Process for isomerizing 1,1,2-trifluoro-1,2-dichloroethane to 1,1,1-trifluoro-2,2-dichloroethane

Abstract

1,1,2-trifluoro-1,2-dichloroethane (Al23a) is isomerized to 1,1,1-tri-fluoro-2,2-dichloroethane (Al23) by contacting it with AlF.sub.3 at temperatures ranging from 180.degree. to 400.degree. C. Advantageously, it is operated with mixtures of Al23a with Al23 and/or other chlorofluorocarbons coming from the preparation of Al23 by hydrofluorination of perchloroethylene.

Description

The present invention generally relates to a process for isomerizing 1,1,2-trifluoro-1,2-dichloroethane (hereinafter referred to as Al23a) to 1,1,1-trifluoro-2,2-dichloroethane (hereinafter referred to as Al23). In particular it relates to the removal of Al23a from its mixtures with Al23 and optionally other chlorofluorocarbons by isomerizing Al23a to Al23.

The need for having available industrial processes for preparing Al23 as free as possible from Al23a has been recognized.

Such need is particularly recognized, for example, by the manufacturers of polyurethane foams, for the production of which Al23 is used as foaming agent. In such case, the Al23a contained therein decomposes and forms HCl, which corrodes the metal circuits of the plants.

The industrially most interesting processes for the preparation of Al23 are based on the hydrofluorination of tetrachloroethylene in the gas phase, in the presence of proper catalysts.

Such a process is described for example in U.S. Pat. No. 4,766,260.

Such a preparation method always gives rise to Al23a in amounts ranging from 5 to 20%, depending on the reaction conditions. Such product is difficult to be distilled-off from Al23.

In principle it is possible to carry out the reaction under such conditions as to minimize the formation of Al23a, for example by using high temperatures (about 360.degree. C.); however, this is of little practical interest because under such conditions the process selectivity towards Al23 is too low, while unacceptable amounts of by-products are obtained.

It is also possible to reduce the Al23a content in the final reaction product by subjecting the mixture of Al23 and Al23a to a treatment with anhydrous HF in the presence of the same catalyst as is used for its preparation, thereby obtaining the preferential fluorination of Al23a to 1,1,1,2-tetrafluoro-2-chloroethane (Al24).

However, the selectivity of such reaction is not high enough, wherefore also the fluorination of considerable amounts of Al23 occurs.

The Applicant has now surprisingly found a process--constituting the object of the present invention--for converting Al23a to Al23 by contacting Al23a, either alone or in admixture with Al23 and/or other chlorofluorocarbons, in the gas phase, with a catalyst consisting of aluminium trifluoride (AlF.sub.3), at temperatures ranging from 180.degree. to 400.degree. C., but preferably from 220.degree. to 320.degree. C.

The aluminium trifluoride utilized herein as a catalyst is generally present in the crystallographic forms .beta., .DELTA. and/or .gamma.. However, little amounts of other crystalline forms are not harmful.

Said AlF.sub.3 can be obtained by fluorination of alumina (Al.sub.2 O.sub.3) with anhydrous HF or other fluorinating agents; or it can be prepared according to other methods of the art, such as, for example, the thermal decomposition of Na.sub.3 AlF.sub.6.

In the case of the fluorination of Al.sub.2 O.sub.3, the AlF.sub.3 obtained has a surface area of 15-30 m.sup.2 /g and granule sizes ranging from 20 to 200 microns (on the average: 80 microns).

The surface area of AlF.sub.3 is not a critical element for the process of the invention, however, an AlF.sub.3 having a high surface area, for example ranging from 15 to 30 m.sup.2 /g, is preferred.

If such AlF.sub.3 is obtained by fluorination of Al.sub.2 O.sub.3 with anhydrous HF it is preferable, although not absolutely necessary, if at least 90% of the alumina contained therein is present in the fluorinated state.

The AlF.sub.3 utilized as a catalyst in the process of the invention can be modified, in order to increase the activity thereof, by addition of little amounts--not exceeding 1% by weight calculated on the catalyst--of transition metals, preferably Fe, Ni, Co, Mn.

Preferably, the process of the invention is utilized for the isomerization of Al23a in its mixtures mainly with Al23 and optionally with other chlorofluorocarbons, which are obtained in the processes for the fluorination of tetrachloroethylene with HF, in the gas phase.

In fact, the presence of products other than the isomers Al23a and Al23, for example Al24 (CF.sub.3 CHClF), in the gaseous mixture obtained from such reaction does not prevent the isomerization of Al23a. That is very advantageous in practice because it eliminates the necessity to carry out an accurate distillation of such products prior to the isomerization reaction. On the other hand, the fact that the reaction mixture directly flows into the isomerization reactor does not sensibly modify the content of the products different from said isomers and present in the reaction mixture, which can be then recovered as such or recycled to the Al23 production.

