CN1035761C - Method for purification of 1,1,1,2-tetrafluoroethane - Google Patents

Method for purification of 1,1,1,2-tetrafluoroethane Download PDF

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CN1035761C
CN1035761C CN92112813.4A CN92112813A CN1035761C CN 1035761 C CN1035761 C CN 1035761C CN 92112813 A CN92112813 A CN 92112813A CN 1035761 C CN1035761 C CN 1035761C
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tetrafluoroethane
reaction
hfc
impurity
reactor
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CN1085888A (en
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大野博基
大井敏夫
中山秀俊
村一男
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Resonac Holdings Corp
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Showa Denko KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound

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Abstract

In the process of preparing 1, 1, 1, 2-tetrafluoroethane by the reaction between trichloroethylene and hydrogen fluoride, crude 1, 1, 1, 2-tetrafluoroethane is highly purified by the following steps: preliminary purification of the crude 1, 1, 1, 2-tetrafluoroethane is carried out to remove hydrogen chloride until the concentration of the hydrogen chloride is not higher than 2%, the 1, 1, 1, 2-tetrafluoroethane after the preliminary purification, which contains one kind or several kinds of unsaturated impurities and hydrogen fluoride which is at least equimolar with the impurity qualities, contacts a fluorination reaction catalyst in a gas phase, and therefore, the content of the unsaturated impurities is lowered.

