CN101117305B - Method for preparing 1,1,1,2-tetrafluoro thane - Google Patents
Method for preparing 1,1,1,2-tetrafluoro thane Download PDFInfo
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- CN101117305B CN101117305B CN200710090530XA CN200710090530A CN101117305B CN 101117305 B CN101117305 B CN 101117305B CN 200710090530X A CN200710090530X A CN 200710090530XA CN 200710090530 A CN200710090530 A CN 200710090530A CN 101117305 B CN101117305 B CN 101117305B
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Abstract
The invention discloses a method for preparing 1, 1, 1, 2-four fluorine hexane (HFC-134a), which uses fluorine hydride (HF) and trichloroethylene (TCE) as raw material. The HFC-134a is made by 1, 1, 1-three fluorine-2-antidolorin (HCFC-133a) through two steps gas phase fluorine reaction. A first reactor is mainly used to perform TCE mixture HCFC-133a. A second reactor is mainly used to perform fluorine HCFC-133a to compound the HFC-134a. The product in the second reactor removes HF and HCFC-133a through distilling separation, then cycles to the first reactor. The contents of product 1, 1- two fluorine (HCFC-1122) is reduced. The HFC-134a and HC1 are separated from the first reactor products to enter after-treatment system by adopting distill tower. The Unreacted TCE cycles to the first reactor and continue reaction. The HF and HCFC-133a of the first reactor and the second reactor are separated by adopting phase separator. The HF cycles to the first reactor and the second reactor and continues reaction and HCFC-133a cycles to the second reactor and continues reaction. The invention is mainly used to prepare1, 1, 1, 2-four fluorine hexane HFC-134a.
Description
Technical field
The present invention relates to a kind of 1,1,1, the preparation method of 2-Tetrafluoroethane relates in particular to and a kind ofly obtains 1 by hydrogen fluoride gas phase catalytic fluorination trieline (TCE), 1,1-three fluoro-2-monochloroethane (HCFC-133a) are then in further gas phase catalytic fluorination HCFC- 133a production 1,1,1, the preparation method of 2-Tetrafluoroethane (HFC-134a).
Background technology
1,1,1, the 2-Tetrafluoroethane is a kind of fluorinated hydrocarbons compound to atmospheric ozone layer safety, mainly is used as the substitute of methyl chlorofluoride (CFC-12) refrigeration agent at present, in addition, also is widely used as whipping agent, solvent, propellant, fire-fighting medium and dry etching agent.
The industrial method that the multiple HFC-134a of preparation is arranged is a raw material with TCE and HF wherein at present, and the synthetic HFC-134a of two step gas phase catalytic fluorinations is the industrial HFC-134a preparation method who generally adopts.CN1045200C discloses the preparation method that a kind of two step gas phase catalytic fluorinations obtain HFC-134a, this method adopts two reactors, first reactor carries out the reaction that hydrogen fluoride gas phase catalytic fluorination TCE obtains HCFC-133a, reacting product stream enters distillation tower to be separated, HF after the separation, HCFC-133a and fresh HF enter second reactor, fluoridize the reaction of HCFC-133a.Whole product streams of second reactor enter first reactor with fresh TCE.Second reactor product stream enters first reactor, helps the transfer of the first reactor internal reaction heat, 1 of other second reactor generation, and 1-difluoro vinylchlorid (HCFC-1122) is fluoridized in first reactor is HCFC-133a.
In this method, be converted into HCFC-133a although help the transfer and the HCFC-1122 of the first reactor reaction heat, but the total overall reaction product of second reactor flows to into first reactor, the catalyzer of first reactor is not obtained fully, effectively utilize, and causes catalyst levels bigger.The temperature of reaction of first reactor is about 300 ℃, makes the content of HCFC-1122 still be in a higher level.
Summary of the invention
The objective of the invention is to overcome the deficiency that exists in the background technology, provide a kind of first reactor catalyst consumption few, temperature of reaction is low, by-products content few 1,1,1, the preparation method of 2-Tetrafluoroethane.