For the purposes of the process of the invention, the contact times of Al23a with the catalyst are not particularly critical. Generally they are maintained from 5 to 100 seconds and preferably from 20 to 50 seconds.

Also the pressure does not exhibit particularly critical values; it can be the atmospheric pressure or a higher pressure.

The following examples are given merely to illustrate the invention, but not to limit the scope thereof.

EXAMPLE 1

Into a tubular reactor made of Inconel 600.RTM. having an inside diameter of 5 cm and a length of 80 cm, equipped with a porous bottom of sintered Inconel 600 and heated by means of heating elements, there were introduced 300 cc (340 g) of AlF.sub.3 having a specific surface of about 20 m.sup.2 /g. Such AlF.sub.3 had been prepared by fluorination of Al.sub.2 O.sub.3 with anhydrous HF till obtaining the fluorination of more than 90% of Al.sub.2 O.sub.3.

The catalyst was treated with anhydrous HF at 250.degree. C. for 2 hours in order to remove the moisture absorbed during the storing time.

About 100 g/h of a mixture containing 14.5 moles-% of Al23a, 63.9 moles-% of Al23 and 21.6 moles-% of other organic chlorofluorocarbons, mainly Al24, were fed at a temperature of 240.degree. C.

The gases leaving the reactor were bubbled in water in order to remove acidity traces, were dried and condensed in a cold trap and then analyzed by means of gas chromatography (G.C.).

The results obtained are reported in Table 1A.

After a 60-65 hour run, the catalyst exhibited exhaustion phenomena, but the activity (expressed as the Al23a fraction isomerized to Al23) could be restored by raising the temperature to 270.degree. C. without affecting the selectivity, expressed as ratio between fed Al23 (sum of the isomers) and recovered Al23, as shown in Table 1B.

By raising the temperature further on (Table 1C) it was possible to maintain the activity as the catalyst got exhausted, the selectivity losses being only negligible.

Lastly, by regenerating the catalyst by means of a treatment with air at 430.degree. C. followed by refluorination with anhydrous HF at 300.degree. C., the original activity was fully restored (Table 1D).

EXAMPLE 2

Into the same reactor utilized in Example 1, 300 cc of AlF.sub.3 having the same characteristics as the one of example 1 were charged.

The reagent mixture was fed without subjecting the catalyst to any preliminary hydrofluorination treatment. By operating in like manner as in example 1, the results reported in Table 2 were obtained.

EXAMPLE 3

Into the same reactor as Example 1 there were charged 310 cc of the same AlF.sub.3, which was treated for 3 hours at 400.degree. C. with air and then was fluorinated for 2 hours at 400.degree. C. with anhydrous HF.

By operating as in example 1, the results reported in Table 3 were obtained.

EXAMPLE 4

Into the reactor of example 1 there were charged 310 cc of an aluminium fluoride containing 0.12% by weight of iron in the form of Fe.sub.2 O.sub.3, which was treated for 2 hours at 300.degree. C. with anhydrous HF.

By operating as in example 1, the results reported in Table 4 were obtained, wherefrom it is evident that the activity is much higher.