Description

Purify 1,1,1, the method for 2-Tetrafluoroethane
The present invention relates to by making 1,1,1, in the 2-Tetrafluoroethane contained at least-kind of unsaturated impurity and hydrogen fluoride (HF) reaction and purify 1,1,1, the method for 2-Tetrafluoroethane.
More specifically, the present invention relates to as the following quid pro quo of CFC-12 and arouse attention 1,1,1, the 2-Tetrafluoroethane (abbreviates " HFC-134 " or " CF as when hereinafter addressing 3CH 2F ") method of purification.CFC-12 is the cooling agent that is widely used in automatic air condition machine, rerigerator etc., and it is to environment, and especially ozonosphere has harm.
One of production method of known CF3CH2F is to use chrome catalysts fluoro 1,1, and 1-three fluoro-2-monochloroethane (are hereinafter addressed and abbreviated " HCFC-133a " or " CF as 3CH 2Cl "), CF 3CH 2Cl is the raw material of using with the preparation trifluoroethanol of industrial-scale production.[special permission bulletin (the patent announcement text that Japan examined) NO.43-10601 and US4158675]; Another kind method is to trifluoro-ethylene (CF 2=add hydrogen fluoride (special permission bulletin NO.62-23728) in CHF); Also having a kind of method is under the situation that palladium catalyst exists, and makes 2,2-two chloro-1,1,1,2-Tetrafluoroethane (CF 3CCl 2F) or 2-chloro-1,1,1,2-Tetrafluoroethane (CF 3CHClF) with H-H reaction (special permission bulletin NO.56-38131).
When producing CF with these methods 3CH 2During F, relevant reaction causes various impurity generation side reactions, and said impurity is relevant with used catalyzer, reaction conditions etc.
The impurity that is caused by byproduct of reaction for example comprises: unsaturated impurity is CF 2=CClF, CClF=CHCl, CF 2=CHCl, CHF=CClF, CF 2=CHF and CHCl=CHF; Chlorofluorocarbon is as CCl 2F 2, CH 2ClF, CH 2ClCClF 2, CF 3CHCl 2And CF 3CHClF; And hydrofluorocarbon, as CF 3CHF 2, CF 3CH 3And CHF 2CHF 2
In these impurity, the CF that is produced 3CH 2F can stand the existence of hydrofluorocarbon, if its poor words still are impatient at the existence of unsaturated impurity and chlorofluorocarbon, has both made their content considerably less.So, must from product, remove these impurity, as being removed with fractionating process.
But, boiling point and CF 3CH 2The impurity that the boiling point of F is close reaches the impurity that exists with the azeotropic mixture form and is difficult to remove with the distillatory method.Especially unsaturated impurity had both made after distillation, and they still can be present in the product with trace.
The difficulty that many methods have been proposed to overcome in the distillation and are run into.
(1). in the method for the production HFC-134a of routine, trieline raw material and HF are introduced into-individual reactor.The gas that produces is mainly by HCFC-133a, and hydrogenchloride (HCl) and unreacted HF form.
If the gas former state of these generations is introduced second reactor, owing to wherein contain a large amount of hydrogenchloride, therefore the reaction of carrying out forms a kind of disadvantageous balance, as the formula (1), and can not generate purpose product HFC-134a effectively.
……(1)
Therefore, these gases need to separate with purification system, remove de-chlorine hydride.
Remaining gas, or so or behind additional H F, be introduced into second reactor.The gas that produces in second reactor is by unreacted HCFC-133a and HF, the mixture that required HFC-134a and by product are formed.Wherein by product mainly is unsaturated impurity and hydrogenchloride.
Gained gas former state offers the 3rd reactor, adds HF at this in unsaturated impurity, reacts.The 3rd reactor gained gas is moved to purification system to reach the purpose of separating and removing de-chlorine hydride.Remaining gas moves to separate realizes separating of the finished product HFC-134a with purification system.Be circulated back to second reactor by isolated HCFC-133a of HFC-134a and HF.
The problem that this method can bring unsaturated impurity reaction efficiency to descend is because be to introduce the 3rd reactor with the form that still contains HCl from second reactor expellant gas.Disadvantageous aspect also has, and reaction needed has bigger capacity because in the effluent air with respect to the HFC-134a that will obtain, contain a large amount of HCFC-133a and HF.Address this problem, must between second and the 3rd reactor, insert a purification system, nature, the expense of device has also just increased thereupon.
(2). as EP-0446869-Ai, provide other method among EP-0449614-A2 and the EP-0449617-A2 in the invention disclosed.
According to these methods, HCFC-133a and HF are supplied with second reactor, reaction product herein is by unreacted raw material HCFC-133a and HF, the product HFC-134a that obtain, by product HCFC-1122 (CF 2=CHCl) and the mixture formed of similar material and hydrogenchloride.
These mixed gas former states are supplied with first reactor.Simultaneously, trieline raw material and HF also supply with it.Trieline and HF reaction generate HCFC-133a and hydrogenchloride; HCFC-1122 and HF reaction transform into HCFC-133a.
Therefore, the gas that generates in first reactor is by HCFC-133a, HFC-134a, HF, hydrogenchloride, the mixture that a small amount of trieline and other by products are formed.The gas of these generations moves to purification system to be separated, and removes de-chlorine hydride, isolates HFC-134a with continuing.Remaining HCFC-133a and HF return second reactor.
Though the characteristics of this method are, consider that trieline and HF react a large amount of heat releases, first diluting reaction gas before reaction, it has following defective:
(a). in this method, because the air-flow that contains hydrogenchloride that comes out from second reactor all is introduced into first reactor, therefore hydrogen cloride concentration will rise in first reactor, and the reaction efficiency of the unsaturated impurity of this method is lower than the efficient of ordinary method (1).
(b). in addition, owing to the gas that generates in second reactor all is introduced into first reactor, the gas volume that first reactor is accepted increases, so the needed capacity of reactive system wants big than ordinary method.
Purpose of the present invention just provides a kind of purification 1,1,1, the novel method of 2-Tetrafluoroethane, and unlikely generation distinctive defective in the prior art as previously described.