In order to realize purpose of the present invention, the present invention separates HCFC-133a from second reactor product stream, one, make in second reactor product stream that enters first reactor and do not contain HCFC-133a, effectively reduce the temperature of reaction of first reactor, and the transformation efficiency of TCE still remains on the higher level, also helps the reaction that HCFC-1122 and HF generate HCFC-133a more, has reduced the content of HCFC-1122 among the target product HFC-134a; The total amount that its two, the second reactor product stream enters first reactor reduces, and on the maintenance basis of the duration of contact suitable with background technology, catalyst levels reduces.
The present invention separates by the product stream of distillation tower to second reactor, cat head component HFC-134a and HCl are circulated to first reactor, tower still component HF utilizes phase separator further to separate with HCFC-133a, and the HF after will separating circulate first reactor to and second reactor, HCFC-133a is circulated to and carries out fluoridation in second fluorination reactor again.
The invention provides a kind of is raw material with trieline and hydrogen fluoride, and two step gas phase catalytic fluorinations produce 1,1,1, the preparation method of 2-Tetrafluoroethane, and it may further comprise the steps:
A. hydrogen fluoride, trieline and isolate 1,1, second reactor product stream behind the 1-three fluoro-2-monochloroethane enters first reactor, 200 ℃～260 ℃ fluoridation takes place in the presence of fluorination catalyst, comprises 1,1 of reaction generation in the product stream, 1-three fluoro-2-monochloroethane, 1,1,1,2-Tetrafluoroethane, hydrogenchloride and unreacted hydrogen fluoride and trieline;
B.1,1,1-three fluoro-2-monochloroethane and hydrogen fluoride enter second reactor, and 300 ℃～380 ℃ are continued fluoridation in the presence of fluorination catalyst, comprise 1 in the product stream of second reactor, 1,1,2-Tetrafluoroethane, 1,1-difluoro vinylchlorid, hydrogenchloride and unreacted hydrogen fluoride and 1,1,1-three fluoro-2-monochloroethane;
C. the product of step a flows to into first distillation tower and separates, and tower still component is 1,1,1-three fluoro-2-monochloroethane, hydrogen fluoride and trieline, cat head component 1,1,1,2-Tetrafluoroethane, 1, technologies such as 1-difluoro vinylchlorid, hydrogenchloride deacidify, dehydration, rectifying obtain target product 1,1,1, the 2-Tetrafluoroethane;
D. step c obtains tower still component and enters second column and separate, and the cat head component is 1,1,1-three fluoro-2-monochloroethane and hydrogen fluoride, and tower still component is the trieline that contains low amount of fluorinated hydrogen, is circulated to first reactor;
E. the product that obtains of step b flows to into the 3rd distillation tower and separates, and tower still component is hydrogen fluoride and 1,1,1-three fluoro-2-monochloroethane, and the cat head component is 1,1,1,2-Tetrafluoroethane, 1,1-difluoro vinylchlorid and hydrogenchloride are circulated to first reactor;
F. the cat head component that obtains of steps d enters phase separator with tower still component that step e obtains and separates, the branch temperature is-30 ℃～60 ℃ mutually, be rich in hydrofluoric inorganic first reactor and second reactor of being circulated to mutually after dividing mutually, be rich in 1,1, the organic phase of 1-three fluoro-2-monochloroethane is circulated to second reactor.
The cat head component of the 3rd distillation tower described in the step e of the present invention enters first reactor, under the low temperature HCFC-1122 in the product is fluoridized to generate HCFC-133a.Also can be with the cat head component 1,1,1 of the 3rd distillation tower described in the step e, 2-Tetrafluoroethane, 1,1-difluoro vinylchlorid enter the 4th distillation tower with hydrogenchloride further separates cat head component hydrogenchloride, discharge from reaction system, tower still component is 1,1,1,2-Tetrafluoroethane and 1,1-difluoro vinylchlorid is circulated to first reactor, can reduce the fluoridation negative impact of the HCl of first reactor, further increase transformation efficiency and the effective product selectivity of TCE TCE.