TABLE 1A__________________________________________________________________________ Operation hoursFeeding 1.5 4 13 21 24.5 29.5 40 57.5 66 80(Moles-%) Obtained products (moles-%)__________________________________________________________________________A123a 14.5 4.2 2.3 5.2 4.5 4.3. 4.0 5.0 4.4 9.8 10.2A123 63.9 75.8 75.6 73.3 74.4 74.9 75.0 74.1 75.0 69.1 68.8Others 21.6 20.0 22.1 21.5 21.1 20.8 21.0 20.9 20.6 21.1 21.0__________________________________________________________________________ Reaction temperature = 240.degree. C.; t = 38 TABLE 1B______________________________________ Operation hoursFeeding 88 91.5 103.5 107 111(Moles-%) Obtained products (moles-%)______________________________________A123a 14.5 2.3 1.8 1.9 3.4 4.5A123 63.9 75.6 77.3 77.6 76.0 73.8Others 21.6 22.1 20.9 20.5 20.6 21.7______________________________________ Reaction temperature = 270.degree. C.; t = 36 TABLE 1C__________________________________________________________________________ Operation hoursFeeding 116 129 133 157 161 164 178 181 184(moles-%) Obtained products (moles-%)__________________________________________________________________________A123a 14.7 3.1 2.2 2.5 2.5 2.7 2.3 2.5 2.7 3.0A123 65.9 76.8 77.7 77.4 77.3 77.5 77.0 76.5 76.3 79.6Others 19.4 20.1 20.1 20.1 20.2 19.8 20.7 21.0 21.0 19.4__________________________________________________________________________ Reaction temperature = 280.degree. C.-320.degree. C.; (t = 36"-33", respectively) TABLE 1D______________________________________ Operation hoursFeeding 4 7 11 24 26(moles-%) Obtained products (moles-%)______________________________________A123a 10.6 0.3 0.2 0.2 5.0 2.3A123 65.4 72.1 72.8 74.2 73.1 75.6Others 24.0 27.6 27.0 25.6 21.9 22.1______________________________________ After regeneration Reaction temperature = 280.degree. C. for tests not exceeding 11 operatio hours, and 240.degree. C. for tests not exceeding 26 operation hours (t = 36" and 38", respectively) TABLE 2__________________________________________________________________________ Operation hoursFeeding 3 7.5 11 14 18 23 26 30 33 38(moles-%) Obtained products (moles-%)__________________________________________________________________________A123a 14.1 13.2 7.5 7.0 0.9 1.3 0.4 0.4 0.3 0.5 0.8A123 70.2 71.6 78.0 78.0 85.0 85.1 85.2 85.4 84.6 84.3 84.2Others 15.7 15.2 14.5 15.0 14.1 13.6 14.6 14.2 15.1 15.2 14.5__________________________________________________________________________ Reaction temperature = 240.degree. C. for test not exceeding 11 operation hours; t = 38 Reaction temperature = 280.degree. C. for the other tests; t = 36 TABLE 3______________________________________ Operation hoursFeeding 2 4.5 12 25 29(moles-%) Obtained products (moles-%)______________________________________A123a 10.6 0.2 0.2 0.2 0.6 0.3A123 65.4 73.2 75.6 74.8 79.0 72.7Others 24.0 26.6 24.2 25.0 20.4 27.0______________________________________ Reaction temperature = 280.degree. C. for tests not exceeding 12 operatio hours; t = 37 Reaction temperature = 260.degree. C. for the other tests; t = 38 TABLE 4______________________________________ Operation hoursFeeding 3.5 7.5 9 13.5 16.5 20(moles-%) Obtained products (moles-%)______________________________________A123a 14.1 0.6 0.1 0.6 0.6 0.3 1.4A123 70.2 69.6 57.4 76.1 75.3 77.4 77.2Others 15.7 29.2 42.5 23.7 24.1 22.3 21.4______________________________________ Reaction temperature = 260.degree. C. for tests not exceeding 7.5 operation hours; t = 38 Reaction temperature = 240.degree. C. for tests not exceeding 13.5 operation hours; t = 40 Reaction temperature = 220.degree. C. for the other two tests; t = 41

Claims

1. A process for removing 1,1,2-trifluoro-1,2-dichloroethane (Al23a) from a mixture comprising 1,1,1-trifluoro-2,2-dichloroethane (Al23) and Al23a, which comprises isomerizing Al23a to Al23 by contacting said mixture in the vapor phase with a catalyst consisting essentially of AlF.sub.3 and transition metals selected from the group consisting of Fe, Mn, Co, and Ni, in an amount of from 0 to 1% by weight, at a temperature of from 200.degree. C. to 400.degree. C.

2. The process of claim 1, wherein said mixture further comprises 1,1,1,2-tetrafluoro-2-chloroethane (Al24).

3. The process of claim 1, wherein said mixture is a reaction mixture obtained from hydrofluorination of perchloroethylene with HF.

4. The process of claim 1, wherein the temperature is within the range of from 220.degree. to 320.degree. C.

5. The process of claim 1, wherein the catalyst is prepared by fluorinating Al.sub.2 O.sub.3 with anhydrous HF.

6. The process of claim 5, wherein at least 90% of the alumina in said catalyst is fluorinated.

7. A process for the production of 1,1,1-trifluoro-2,2-dichloroethane (Al23) which comprises:

(a) contacting tetrachloroethylene with HF to produce a mixture of hydrofluorination products, including 1,1,2-trifluoro-1,2-dichloroethane (Al23a) and Al23; and

(b) isomerizing Al23a to Al23 by contacting said mixture in the vapor phase with a catalyst consisting essentially of AlF.sub.3 and transition metals selected from the group consisting of Fe, Mn, Co, and Ni, in an amount of from 0 to 1% by weight, at a temperature of from 200.degree. C. to 400.degree. C.

8. The process of claim 7, wherein the mixture reacted in step (a) further comprises 1,1,1,2-tetrafluoro-2-chloroethane (Al24).

9. The process of claim 7, wherein the temperature in step (b) is within the range of from 220.degree. to 320.degree. C.

10. The process of claim 7, wherein the catalyst is prepared by fluorinating Al.sub.2 O.sub.3 with anhydrous HF.

11. The process of claim 10, wherein at least 90% of the alumina in said catalyst is fluorinated.