Consider the defective of prior art mentioned above, the present invention has carried out arduous research in the hope of developing the method for purification HFC-134a commericially feasible, economic.They find immediately with trieline and hydrogen fluoride reaction system HFC-134a the time, can economy obtain quite a large amount of high purity HFC-134a that does not contain unsaturated impurity easily, this method is, make HFC-134a in vapour phase with a catalyst reaction and from reaction mixture, reclaim HFC-134a, wherein the HFC-134a before the reaction contains at least a unsaturated impurity, hydrogen chloride content wherein is lower than 2mol%, and contain at least hydrogen fluoride with mol ratios such as unsaturated impurity, preferably need not to add in addition HF, the present invention finds to finish according to this.
Before this, the method that makes trieline and HF reaction conduct produce HFC-134a known in the state of the art.This reaction can not be finished in a step, need finish through two different step processes of condition.Specifically, the first step is reacted as the formula (2), and trieline and HF reaction just generates the reaction of HCFC-133a:
(2) second step reactions are by in the preamble shown in (1) formula, i.e. the reaction of HCFC-133a and HF reaction generation HFC-134a.
The reaction of second step is to make HCFC-133a and HF reaction then generate HFC-134a, and this reaction is a balanced reaction, contains the unsaturated impurity that can form azeotropic mixture with HFC-134a in the reaction product.These unsaturated impurity are difficult to separate from HFC-134a, thereby cause various processing mentioned above.
The disclosed method of method (Japanese patent application NO.4-19249 and NO.4-199827) that the former inventor once proposed a kind of HFC-134a of production comprises that going on foot the products that react with first and second delivers to a thick purification step together, use an equipment of simplifying to realize the removal of HCl by product and concentrating of HFC-134a, thereby obtain such as simplifying distillation procedure and the benefit that reduces energy expenditure.
The invention provides a kind of purification by trieline and hydrogen fluoride reaction make thick 1,1,1, the method of 2-Tetrafluoroethane comprises the steps: thick 1,1,1, the 2-Tetrafluoroethane carries out preliminary purification, removes hydrogenchloride to its concentration and is not more than 2%, then will be through 1 of preliminary purification, 1,1, the 2-Tetrafluoroethane contacts with fluoridation catalyst in vapour phase, thereby reduces the content of unsaturated impurity, after the said purification just 1,1,1, contain in the 2-Tetrafluoroethane one or more unsaturated impurity and at least with the hydrogen fluoride of unsaturated impurity equimolar amount.
The present invention relates to a kind of economy, easily row, the purify method of HFC-134a efficiently, this HFC-134a is the HFC-134a that concentrates and reduced at least a wherein contained unsaturated impurity level through thick purification step.Description realizes the method for this purification.By the HFC-134a that the previously presented thick method of purification of the inventor concentrated, hydrogen chloride content wherein must limit less than 2mol%, and is preferred, wherein do not conform to hydrogenchloride.
If hydrogen chloride content surpasses 2mol%, the reaction that unsaturated impurity adds HF will be suppressed.Proportional ground significantly increases this reversed reaction with the increase of hydrogen cloride concentration.As a result, reaction efficiency descends greatly, and having to even is high reaction temperature.
The rising of temperature of reaction causes reaction and the decomposition of HFC-134a and HCFC-133a, shown in (3) and formula (4), thereby makes and reduces under the amount of HFC-134a.Degradation production can reduce activity of such catalysts.
……(3)
……(4)
For these reasons, hydrogen cloride concentration must be no more than 2mol%.Preferred this concentration is 0.
The inventive method needn't be added HF to reactant gases, because through containing the HF as azeotropic component among the thick HFC-134a that purifies.When HF and unsaturated impurity at least with etc. molar ratio when existing, required reaction is promptly carried out with high-level efficiency.After reaction was finished, unreacted HF recycled rather than loses and slattern.
The concentration requirement of HCFC-133a among the HFC-134a is no more than 10mol%.If concentration surpasses 10mol%, operation just can not be accomplished economy, because the decrease in efficiency of reaction, reactive system also needs to strengthen.
The concentration requirement of HFC-134a is no less than 70mol%.If concentration is limit less than this, operation can be undesirable, because can run into the defective the same with the situation of HCFC-133a.
Order contains said components and is that the HFC-134a that concentrates attitude contacts with catalyzer in vapour phase.
The employed catalyzer of the inventive method needs only fluoridation to be shown catalytic activity.Specifically, the catalyzer that can effectively use is fluorination catalyst herein, it comprises the metallic compound in 1 B, 2A in the long period periodic table of elements, 2B, 4B, 5A, 5B, 6A, 7A and 8 families, and at least one element should be selected from Cu, Mg, Zn, Pb, V, Bi, Cr, Mn, Fe, Co and Ni.These catalyzer can be attached on alumina catalyst support, aluminum fluoride or the activated carbon.
Can make catalyzer by the method for any routine in the prior art.Such as, aluminum oxide is immersed in the cobalt chloride solution aluminum oxide behind the dry dipping, roasting exsiccant aluminum oxide in the air of circulation then.Zhi Bei catalyzer should be used the hydrogen fluoride activity earlier before being used for reaction like this.
Temperature of reaction should be between 130 ℃ and 280 ℃ scope, preferably between 150 ℃ and 250 ℃.If temperature of reaction is lower than the lower limit of above-mentioned scope, the speed of response of unsaturated impurity will be too slow.And if temperature of reaction surpasses the upper limit, the reaction of previously described HFC-134a and HCFC-133a and decomposition will take place, and this is disadvantageous.
After reaction finishes, reaction product can be by economic, easily row, purification efficiently, obtain not contain high-purity HFC-134a of unsaturated impurity, because reclaimed unreacted HF, small amount of H CFC-133a among the concentrated HFC-134a and other hydrocarbon are because of distilling under the situation that does not have HF, separated effectively going out generates any azeotropic mixture and be unlikely between them.
According to the present invention, extremely difficult before this from CF 3CH 2The unsaturated impurity of removing among the F can be economical, easy row and being removed efficiently.So the present invention can produce highly purified CF 3CH 2F
Below, in conjunction with non-restrictive example hereinafter the present invention is described more specifically.
Catalyst preparation example 1