For the HF that controls reactive system and the mol ratio of organic materials, a large amount of HF is circulated to first reactor and second reactor by phase separator.Among the present invention, fresh HF raw material can or enter reactive system by first reactor, second reactor simultaneously by any one reactor in first reactor, second reactor.
The isolating hydrogen fluoride of step e described in the step f of the present invention, 1,1,1-three fluoro-2-monochloroethane and the isolating hydrogen fluoride of steps d, 1,1,1-three fluoro-2-monochloroethane both can mix the back and separate in same phase separator, also can be separated respectively.The temperature of branch mutually of dividing device mutually be HCFC-133a can with the isolating key of HF, temperature is low more, separating effect is good more.Generally, dividing the temperature of branch mutually of device mutually is-30 ℃～40 ℃, preferred-10 ℃～20 ℃.
Among the present invention, the transformation efficiency of TCE is greater than 95% in first reactor, even greater than 99%, the time of the distillation Tata still enrichment TCE of the described separation of steps d TCE and HF, HCFC-133a is longer, so intermittence of the present invention is circulated to first reactor with the TCE that contains small amount of H F of knockout tower still and further reacts.
The type of reactor that is used for fluoridation is not crucial, can use tubular reactor, fluidized-bed reactor etc.In addition, adiabatic reactor or isothermal reactor also can be used to the present invention.
In fluoridation, chromic oxide, chromium fluoride, fluorizated chromic oxide, aluminum fluoride, fluorizated aluminum oxide, the known fluorination catalysts such as chromic oxide that are carried on the chromic oxide on gac, aluminum fluoride, the magnesium fluoride and contain multiple metal (as Zn, Co, Ni, Ge, In etc.) all are applicable to the present invention.The present invention preferably contains the chromium-based catalysts of Al, Zn, Mg, Ni as fluorination catalyst, and its preparation method is seen Chinese patent CN1651137A.
The reaction pressure of first reactor is 0MPa～2.0MPa, preferred 0.5MPa～1.5MPa, more preferably 0.8MPa～1.2MPa; The mol ratio of HF and TCE is 3～15:1, preferred 6～8:1; Be 1 second～30 seconds duration of contact, preferred 5 seconds～10 seconds; Temperature of reaction is 200 ℃～300 ℃, preferred 220 ℃～260 ℃.
The reaction pressure of second reactor is 0MPa～2.0MPa, preferred 0.5MPa～1.5MPa, more preferably 0.8MPa～1.2MPa; The mol ratio of HF and HCFC-133a is 3～15:1, is preferably 8～12:1; Be 1～30 second duration of contact, is preferably 5 seconds～10 seconds; Temperature of reaction is 300 ℃～380 ℃, preferred 330 ℃～350 ℃.The pressure of first reactor and second reactor can be the same or different.
The present invention can suitably select according to the working pressure of the level of equipment, general facilities, reactive system and the isolating component of desire etc. to the operational condition of distillation tower without limits.Working pressure is 0.2MPa～2.0MPa, preferred 0.5MPa～1.5MPa, more preferably 0.8MPa～1.2MPa.Generally speaking, the working pressure of distillation tower is consistent with reactive system.
By implementing the present invention, the transformation efficiency of TCE can reach 99.5% in first reactor, and the selectivity of active principle (HCFC-133a+HFC-134a) can reach 98%; The transformation efficiency of HCFC-133a is greater than 25% in second reactor, and the selectivity of HFC-134a is greater than 95%; The content of HCFC-1122 is lower than 100ppm among the thick product HFC-134a.Simultaneously, the volume and the catalyst consumption of first reactor reduce than background technology, and because temperature of reaction is lower, have delayed the knot charcoal speed of catalyst surface, make life of catalyst obtain prolongation.
Description of drawings
The present invention is described in more detail with reference to Fig. 1, Fig. 2
Fig. 1 represents that HFC-134a and HCl are circulated to 1,1,1 of first reactor in second reactor product stream, the process flow sheet of 2-Tetrafluoroethane preparation.
Fig. 2 represents that HFC-134a is circulated to 1,1,1 of first reactor in second reactor product stream, the process flow sheet of 2-Tetrafluoroethane preparation.
