl of multiple metal (as Zn, Co, Ni, Ge, In etc.)
5Or TiCl
4Deng.The fluorination catalyst difference that adopts, reaction conditions difference then comprises the mol ratio of temperature of reaction, reaction pressure, duration of contact and material.
The type of reactor that the present invention is used for fluoridation is not crucial, can use tubular reactor, fluidized-bed reactor etc.In addition, adiabatic reactor or isothermal reactor are also available.
Advantage of the present invention: target product 1,1,1,3, the 3-pentafluoropropane is separated from reaction product easily, and does not contain HCFC-1233zd.
Description of drawings
Fig. 1 represents 1,1,1,3, preparation technology's schema of 3-pentafluoropropane.
Label meaning in Fig. 1 is as follows.Pipeline: 1,2,4,6,7,9,10,12,13,15,16,17,18,19,20,21,23,24,26,27,28 and 29; First reactor: 3; Second reactor: 5; The 3rd reactor: 20; First distillation tower: 8; Second column: 11; The 3rd distillation tower: 22; First phase separator: 14; First phase separator 25.
Embodiment
The present invention is described in more detail with reference to Fig. 1.The mixture of fresh HCC-240fa or HCC-240fa and HF is through pipeline 1, enter by pipeline 2 in first reactor 3 that is filled with fluorination catalyst with the HF that re-uses through pipeline 16,17 circulation and to react, the reaction product pipeline 4,7 of flowing through enters first distillation tower 8 and separates; The cat head component HCl of first distillation tower 8 discharges system, and tower still component HF, HCFC-1233zd, HCFC-1234ze and HFC-245fa enter second column 11 by pipeline 9 and separate; The tower still component of second column 11 is HF, HCFC-1233zd and HFC-245fa, and tower still component enters first phase separator 14 and is separated; The upper strata of first phase separator 14 is the inorganic phase that is rich in HF, and its part enters first reactor by pipeline 16,17 circulations, and its another part enters second reactor 5 by pipeline 16,18 circulations; The lower floor of first phase separator 14 is the organic phase that is rich in HCFC-1233zd and HFC-245fa, and it enters second reactor 5 by pipeline 15 circulations; The HF and HCFC-1233zd, the HFC-45fa that enter second reactor 5 react under the effect of catalyzer, reacting product stream enters first distillation tower 8 by pipeline 6 with first reactor reaction product stream to be separated, the tower still component of first distillation tower 8 is HF, HCFC-1233zd, HFC-1234ze and HFC-245fa, enters second column 11 by pipeline 9 and separates; Distillation tower 11 cat head components are HFC-1234ze, enter three reactor 20 that fluorination catalyst be housed with HF through pipeline 28 by pipeline 13 and react, and the 3rd reactor 20 reacting product streams enter the 3rd distillation tower 22 by pipeline 21; The 3rd distillation tower 22 cat head components are unreacted HFC-1234ze, are circulated to the 3rd reactor 22 through pipeline 24,28 and re-use; The 3rd distillation tower 22 tower still components are HF and HFC-245fa, enter second phase separator 25 through pipeline 23 and are separated; Second phase separator 25 the upper strata be the inorganic phase that is rich in HF, being circulated to the 3rd reactor 22 re-uses, lower floor is the organic phase that is rich in HFC-245fa, enters the product after-treatment system by pipeline 29, can obtain purpose product HFC-245fa by deacidification, dehydration, rectifying.
Further to the detailed description of the invention, but do not limit the present invention below in conjunction with embodiment.
Embodiment 1
At internal diameter is to add 50 milliliters of chromium-based fluorination catalysts that contain Al, Zn, Mg, Ni in the carbon steel pipe of 38mm, and method for preparing catalyst is seen Chinese patent CN1651137A.First reactor is warming up to 200 ℃, feeding HF and HCC-240fa reacts, the mol ratio of control HF and HCC-240fa is 15, be 7.5 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is after HCl and HF are removed in washing, alkali cleaning, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 1.
With embodiment 1 identical operations, different is to change temperature of reaction into 150 ℃, the results are shown in Table 1.
With embodiment 1 identical operations, different is to change temperature of reaction into 250 ℃, the results are shown in Table 1.
With embodiment 1 identical operations, different is to change temperature of reaction into 350 ℃, the results are shown in Table 1.
Embodiment 5
With embodiment 1 identical operations, different is to change 5 seconds duration of contact into, the results are shown in Table 1.