The aluminum oxide that 100ml has activated (choosing of Nikki Universal K.K system is sold with product code name " NST-3 ") is dipped in by 52ml and purifies waste water and 3.6g cobalt chloride (CoCl 2) in the solution that forms, absorbed the solution of whole volumes to aluminum oxide.Then, dry in 90 ℃ water-bath by solution wetted aluminum oxide.
In the air circulating type hot air drying cabinet, with 110 ℃ of further dry catalysts 10 hours.Drying catalyzer is inserted in the glass roasting pipe, with air speed (SVo) 500hr -1Be heated to 400 ℃ in the flowing air, obtain catalyzer.
Catalyst preparation example 2
Except using 6.67g nickelous chloride (NiCl 26H 2O) replace beyond the cobalt chloride, the method that repeats catalyst preparation example 1 makes catalyzer.
Raw material example 1
Make trieline (CCl 2=CHCl) under participating in, chrome catalysts reacts the thick purified product that obtains (mol%) composed as follows with vapour phase hydrogen fluoride:
CF 3CH 2F?81.4350，CF 3CH 2Cl?6.2400，CHF 2CHF 2?0.1600，
CF 3CHF 2?0.5320，CF 3CH 3?0.5360，CF 3CHClF?0.5310，
CF 3CClF 20.0540, CF 2=CHCl 0.4420, and CHCl=CHF 0.0020, HF9.5060 and HCl 0.5620.
Raw material example 2 (Comparative Examples)
The thick purified product (mol%) composed as follows that obtains with reaction with raw material example 1 same procedure:
CF 3CH 2F?71.4527，CF 3CH 2Cl?12.2160，CHF 2CHF 2?0.1820，
CF 3CHF 2?0.5620，CF 3CH 3?0.6420，CF 3CHClF?0.5880，
CF 3CClF 20.0570, CF 2=CHCl 0.5820, and CHCl=CHF 0.0032, HF8.3031 and HCl 5.4120.
Embodiment 1
Ferrochrome 600 type reactors, during internal diameter 1, long 1m inserts the catalyzer that makes in the 80ml catalyst preparation example 1 in it.Before the reaction, use HF and 100%HF fluorination catalyst to make its activation through nitrogen dilution.
The treatment condition of handling catalyzer with HF are as follows:
The concentration of HF: 25 to 100%
Treatment temp: 250 ℃ to 350 ℃
Treatment time: about 10 hours
In the presence of the catalyzer of the preparation as mentioned before that has activated, with the raw material supplying reactor of raw material example 1,200 ℃ of temperature of reaction, air speed (SVo) is 1000hr -1Remove the acid in the eluting gas, the gas gas chromatographic analysis that obtains.Then, find (mol%) composed as follows:
CF 3CH 2F?90.5407，CF 3CH 2Cl?7.4412，CHF 2CHF 2?0.1779，
CF 3CHF 2?0.5916，CF 3CH 3?0.5960，CF 3CHClF?0.5904，
CF 3CClF 20.060, and CH 2ClCHF 20.0021.
Find CF 3CH 2F does not contain the unsaturated impurity that can measure, shows by handling to have removed impurity substantially.Do not find the products C F that wants 3CH 2The loss of F is not measured other by products and is increased or reduce.
After this, under condition mentioned above, react and carried out continuously 1000 hours.During successive reaction, do not measure the decline of unsaturated impurity removal efficacy, in fact, required product C F 3CH 2F does not find loss yet.
As mentioned above, handle eluting gas to remove acidic component, distillation is further purified, and analyzes then.As a result, the gas composition following (mol%) after discovery is purified.
CF 3CH 2F?99.9976，CHF 2CHF 2?0.0020，CF 3CH 3?0.0001，
CF 3CHF 20.0002, and CF 3CHClF 0.0001.
As a result, obtained to contain anything but high-purity HFC-134a of saturated impurity.
Embodiment 2
Except the catalyzer that makes with catalyst preparation example 2 described methods replaces, repeat embodiment 1 method and react.Eluting gas is treated to be removed acidic components and analyzes with gas-chromatography.
Analytical results clearly illustrates that the CF that makes 3CH 2Do not detect unsaturated impurity among the F, fact proved and almost all removed impurity, and in fact do not find required goods CF 3CH 2The loss of F.
Comparative Examples 1
Raw material with the replacement of the raw material in the raw material example 2 raw material example 1 repeats embodiment 1 method and reacts.Then, use the gas chromatographic analysis effluent air.Found that its (mol%) composed as follows:
CF 3CH 2F?81.8828，CF 3CH 2Cl?15.5915，CHF 2CHF 2?0.2101，
CF 3CHF 2?0.6511，CF 3CH 3?0.7446，CF 3CHClF?0.6808，
CF 3CClF 2?0.0658，CF 2＝CHCl?0.1484，CHCl＝CHF?0.0020，
CH 2ClCHF 20.0017, and CClF 2CH 2Cl 0.0212.
Because CF 3CH 2Hydrogen cloride concentration height among the F, operational verification are uneconomic, and be about 77.8% because the removal efficient of unsaturated impurity is reduced to, desired product CF 3CH 2F and loss are for about 1.1%.
Then, temperature of reaction rises to 280 ℃, eluting gas is handled removed acidic component.Use the gas chromatographic analysis resulting gas.
Detected result clearly illustrates that operation is uneconomic, though because the removal efficient of unsaturated impurity rises to 92%, can not reach 100% resembling in embodiment 1 and 2, desired product CF 3CH 2The loss of F rises to about 4.1%.
Keep 280 ℃ of temperature of reaction, successive reaction 500 hours, the removal efficient of unsaturated impurity reduces to about 80%.Observe catalyzer, find that it is deposited on carbon and has suffered.
Comparative Examples 2
Carry out conventional operation, undertaken by the method for preamble described (1) formula in other words.The aluminum oxide that has activated is immersed in the chromium chloride solution to it the aqueous solution is all absorbed.Dry then, calcining obtains fluoridation catalyst.
When packing this catalyzer of 80ml into internal diameter 1, long 1 meter Inconel(nickel alloys) 600 type reactors, become second reactor.
In addition, the reactor that the catalyst loading that makes by catalyst preparation example 1 with 80ml is identical with second reactor becomes the 3rd reactor.
Before reaction was carried out, the catalyzer in the second and the 3rd reactor activated with partially fluorinated the making it of HF, and activation condition is the same with the condition described in the embodiment 1.
At first, second reactor is heated to 350 ℃ in nitrogen environment.Then, stop for nitrogen.Hydrogen fluoride and HCFC-133a supply with the flow velocity of 1060ml/min and 260ml/min respectively.
Eluting gas is treated remove acidic component after, with gc analysis it.Find its (mol%) composed as follows:
CF 3CH 2F?3.88，CF 3CH 2Cl?15.95，CF 2＝CHCl?0.024
Other by products 0.106, HCl 4.0, and HF 76.04
Heating the 3rd reactor to 240 ℃ under nitrogen environment, used the same of method and second reactor.Stop for nitrogen.Introduce the 3rd reactor from gas (the forming as implied above) former state that second reactor flows out.The treated acidic component of removing of eluting gas, use then gc analysis it.Find its (mol%) composed as follows:
CF 3CH 2F?19.3248，CF 3CH 2Cl?80.1352
CF 2=CHCl 0.0072, other by products 0.5328
The result shows from CF 3CH 2The efficient that F removes unsaturated impurity is about 94%, shows that processing is not very effective.
In addition, operate uneconomical because from required CF 3CH 2The low-purity of F is looked, and operation efficiency is starkly lower than the efficient of embodiment 1 or 2.

