DE1643744B1 - Process for the continuous production of mixtures containing mainly tetrachlorophthalic dinitrile from chlorinated phthalic dinitriles - Google Patents

Description

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From the German Auslegeschrift 1191 358, loading is known continuously at such a speed, that chlorinated phthalic acid dinitriles, dar- passed through the catalyst layer that the including tetrachlorophthalic acid dinitrile, counter-set in lively motion by surrounding particles of the layer of phthalic acid dinitrile with chlorine in opposite directions and constant mixing with one another of activated charcoal as a catalyst, which is given 5 without the gas flow from the reaction chamber if carried out with potassium chloride, calcium chloride, barium. The catalyst particles chloride, acid clay, kaolin or aluminum oxide are in a state of flow and form a is activated. Fluidized bed in which the reaction takes place according to the process

It has now been found that the main thing ren plays the invention. As a rule, 30 to 600, preferably 120 to 480, volumes of chlorinated phthalic dinitriles are introduced into the fluidized bed for 10 hours per mixture containing tetrachlorophthalic dinitrile through chlorine parts of total gas, based on one part by volume of catalysis of phthalic dinitrile in the presence of a catalyst. With regard to the production and catalyst with chlorine at elevated temperature, the fluidized bed and procedures can be used advantageously if the chlorination when using flow systems is referred to at a temperature of 300 to 700 ° C, in particular chapter "Dust flow process" of the above Works at 450 to 600 ° C, in one of silica gel and / or from U11 ma η η, Vol. 1, p. 916, referenced.
Petroleum coke formed as a catalyst by fluidized bed- The reaction can be carried out as follows: leads. One passes continuously chlorine, phthalic acid dinitrile

The process according to the invention delivers in the vaporization and optionally inert gas from below into a tetrachloro reaction tube similar to the known process, in which the fluidized bed of the fluidized phthalic acid dinitrile is in a higher space-time yield; the catalyst particles is located. The fluidized bed means that far fewer cracking products are formed on the catalyst during the reaction at the reaction temperature, the life span and activity of the catalyst is maintained. At the upper end of the reaction tube% capacitors will therefore be maintained over a long time and the reaction mixture cooled, and scored extending abeine consistently high yield of end product. 25 outgoing chlorinated phthalic acid dinitriles

In general, phthalic acid dinitrile is used and separated off. The tetrachlorophthalic acid dinitrile is made from

Chlorine in a molar ratio of 1: 4. Prefer them in the usual way, for. B. by recrystallization

one works wisely with an excess of chlorine, isolated from trichlorobenzene.

z. B. up to 120 mole percent. The chlorine can be It is also possible to use the phthalic acid dinitrile in

if necessary, by means of inert gases, such as nitrogen, chlorine, in liquid or solid form, to be added to the reaction

be diluted with hydrogen or carbon tetrachloride. and it is only converted into vapor form in the reaction chamber.

It is advantageous to choose the volume ratio to convert chlorine.

to inert gas from 1: 0.1 to 1: 1, preferably from

1: 0.3 to 1: 0.7. Finding produced tetrachlorophthalic acid dinitrile

For the implementation one uses in general 35 with copper, iron or nickel salts are obtained

Temperatures from 300 to 700 ° C, preferably 450 green phthalocyanines, which are used as pigment dyes

up to 600 ° C. Appropriately leads one to turn the implementation.

at atmospheric pressure. But it is also possible The parts indicated in the examples mean

borrowed, the reaction under slightly reduced pressure, parts by weight. They relate to the volume parts

z. B. 300 mm Hg, or slightly increased pressure, e.g. B. 40 as kilograms to liters,
up to 1.5 atm.