At Fig. 1, the label meaning in 2 is as follows.Pipeline: 1,2,4,6,7,9,10,11,13,14,15,16,17,18,19,21,23,24,26 and 27; First reactor: 3; Second reactor: 20; First distillation tower: 5; Second column: 8; The 3rd distillation tower: 22; The 4th distillation tower: 25; Phase separator: 12.
Embodiment
The present invention is described in more detail with reference to Fig. 1.The mixture of fresh TCE or TCE and HF is through pipeline 1, with the HF logistics that recycles, the TCE logistics that recycles and from second reactor product stream isolated HFC-134a and HCl enter in first reactor 3 that is filled with fluorination catalyst by pipeline 2 and react, the reaction product pipeline 4 of flowing through enters first distillation tower 5 and separates; First distillation tower, 5 cat head component HFC-134a and HCl enter the product after-treatment system by pipeline 7, can obtain the HFC-134a product by deacidification, dehydration, rectifying, and tower still component enters second column 8 by pipeline 6 and separates; The TCE that second column 8 tower stills contain small amount of H F enters first reactor by pipeline 9 circulations, and cat head component HCFC-133a and HF enter phase separator 12 by pipeline 10,11 and be separated; The upper strata of phase separator 12 is the inorganic phase that is rich in HF, its part enters first reactor by pipeline 13,14 circulations, its another part enters second reactor 20 by pipeline 16,17 circulations, the lower floor of phase separator 12 is the organic phase that is rich in HCFC-133a, enters second reactor by pipeline 15,17 circulations; The HF and the HCFC-133a that enter second reactor 20 react under the effect of fluorination catalyst, and reacting product stream enters the 3rd distillation tower 22 by pipeline 21 to be separated; The cat head component of the 3rd distillation tower 22 is HFC-134a and the HCl that contains HCFC-1122, enter first reactor by pipeline 24,14, reduce the HCFC-1122 in the product, tower still component HF and HCFC-133a enter phase separator 12 by pipeline 23,11 and are separated.
The reaction conditions of first reactor is: 220 ℃ of temperature of reaction, reaction pressure 0.05MPa, HF and TCE mol ratio 8:1,5 seconds duration of contact; The reaction conditions of second reactor is: 330 ℃ of temperature of reaction, and reaction pressure 0.05MPa, HF and HCFC-133a mol ratio 10:1,6 seconds duration of contact, reaction result sees Table 1.
With embodiment 1 identical operations, different is changes the temperature of reaction of first reactor into 260 ℃, and reaction result sees Table 1.
Embodiment 3
With embodiment 1 identical operations, different is changes the temperature of reaction of second reactor into 350 ℃, and reaction result sees Table 1.
Embodiment 4
With embodiment 1 identical operations, different is changes the temperature of reaction of first reactor into 260 ℃, and the temperature of reaction of second reactor changes 350 ℃ into, and reaction result sees Table 1.
Table 1
| |
1 | 2 | 3 | 4 |
| The first reactor reaction temperature (℃) | 220 | 260 | 220 | 260 |
| The second reactor reaction temperature (℃) | 330 | 330 | 350 | 350 |
| The first reactor TCE transformation efficiency (mole %) | 98.3 | 98.7 | 98.3 | 98.7 |
| The selectivity of the first reactor HCFC-133a+HFC-134a (mole %) | 97.6 | 96.9 | 97.6 | 96.9 |
| The second reactor HCFC-133a transformation efficiency (mole %) | 25.3 | 25.3 | 28.5 | 28.5 |
| The selectivity of the second reactor HFC-134a (mole %) | 97.1 | 97.1 | 95.9 | 95.9 |
| The content (ppm) of HCFC-1122 among the thick product HFC-134a | 60 | 80 | 90 | 100 |
Embodiment 5:
The present invention is described in more detail with reference to Fig. 2.Shown in Figure 11,1,1, on the 2-Tetrafluoroethane preparation method basis, increased the 4th distillation tower 25 that separates HFC-134a and HCl in second reactor product stream.In this case, the cat head component HFC-134a of the 3rd distillation tower 22 and HCl directly do not circulate and enter first reactor, further separate but enter the 4th distillation tower 25 by pipeline 24; The tower still component HFC-134a of the 4th distillation tower 25 enters first reactor by pipeline 26,14 circulations, reduces the HCFC-1122 in the product, and cat head component HCl removes acid system by pipeline 27.