Claims (4)

  1. A purification by trieline and hydrogen fluoride reaction make thick 1,1,1, the method of 2-Tetrafluoroethane comprises the steps: thick 1,1,1, the 2-Tetrafluoroethane carries out preliminary purification, removes de-chlorine hydride to its concentration and is not higher than 2%, after the preliminary purification 1,1,1, in the 2-Tetrafluoroethane 1,1,1, the content of 2-Tetrafluoroethane is not less than 70mol%, 1,1, and the content of 1-trifluoro one 2 monochlorethanes is not more than 10ml%; Make 1,1,1 after the preliminary purification that contains one or more unsaturated impurity, the 2-Tetrafluoroethane with contact with fluoridation catalyst in vapour phase with the hydrogen fluoride of this unsaturated impurity equimolar amount at least, thereby reduce the content of unsaturated impurity.
  2. 2. the method for claim 1, wherein 1,1,1 after the preliminary purification, the 2-Tetrafluoroethane contains at least the hydrogen fluoride with unsaturated impurity equimolar amount, need not further to add hydrogen fluoride when making it to contact with catalyzer.
  3. 3. the method for claim 1, catalyzer wherein is the compound that is selected from least a metal of Cu, Mg, Zn, Pb, V, Bi, Cr, Mn, Fe, Co and Ni.
  4. 4. the method for claim 1, wherein 1,1,1 after the preliminary purification, the 2-Tetrafluoroethane is to carry out under 130 ℃ to 280 ℃ temperature with contacting of catalyzer.
CN92112813.4A 1991-04-19 1992-10-17 Method for purification of 1,1,1,2-tetrafluoroethane Expired - Lifetime CN1035761C (en)