Embodiment 6
With embodiment 1 identical operations, different is to change 10 seconds duration of contact into, the results are shown in Table 1.
Embodiment 7
With embodiment 1 identical operations, different is to change 30 seconds duration of contact into, the results are shown in Table 1.
Embodiment 8
With embodiment 1 identical operations, different is changes the mol ratio of HF and HCC-240fa into 5, the results are shown in Table 1.
Embodiment 9
With embodiment 1 identical operations, different is changes the mol ratio of HF and HCC-240fa into 10, the results are shown in Table 1.
With embodiment 1 identical operations, different is changes the mol ratio of HF and HCC-240fa into 20, the results are shown in Table 1.
Embodiment 11
With embodiment 1 identical operations, different is to change reaction pressure into 0.3MPa, the results are shown in Table 1.
With embodiment 1 identical operations, different is to change reaction pressure into 0.6MPa, the results are shown in Table 1.
With embodiment 1 identical operations, different is to change reaction pressure into 1.0MPa, the results are shown in Table 1.
Table 1
| Embodiment | Reaction conditions | Reaction product organism composition/% | |||||
| Temperature/℃ | Pressure/MPa | The duration of contact/second | Mol ratio HF/HCC-240fa | HCFC-1233zd | HFC-1234ze | HFC-245fa | |
| 1 | 200 | 0.1 | 7.5 | 15 | 92.1 | 6.5 | 1.4 |
| 2 | 150 | 0.1 | 7.5 | 15 | 95.6 | 4.1 | 0.3 |
| 3 | 250 | 0.1 | 7.5 | 15 | 86.5 | 8.9 | 4.6 |
| 4 | 350 | 0.1 | 7.5 | 15 | 75.8 | 13.5 | 10.7 |
| 5 | 200 | 0.1 | 5 | 15 | 98.0 | 1.9 | 0.1 |
| 6 | 200 | 0.1 | 10 | 15 | 89.8 | 7.4 | 2.8 |
| 7 | 200 | 0.1 | 30 | 15 | 65.3 | 19.7 | 15.0 |
| 8 | 200 | 0.1 | 7.5 | 5 | 99.0 | 1.0 | 0 |
| 9 | 200 | 0.1 | 7.5 | 10 | 97.4 | 2.4 | 0.2 |
| 10 | 200 | 0.1 | 7.5 | 20 | 89.5 | 7.8 | 2.7 |
| 11 | 200 | 0.3 | 7.5 | 15 | 86.4 | 9.1 | 4.5 |
| 12 | 200 | 0.6 | 7.5 | 15 | 75.6 | 13.2 | 11.2 |
| 13 | 200 | 1.0 | 7.5 | 15 | 64.3 | 16.7 | 19.0 |
Embodiment 14
At internal diameter is to add 50 milliliters of chromium-based fluorination catalysts that contain Al, Zn, Mg, Ni in the carbon steel pipe of 38mm, method for preparing catalyst is seen Chinese patent CN1651137A, second reactor is warming up to 350 ℃, feeding HF and HCFC-1233zd reacts, the mol ratio of control HF and HCFC-1233zd is 6, be 10 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is after HCl and HF are removed in washing, alkali cleaning, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change temperature of reaction into 250 ℃, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change temperature of reaction into 330 ℃, the results are shown in Table 2.
Embodiment 17
With embodiment 14 identical operations, different is to change temperature of reaction into 380 ℃, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change 5 seconds duration of contact into, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change 15 seconds duration of contact into, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change 30 seconds duration of contact into, the results are shown in Table 2.
With embodiment 14 identical operations, different is changes the mol ratio of HF and HCFC-1233zd into 3 and the results are shown in Table 2.
With embodiment 14 identical operations, different is changes the mol ratio of HF and HCFC-1233zd into 10, the results are shown in Table 2.
Embodiment 23
With embodiment 14 identical operations, different is changes the mol ratio of HF and HCFC-1233zd into 15, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change reaction pressure into 0.3MPa, the results are shown in Table 2.
Embodiment 25
With embodiment 14 identical operations, different is to change reaction pressure into 0.6MPa, the results are shown in Table 2.
With embodiment 14 identical operations, different is to change reaction pressure into 1.0MPa, the results are shown in Table 2.