The reaction conditions of first reactor is: 220 ℃ of temperature of reaction, reaction pressure 0.05MPa, HF and TCE mol ratio 8:1,5 seconds duration of contact; The reaction conditions of second reactor is: 330 ℃ of temperature of reaction, and reaction pressure 0.05MPa, HF and HCFC-133a mol ratio 10:1,6 seconds duration of contact, reaction result sees Table 2.
Embodiment 6
With embodiment 5 identical operations, different is changes the temperature of reaction of first reactor into 260 ℃, and reaction result sees Table 2.
With embodiment 5 identical operations, different is changes the temperature of reaction of second reactor into 350 ℃, and reaction result sees Table 2.
With embodiment 5 identical operations, different is changes the temperature of reaction of first reactor into 260 ℃, and the temperature of reaction of second reactor changes 350 ℃ into, and reaction result sees Table 2.
Table 2
| Embodiment | 5 | 6 | 7 | 8 |
| The first reactor reaction temperature (℃) | 220 | 260 | 220 | 260 |
| The second reactor reaction temperature (℃) | 330 | 330 | 350 | 350 |
| The first reactor TCE transformation efficiency (mole %) | 99.2 | 99.5 | 99.2 | 99.5 |
| The selectivity of the first reactor HCFC-133a+HFC-134a (mole %) | 98.5 | 97.9 | 98.5 | 97.9 |
| The second reactor HCFC-133a transformation efficiency (mole %) | 25.3 | 25.3 | 28.5 | 28.5 |
| The selectivity of the second reactor HFC-134a (mole %) | 97.1 | 97.1 | 95.9 | 95.9 |
| The content (ppm) of HCFC-1122 among the thick product HFC-134a | 50 | 60 | 80 | 90 |
Claims (3)
1. one kind 1,1, the preparation method of 2-Tetrafluoroethane is a raw material with hydrogen fluoride and trieline, may further comprise the steps:
A. hydrogen fluoride, trieline and isolate 1,1, second reactor product stream behind the 1-three fluoro-2-monochloroethane enters first reactor, 200 ℃～260 ℃ fluoridation takes place in the presence of fluorination catalyst, comprises 1,1 of reaction generation in the product stream, 1-three fluoro-2-monochloroethane, 1,1,1,2-Tetrafluoroethane, hydrogenchloride and unreacted hydrogen fluoride and trieline;
B.1,1,1-three fluoro-2-monochloroethane and hydrogen fluoride enter second reactor, and 300 ℃～380 ℃ are continued fluoridation in the presence of fluorination catalyst, comprise 1 in the product stream of second reactor, 1,1,2-Tetrafluoroethane, 1,1-difluoro vinylchlorid, hydrogenchloride and unreacted hydrogen fluoride and 1,1,1-three fluoro-2-monochloroethane;
C. the product of step a flows to into first distillation tower and separates, and tower still component is 1,1,1-three fluoro-2-monochloroethane, hydrogen fluoride and trieline, cat head component 1,1,1,2-Tetrafluoroethane, 1, technologies such as 1-difluoro vinylchlorid, hydrogenchloride deacidify, dehydration, rectifying obtain target product 1,1,1, the 2-Tetrafluoroethane;
D. step c obtains tower still component and enters second column and separate, and the cat head component is 1,1,1-three fluoro-2-monochloroethane and hydrogen fluoride, and tower still component is the trieline that contains low amount of fluorinated hydrogen, is circulated to first reactor;
E. the product that obtains of step b flows to into the 3rd distillation tower and separates, and tower still component is hydrogen fluoride and 1,1,1-three fluoro-2-monochloroethane, and the cat head component is 1,1,1,2-Tetrafluoroethane, 1,1-difluoro vinylchlorid and hydrogenchloride are circulated to first reactor;
F. the cat head component that obtains of steps d enters phase separator with tower still component that step e obtains and separates, the branch temperature is-30 ℃～60 ℃ mutually, be rich in hydrofluoric inorganic first reactor and second reactor of being circulated to mutually after dividing mutually, be rich in 1,1, the organic phase of 1-three fluoro-2-monochloroethane is circulated to second reactor.
