Method of removing 1,1,2-cryptor-1,2-dichloroethane from a mixture with 1, 1,1-cryptor-2,2-dichloroethane

 

(57) Abstract:

1,1,2, -Cryptor-1,2-dichloroethane /AA/ someresult in 1,1,1-Cryptor-2,2-dichloroethane /a/ interacting with AlF3at temperatures between 180o400oC.

Mostly this method is developed for mixtures AA with a and/or with other chlorpheniramine hydrocarbons formed when receiving a accession of hydrogen fluoride to perchloroethylene. 4 C. p. F.-ly, 7 PL.

The invention relates to methods isomerization,1,2 trifter-1,2-dichloroethane (hereinafter designated as AA/ 1,1,1-Cryptor-2,2-dichloroethane (hereinafter designated as a/. In particular, the invention involves the removal AA from its mixtures with a and possibly with other chlorpheniramine hydrocarbons by isomerization AA and a.

Was aware of the need for the development of available industrial methods of obtaining a, not containing AA.

In particular, such a need is recognized, for example, manufacturers of polyurethane foams, upon receipt of which as a foaming agent used a. In this case contained AA decomposes and forms HCl, which corrode metal kommunikasie /accession hydrogen fluoride/ trichloroethylene in the gas phase in the presence of suitable catalysts.

This method is described, for example, in U.S. patent N 4766260.

This method of obtaining always leads to the formation of AA in quantities of 5 to 20% depending on the reaction conditions. This product is difficult Argonauts of a.

It is possible to conduct the reaction under such conditions, to minimize the formation of AA, for example, by using high temperatures /about 360oC/ however it is not of practical interest, since under these conditions the selectivity of the process is relatively a too small, while the reaction by-products are obtained in unacceptable quantities.

It is also possible to reduce the content AA in the final reaction product, subjecting the mixture a and AA processing anhydrous HF in the presence of the same catalyst, which is used to obtain, thereby achieving the preferred fluorination AA in 1,1,1,2-titrator-2-chlorate /a/.

However, the selectivity of this reaction is not large enough and as a result it also happens fluoridation of significant quantities of a.

The applicant has found a process which is the subject of this invention, for the conversion AA in a interaction AA or in pure form or in a mixture of relatively at temperatures of about 220 to 320oC, with a catalyst consisting of aluminum TRIFLUORIDE /AlF3/.

Used here as a catalyst of aluminum TRIFLUORIDE is usually located in the crystallographic forms of beta, Delta and/or gamma. However, small amounts of other crystalline forms do not render harmful influence. Specified AlF3can be obtained by fluorinating agents; or it may be obtained in other ways known in this field, such as, for example, by thermal decomposition of Na3AlF6.

In the case of fluoridation Al2O3get AlF3has a surface area of 15 to 30 m2/g and a particle size of 20 to 200 μm / an average of 80 mcm /. The surface area of the AlF3is not a crucial part of the method of this invention, however, preferred AlF3is AlF3having a high surface area , for example, in the range of 15 to 30 m2/,

If AlF3obtained by fluorination Al2O3anhydrous HF, preferably, although not necessarily, to not less than 90% of the alumina contained in it, was in fluorinated condition.

To increase the activity of AlF3used as ka is usausa 1 wt. per weight of catalyst transition metal, preferably Fe, Ni, Co, Mn.

The method is used preferably for the isomerization AA located in mixtures mainly with a and possibly with other chlorpheniramine hydrocarbons formed in the process of gas-phase trichloroethylene HF.

In fact, the presence in the gaseous mixture obtained by such a reaction, in addition to the isomers Ia and a other products, for example A /CF3CHClF/, does not interfere with the isomerization AA. In practice this is very useful because it eliminates the need for a thorough distillation of such products before isomerization reaction. On the other hand, the fact that the reaction mixture is directly fed into the reactor for isomerization, is not significantly change the content of products, differing from the above isomers and present in the reaction mixture, which can then be allocated as such or re-directed in the process of obtaining a.

In the process the contact times AA with the catalyst are not particularly critical. Usually they support 5 to 100, preferably 20 to 50 C.

The pressure is especially crucial given the purpose of the invention, and not to limit the scope of its claims.