Table 2
| Embodiment | Reaction conditions | Reaction product organism composition/% | |||||
| Temperature/℃ | Pressure/MPa | The duration of contact/second | Mol ratio HF/HCFC-1233zd | HCFC-1233zd | HFC-1234ze | HFC-245fa | |
| 14 | 350 | 0.1 | 10 | 6 | 28.5 | 50.7 | 20.8 |
| 15 | 250 | 0.1 | 10 | 6 | 64.9 | 22.6 | 12.5 |
| 16 | 330 | 0.1 | 10 | 6 | 53.5 | 30.8 | 15.7 |
| 17 | 380 | 0.1 | 10 | 6 | 19.5 | 63.0 | 17.5 |
| 18 | 350 | 0.1 | 5 | 6 | 41.7 | 43.7 | 14.6 |
| 19 | 350 | 0.1 | 15 | 6 | 20.3 | 48.1 | 26.2 |
| 20 | 350 | 0.1 | 30 | 6 | 17.5 | 45.1 | 37.4 |
| 21 | 350 | 0.1 | 10 | 3 | 40.5 | 45.5 | 13.6 |
| 22 | 350 | 0.1 | 10 | 10 | 20.0 | 49.4 | 30.6 |
| 23 | 350 | 0.1 | 10 | 15 | 15.2 | 45.7 | 39.1 |
| 24 | 350 | 0.3 | 10 | 6 | 21.6 | 49.5 | 28.9 |
| 25 | 350 | 0.6 | 10 | 6 | 15.9 | 40.4 | 43.7. |
| 26 | 350 | 1.0 | 10 | 6 | 10.5 | 29.2 | 60.3 |
At internal diameter is to add 50 milliliters in the carbon steel pipe of 38mm to contain Al, Zn, Mg, the chromium-based fluorination catalyst of Ni, method for preparing catalyst is seen Chinese patent CN1651137A, be warming up to 350 ℃, feed HCFC-1233zd, HFC-245fa and HF react, the molar ratio of control HFC-245fa and HCFC-1233zd is 0.25: 1, HF and mol ratio (HCFC-1233zd+HFC-245fa) are 6, be 5 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is through washing, after HCl and HF are removed in alkali cleaning,, the results are shown in Table 3 with organic composition in the gas chromatographic analysis reaction product.
With embodiment 27 identical operations, different is with the molar ratio of HFC-245fa and HCFC-1233zd is 0.5: 1, the results are shown in Table 3.
With embodiment 27 identical operations, different is with the molar ratio of HFC-245fa and HCFC-1233zd is 1: 1, the results are shown in Table 3.
Table 3
| Embodiment | The HFC-245fa/HCFC-1233zd molar ratio | Reaction product organism composition/% | ||
| HCFC-1233zd | HFC-1234ze | HFC- | ||
| 27 | 0.25∶1 | 20.6 | 53.9 | 20.5 |
| 28 | 0.5∶1 | 15.0 | 62.7. | 22.3 |
| 29 | 1∶1 | 10.3 | 52.1 | 37.6 |
Embodiment 30:
At internal diameter is to add 50 milliliters of chromium-based fluorination catalysts that contain Al, Zn, Mg, Ni in the carbon steel pipe of 38mm, method for preparing catalyst is seen Chinese patent CN1651137A, the 3rd reactor is warming up to 150 ℃, feeding HF and HFC-1234ze reacts, the mol ratio of control HF and HFC-1234ze is 2, be 7.5 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is after HCl and HF are removed in washing, alkali cleaning, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 2.
Embodiment 31
With embodiment 30 identical operations, different is to change temperature of reaction into 100 ℃, the results are shown in Table 2.
Embodiment 32
With embodiment 30 identical operations, different is to change temperature of reaction into 200 ℃, the results are shown in Table 2.
Embodiment 33
With embodiment 30 identical operations, different is to change temperature of reaction into 250 ℃, the results are shown in Table 2.
Embodiment 34
With embodiment 30 identical operations, different is to change 5 seconds duration of contact into, the results are shown in Table 2.
Embodiment 35
With embodiment 30 identical operations, different is to change 10 seconds duration of contact into, the results are shown in Table 2.
Embodiment 36
With embodiment 30 identical operations, different is to change 30 seconds duration of contact into, the results are shown in Table 2.
Embodiment 37
With embodiment 30 identical operations, different is changes the mol ratio of HF and HFC-1234ze into 1, the results are shown in Table 2.
Embodiment 38
With embodiment 30 identical operations, different is changes the mol ratio of HF and HFC-1234ze into 3, the results are shown in Table 2.
Embodiment 39
With embodiment 30 identical operations, different is changes the mol ratio of HF and HFC-1234ze into 5, the results are shown in Table 2.