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JP3115551A JP2897454B2 (en) 1991-04-19 1991-04-19 Purification method of 1,1,1,2-tetrafluoroethane
CN92112813.4A CN1035761C (en) 1991-04-19 1992-10-17 Method for purification of 1,1,1,2-tetrafluoroethane

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JP3115551A JP2897454B2 (en) 1991-04-19 1991-04-19 Purification method of 1,1,1,2-tetrafluoroethane
CN92112813.4A CN1035761C (en) 1991-04-19 1992-10-17 Method for purification of 1,1,1,2-tetrafluoroethane

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FR2694556B1 (en) * 1992-08-05 1994-09-23 Atochem Elf Sa Process for the purification of 1,1,1,2-tetrafluoroethane.
EP0648727B1 (en) * 1993-10-13 1997-08-27 Elf Atochem S.A. Process for the purification of 1,1,1,2-Tetrafluorethane
FR2711135B1 (en) * 1993-10-13 1995-11-17 Atochem Elf Sa Process for the purification of 1,1,1,2-tetrafluoroethane.
DE4335179A1 (en) * 1993-10-15 1995-04-20 Solvay Fluor & Derivate Process for the preparation of pentafluoroethane and the purification of 1,1,1,2-tetrafluoroethane
US5723429A (en) * 1994-03-11 1998-03-03 E. I. Du Pont De Nemours And Company Azeotropic or azeotrope-like compositions of tetrafluoroethane and chlorotetrafluoroethane
US5470442A (en) * 1994-03-11 1995-11-28 E. I. Du Pont De Nemours And Company Separating and removing impurities from tetrafluoroethanes by using extractive distillation
FR2736050B1 (en) 1995-06-29 1997-08-01 Atochem Elf Sa PROCESS FOR PRODUCING DIFLUOROMETHANE
CN105438810A (en) * 2015-12-15 2016-03-30 爱彼思（苏州）自动化科技有限公司 Automatic clamping machine
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

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