The catalysts used are silica gel and / or example

Petroleum coke, generally with an average particle size of 0.1 mm, borrowed through a vertical reaction tube of 4 cm. Silica gel can be used with a diameter in which there is 0.25 parts by volume of spherical i granular form or, preferably, spherically shaped coke with a grain size of 0.1 mm. Petroleum coke is understood here to mean a mixture of carbons per hour from below which, in cracking processes, consists of 0.017 parts of phthalic acid dinitrile vapor, 25 parts by volume of petroleum, petroleum fractions, aliphatic hydrochloric acid, and 15 parts by volume of nitrogen. The reaction substances or corresponding mixtures are obtained (cf. 5 hours at a temperature of 550 ° C in the UllmannsEncyklopadie der technischen Chemie, Vol. 6, 50 swirling catalyst layers. The sub-p. 625 ff.). They differ among other things in the limiting reaction products are collected at the upper type of extraction, their surface and catalytic end of the reaction device. One of the effectiveness of activated carbons. The silica mentioned holds 0.151 parts of a gel and / or petroleum coke catalysts melting at 238 to 247 ° C, mixtures of chlorinated phthalic acid dinitriles with an additional activator in the form of compounds 55 Content of 0.143 part of tetrachlorophthalic acid dinitrile of metals of the 1st, 2nd and / or 8th subgroup des (81% of theory).
Periodic table containing z. B. by water. .
ken the catalysts with solutions corresponding to the example
Salts are incorporated. Preferred activators are through the reaction tube described in Example 1, the chlorides, sulfates, acetates, nitrates of iron, in which 0.35 parts by volume of spherical petroleum coke is copper, zinc, platinum or palladium. Advantageously, from 0.2 to 0.4 mm grain size, one uses 0.1 to 5, in particular 0.3 to 2 weight percent at a temperature of 580 ° C in the catalyst percent activator, based on the total catalyst layer from below every hour a mixture of 0.019 teizor and calculated as metal, regardless of this, len phthalic acid dinitrile vapor, 50 parts by volume of chlorine as it is actually present in the catalyst. Phosphates 65 and 20 parts by volume of nitrogen. After 3 hours, or borates are terminated according to the method of the invention, the reaction. 0.108 parts are obtained which are not contained in the catalysts. a mixture that melts at 235 to 241 ° C

The starting materials and optionally the inert gas-rated phthalic acid dinitrile with a content of

■ 0.099 parts of tetrachlorophthalic acid dinitrile (83.7% of theory).

Example 3

A mixture of 0.019 parts of phthalic acid dinitrile vapor and 50 parts by volume of chlorine is passed through the reaction tube described in Example 1, which contains 0.3 parts by volume of spherical silica gel 0.1 mm in particle size, at a temperature in the catalyst layer of 580 ° C. from below . The reaction is terminated after 3 hours. 0.1 part of a ^{mixture of chlorinated phthalic acid dinitriles which melts at 228 to 235 °} C. and a content of 0.089 part of tetrachlorophthalic acid dinitrile (75.2% of theory) is isolated.

Example 4

Through the reaction tube described in Example 1, in which there are 0.25 parts by volume of spherical silica gel 0.1 mm in size and still containing 0.003 part iron (III) chloride, is passed through the catalyst layer at a temperature of 550 ° C below an hourly mixture of 0.019 parts of phthalic acid dinitrile, 35 parts by volume of chlorine and 10 parts by volume of nitrogen. The reaction is terminated after 3 hours. This gives 0.102 parts of a chlorinated at 234 to 24O ⁰ C melting Phthalsäuredinitrile mixture containing 0.093 parts Tetrachlorphthalsäuredinitril (78.5% of theory).

Example 5

Through the reaction tube described in Example 1, which contains 0.25 parts by volume of spherical silica gel 0.1 mm in size and still containing 0.006 parts of palladium, a mixture is passed hourly from below at a temperature of 550 ° C. in the catalyst layer 0.019 parts of phthalic acid dinitrile vapor, 22 parts by volume of chlorine and 10 parts by volume of nitrogen. The reaction is terminated after 3 hours. 0.111 part of a ^{mixture of chlorinated phthalic acid dinitriles which melts at 243 to 0} C and a content of 0.106 parts of tetrachlorophthalic acid dinitrile (89.5% of theory) is obtained.

Claims (1)

Claim: Process for the continuous production of mixtures containing mainly tetrachlorophthalic dinitrile from chlorinated phthalic dinitriles by chlorination of phthalic dinitrile in the presence of a catalyst with chlorine at an elevated temperature, characterized in that the chlorination is carried out at a temperature of 300 to 700 ^° C., in particular 450 to 600 ° C in a fluidized bed formed from silica gel and / or petroleum coke as a catalyst.