Embodiment 40
With embodiment 30 identical operations, different is to change reaction pressure into 0.3MPa, the results are shown in Table 2.
Embodiment 41
With embodiment 30 identical operations, different is to change reaction pressure into 0.6MPa, the results are shown in Table 2.
Embodiment 42
With embodiment 30 identical operations, different is to change reaction pressure into 1.0MPa, the results are shown in Table 2.
The reaction result of table 3 the 3rd reactor
| Embodiment | Reaction conditions | Reaction product organism composition/% | ||||
| Temperature/℃ | Pressure/MPa | Duration of contact/s | Mol ratio HF/HFC-1234ze | HFC-1234ze | HFC-245fa | |
| 30 | 150 | 0.1 | 7.5 | 2 | 32.7 | 67.3 |
| 31 | 100 | 0.1 | 7.5 | 2 | 33.1 | 66.9 |
| 32 | 200 | 0.1 | 7.5 | 2 | 40.2 | 59.8 |
| 33 | 250 | 0.1 | 7.5 | 2 | 46.9 | 53.1 |
| 34 | 150 | 0.1 | 5 | 2 | 35.0 | 65.0 |
| 35 | 150 | 0.1 | 10 | 2 | 28.5 | 71.5 |
| 36 | 150 | 0.1 | 30 | 2 | 19.8 | 80.2 |
| 37 | 150 | 0.1 | 7.5 | 1 | 41.8 | 58.2 |
| 38 | 150 | 0.1 | 7.5 | 3 | 29.4 | 70.6 |
| 39 | 150 | 0.1 | 7.5 | 5 | 26.6 | 73.4 |
| 40 | 150 | 0.3 | 7.5 | 2 | 25.7 | 74.3 |
| 41 | 150 | 0.6 | 7.5 | 2 | 16.3 | 83.7 |
| 42 | 150 | 1.0 | 7.5 | 2 | 6.4 | 93.6 |
Claims (2)
1, a kind of 1,1,1,3, the preparation method of 3-five fluorine propylene may further comprise the steps:
A. hydrogen fluoride, 1,1,1,3, the 3-pentachloropropane enters first reactor, reacts in the presence of fluorination catalyst, reaction conditions is: reaction pressure 0MPa～1.0MPa, hydrogen fluoride and 1,1,1,3, the mol ratio 5～20 of 3-pentachloropropane, 2 seconds～30 seconds duration of contact, 150 ℃～350 ℃ of temperature of reaction comprise the 1-chloro-3 that reaction generates in the product stream, 3,3-trifluoro propene, hydrogenchloride and unreacted hydrogen fluoride;
B.1-chloro-3,3, and 3-trifluoro propene and hydrogen fluoride enter second reactor, react in the presence of fluorination catalyst, reaction conditions is: reaction pressure 0MPa～1.0MPa, hydrogen fluoride and 1-chloro-3,3,3-trifluoro propene and 1,1,1,3, the mol ratio 3～15 of 3-five fluorine propylene total amounts, 5 seconds～30 seconds duration of contact, 250 ℃～380 ℃ of temperature of reaction comprise 1,1 of generation in the product stream, 1,3-tetrafluoeopropene, 1,1,1,3,3-pentafluoropropane, hydrogenchloride and unreacted hydrogen fluoride and 1-chloro-3,3, the 3-trifluoro propene;
C. hydrogen fluoride and 1,1,1, the 3-tetrafluoeopropene enters the 3rd reactor, existence at catalyzer issues angry phase catalytic fluorination reaction, and reaction conditions is: reaction pressure 0MPa～2.0MPa, hydrogen fluoride and 1,1,1, the mol ratio 1～5 of 3-tetrafluoeopropene, 2 seconds～20 seconds duration of contact, 50 ℃～250 ℃ of temperature of reaction comprise 1,1 of reaction generation in the product stream, 1,3,3-pentafluoropropane and unreacted hydrogen fluoride, 1,1,1, the 3-tetrafluoeopropene;
D. the product that obtains of step a, b flows to into first distillation tower and separates, and tower still component is 1,1,1,3,3-pentafluoropropane, 1-chloro-3,3, and 3-trifluoro propene, 1,1,1,3-tetrafluoeopropene and hydrogen fluoride, the cat head component is a hydrogenchloride, discharges reactive system;
E. the tower still component of steps d first distillation tower enters second column and separates, and tower still component is 1,1,1,3,3-pentafluoropropane, 1-chloro-3,3,3-trifluoro propene and hydrogen fluoride, the cat head component is 1,1,1, the 3-tetrafluoeopropene, 1,1,1, the 3-tetrafluoeopropene enters the 3rd reactor and reacts;