2. according to claim 11,1,1,2-Tetrafluoroethane preparation method is characterized in that the cat head component 1 of the 3rd distillation tower described in the step e, 1,1,2-Tetrafluoroethane, 1,1-difluoro vinylchlorid also can enter the 4th distillation tower with hydrogenchloride to be separated, cat head component hydrogenchloride is discharged from reaction system; Tower still component is 1,1,1,2-Tetrafluoroethane and 1, and 1-difluoro vinylchlorid is circulated to first reactor.
3. according to claim 1 and 21,1,1,2-Tetrafluoroethane preparation method is characterized in that fresh hydrogen fluoride raw material enters first reactor and/or second reactor.
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| CN103524292B (en) * | 2013-10-11 | 2015-01-21 | 太仓中化环保化工有限公司 | Dehydration system of 1, 1, 1, 2-tetrafluoroethane crude product |
| CN103497087B (en) * | 2013-10-11 | 2015-03-25 | 太仓中化环保化工有限公司 | Dehydration method of crude product of 1,1,1,2-tetrafluoroethane |
| CN105037079A (en) * | 2015-06-02 | 2015-11-11 | 江苏三美化工有限公司 | Rectification technique of 1,1,1,2-tetrafluoroethane |
| CN108623431A (en) * | 2018-06-28 | 2018-10-09 | 江苏三美化工有限公司 | A method of 1,1,1,2- tetrafluoroethane is purified by purification reaction |
| CN111686670B (en) * | 2020-06-28 | 2021-10-15 | 安徽威驰化工有限责任公司 | Cold treatment device and method for 2-ethoxypropylene |
Citations (5)
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| CN1057253A (en) * | 1990-03-29 | 1991-12-25 | 帝国化学工业公司 | 1,1,1, the preparation method of 2-Tetrafluoroethane |
| CN1082019A (en) * | 1992-08-10 | 1994-02-16 | 昭和电工株式会社 | 1,1,1, the production method of 2-Tetrafluoroethane |
| CN1088196A (en) * | 1992-08-05 | 1994-06-22 | 昭和电工株式会社 | 1,1,1, the production method of 2-Tetrafluoroethane |
| US5426251A (en) * | 1991-11-27 | 1995-06-20 | Daikin Industries, Ltd. | Process for preparing 1,1,1-trifluoro-2-chloroethane and/or 1,1,1,2-tetrafluoroethane |
| CN1153160A (en) * | 1995-12-27 | 1997-07-02 | 西安近代化学研究所 | Process for producing 1,1,1,2-tetrafluoroethane |
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- 2007-04-11 CN CN200710090530XA patent/CN101117305B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057253A (en) * | 1990-03-29 | 1991-12-25 | 帝国化学工业公司 | 1,1,1, the preparation method of 2-Tetrafluoroethane |
| CN1059511A (en) * | 1990-03-29 | 1992-03-18 | 帝国化学工业公司 | 1,1,1, the preparation method of 2-Tetrafluoroethane |
| US5426251A (en) * | 1991-11-27 | 1995-06-20 | Daikin Industries, Ltd. | Process for preparing 1,1,1-trifluoro-2-chloroethane and/or 1,1,1,2-tetrafluoroethane |
| CN1088196A (en) * | 1992-08-05 | 1994-06-22 | 昭和电工株式会社 | 1,1,1, the production method of 2-Tetrafluoroethane |
| CN1082019A (en) * | 1992-08-10 | 1994-02-16 | 昭和电工株式会社 | 1,1,1, the production method of 2-Tetrafluoroethane |
| CN1153160A (en) * | 1995-12-27 | 1997-07-02 | 西安近代化学研究所 | Process for producing 1,1,1,2-tetrafluoroethane |
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