Example 1. In a tubular reactor made of Inconel 600/R/and having an inner diameter of 5 cm and a length of 80 cm, equipped with a porous base sintered Inconel 600 and heating elements were placed 300 cm3/340 g/ AlF3having a specific surface area of about 20 m2/, Such AlF3received by fluorination Al2O3anhydrous HF, which held up until more than 90% of Al2O3not proftherese.

To remove moisture absorbed during storage, the catalyst was treated with anhydrous HF at 250oC for 2 h

To the reactor was applied at 240oC at a rate of 100 g/h of a mixture containing a 14.5 mol. AA, and 63.9 mol. A and 21.6 mol. other harversters hydrocarbons, mainly A.

Gases leaving the reactor were barbotirovany through the water for removal of traces of acid, dried, are condensed in the cooled trap and analyzed by the method of gas chromography /GC/.

The results obtained are presented in table.1.

After 60 65 h work began to appear the phenomenon of depletion of the catalyst, but the activity /expressed as a proportion of AA, samaritana in a/ you could restore avamys a /sum of isomers and/ allocated a, as can be seen from table.2.

By further increasing the temperature /table.3/ it is possible to save the activity as the catalyst was dried up, the losses in selectivity were almost insignificant.

And, finally, the initial activity was fully restored /table. 4/ by regeneration of the catalyst is carried out by treatment with air at 430oC followed by re-fluoridation anhydrous HF at 300oC

Example 2. In the same reactor as in example 1, were placed 300 cm3AlF3whose characteristics are given in example 1.

Into the reactor was fed a mixture of the reagents and perform the reaction in the presence of a catalyst which is not subjected to any pre-hydropericardium. The reaction was conducted in the same manner as in example 1 and the results are shown in table.5.

Example 3. In the same reactor as in example 1, were placed 310 cm3the same AlF3, which was treated with air at 400oC for 3 h, and then was ferromoly 400oC for 2 h in anhydrous HF.

The reaction was conducted in the same manner as in example 1 and the results are shown in table.6.

The reaction was conducted in the same manner as in example 1, and the results are shown in table.7, from which it is evident that the activity of this catalyst is much higher.

1. Method of removing 1,1,2-Cryptor-1,2-dichloroethane from mixtures with 1,1,1-Cryptor-2,2-dichloroethane, characterized in that it includes the isomerization 1,1,2-Cryptor-1,2-dichloroethane in 1,1,1-Cryptor-2, 2-dichloroethane by contacting the above-mentioned mixture in the vapor phase with a catalyst essentially consisting of AlF3when 200 400oC.

2. The method according to p. 1, characterized in that use the original this mixture, optionally containing 1,1,1, 2-titrator-2-chlorate.

3. The method according to PP.1 and 2, characterized in that as the source of the mixture subjected to isomerization, using the reaction mixture obtained by hydropericardium of perchloroethylene hydrogen fluoride.

4. The method according to PP. 1 to 3, characterized in that the process is conducted at 220 - 320oC.

5. The method according to PP.1 to 4, characterized in that the use of a catalyst, optionally containing one or more transition metals selected from Fe, Mn, Co, Ni.

 

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FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to preparation of alkylaromatic intermediates including perfluorinated carbon atom utilized in production of agrochemically important active compounds. Intermediates simultaneously containing aniline function are obtained from homocyclic arylcarbamoyl fluoride including at least one perhalogenated carbon atom preferably bearing at least two halogen atoms capable of being replaced by fluorine atoms when in liquid-phase contact with hydrofluoric acid and water. During this reaction, molar ratio of hydrofluoric acid to arylcarbamoyl fluoride is maintained equal to 4, preferably to 5 and not higher than 11. Water is added to reaction mixture (at 10 to 90°C) when only one exchangeable halogen atom remains unreplaced. Arylcarbamoyl fluoride is obtained in situ by adding corresponding isocyanate to liquid hydrofluoric acid at temperature not exceeding 10°C. Process is carried out continuously in two reactors, the first one serving for halogen exchange reaction and the second for addition of water. Temperature 40°C is maintained until only one exchangeable halogen atom remains unreplaced.

EFFECT: increased yield and improved quality of desired product and economical characteristics.

9 cl, 4 ex

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