F. the step e tower still component that obtains second column enters first phase separator, phase separation temperature is-20 ℃～30 ℃, be rich in hydrofluoric inorganic first reactor and second reactor of being circulated to respectively mutually, be rich in 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3, the organic phase of 3-trifluoro propene is circulated to second reactor and re-uses;
G. the product that obtains of step f flows to into the 3rd distillation tower and separates, and tower still component is 1,1,1,3,3-pentafluoropropane and hydrogen fluoride, and the cat head component is 1,1,1, the 3-tetrafluoeopropene, 1,1,1, the 3-tetrafluoeopropene enters the 3rd reactor and reacts;
H. the tower still component of the 3rd distillation tower that obtains of step g enters second phase separator, and phase separation temperature is-20 ℃～30 ℃, is rich in to be circulated to the 3rd reactor hydrofluoric inorganic the branch mutually, be rich in 1,1,1,3, the 3-pentafluoropropane enters after-treatment system, after operations such as deacidification, rectifying, obtain target product 1,1,1,3, the 3-pentafluoropropane.
2, according to claim 11,1,1,3, the preparation method of 3-pentafluoropropane is characterized in that the reaction conditions of first reactor described in the step a is: reaction pressure 0.3MPa～0.6MPa, hydrogen fluoride and 1,1,1,3, the mol ratio 10～15 of 3-pentachloropropane, 5 seconds～10 seconds duration of contact, 200 ℃～250 ℃ of temperature of reaction; The reaction conditions of second reactor described in the step b is: reaction pressure 0.3MPa～0.6MPa, hydrogen fluoride and 1-chloro-3,3,3-trifluoro propene and 1,1,1,3, the mol ratio 6～10 of 3-pentafluoropropane total amount, 10 seconds～15 seconds duration of contact, 300 ℃～350 ℃ of temperature of reaction; The reaction conditions of the 3rd reactor described in the step c is: reaction pressure 0.6MPa～1.0MPa, hydrogen fluoride and 1,1,1, the mol ratio 1～3 of 3-tetrafluoeopropene, 5 seconds～10 seconds duration of contact, 100 ℃～150 ℃ of temperature of reaction.
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| EP2341040A1 (en) * | 2008-09-25 | 2011-07-06 | Central Glass Company, Limited | Process for producing 1,3,3,3-tetrafluoropropene |
| US8436217B2 (en) | 2011-04-25 | 2013-05-07 | Honeywell International Inc. | Integrated process to co-produce 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene |
| CN103214342A (en) * | 2013-03-29 | 2013-07-24 | 浙江衢化氟化学有限公司 | Synthetic method of 1,1,1,3,3-perfluoropropane |
| US8664456B2 (en) | 2012-03-28 | 2014-03-04 | Honeywell International Inc. | Integrated process for the co-production of trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane |
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| EP2341040A1 (en) * | 2008-09-25 | 2011-07-06 | Central Glass Company, Limited | Process for producing 1,3,3,3-tetrafluoropropene |
| EP2341040A4 (en) * | 2008-09-25 | 2014-03-05 | Central Glass Co Ltd | Process for producing 1,3,3,3-tetrafluoropropene |
| US9051231B2 (en) | 2008-09-25 | 2015-06-09 | Central Glass Company, Limited | Process for producing 1,3,3,3-tetrafluoropropene |
| US8436217B2 (en) | 2011-04-25 | 2013-05-07 | Honeywell International Inc. | Integrated process to co-produce 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene |
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| CN111875473A (en) * | 2020-06-09 | 2020-11-03 | 浙江省化工研究院有限公司 | Preparation method of HFC-365mfc and HFC-245fa |
| CN111875473B (en) * | 2020-06-09 | 2022-08-02 | 浙江省化工研究院有限公司 | Preparation method of HFC-365mfc and HFC-245fa |
| CN113501743A (en) * | 2021-08-19 | 2021-10-15 | 山东华安新材料有限公司 | Preparation method of 1,1,1,3, 3-pentafluoropropane |
| CN113501743B (en) * | 2021-08-19 | 2024-03-29 | 山东华安新材料有限公司 | Preparation method of 1, 3-pentafluoropropane |
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