DE2012898A1 - Process for the production of chlorinated hydrocarbons - Google Patents

Description

The invention relates to a process for the production of chlorinated. Hydrocarbons ₀

Oemitß of the invention there is provided a process for the production of chlorinated hydrocarbons, in which chlorine with an unsaturated aliphatic hydrocarbon, an aromatic hydrocarbon or a halogenate derivative of such hydrocarbons is reacted in a liquid 'phase, characterized ₉ that as the chlorine source a gasförmi = * gee _s is used mixture of chlorine and nitric oxide which reacted with the liquid phase in contact

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Mixtures of chlorine and nitrogen oxide containing only 0.00005 moles or even less nitrogen oxide per mole of chlorine can be used. The gas mixture preferably contains at least 0.1 mol of NO per mol of chlorine.

The gas mixture is advantageously produced by the decomposition of Hitrosyl chloride (NOCl), so that the molar ratio of NO to Cl ₂ in the gas mixture is 2: 1. Nltrosylchlorid, according to known techniques in the presence or absence of a catalyst at temperatures ranging from 200 to 800 ⁰ C, preferably J00 to 600 ° C, decomposes * "Larger molar ratios of NO to Cl ₂ than 2: 1 may be but optionally also be used.

The liquid phase used is one which is inert with respect to the nitrogen oxide under the reaction conditions. It preferably consists of a medium in which the nitrogen oxide is practically insoluble under the reaction conditions, so that the nitrogen oxide emerges from the medium largely unabsorbed. If the gas mixture is obtained by the decomposition of nitrosyl chloride, then the liquid medium should preferably also over against NOCl, which has not decomposed, and against any oxides of nitrogen which are initially present in the NOCl and which are found in the gaseous clouding to the chlorinator can inert leg ₀ it is especially preferred _a is a liquid organic phase to be used "In a suitable manner, these are a aliphatiachen hydrocarbon or an aromatic hydrocarbon, or derivatives thereof, such as" Kalogen- or nitro derivatives, particularly suitable organic media lj, 2-dichloroethane _{3 are} the tetrachloroethanes, the chlorofithylenes, and the nitro and chlorobenzoic oils. The process can be operated in such a way that the reaction only takes place between the chlorine component of the gas mixture and the organic medium, which is, for example, dichloro-ethylene.

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SAD OWQlNAL

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Very brittle results can be obtained "., Run one olefinic coal / asserstojTe and chlorine! types olefinic Kohlfinwaoserstoffe, like ζ „BY ethylene, and chlorofithylene or mixtures thereof, al2 organic Realrcionteilrihmer., the i: a the medium introduced is used.

A particularly advantageous, uncomplicated process is obtained by using the chlorohydrocarbon as the flow phase, which is formed during the reaction of chlorine in the gas mixture with the hydrocarbon or the chlorohydrohydrocarbon, which is converted into the liquid phase introduced wire], so that the problem of the separation of the contaminated product is reduced or eliminated ²

A particularly useful method for the U-erfindungBgemfißeß irstelliing of l _s 2 "DichloTol ⁱ .than obtained when a gas" genilßchi which nitric oxide and chlorine and which contains lat obtained by thermal or catalytic decomposition of Nltrosylchlorid, in contact with a liquid phase brings the 1,2-dichloroethane · contains ₃ in which the chlorine reacts with the ethylene introduced into the phase.

This process can be carried out under subatmospheric pressure or superatmospheric pressure; reaction temperatures in the range from 20 ° C to the boiling point of the medium give usable results «. For example, temperatures may be used at about atmospheric pressure in the range from '40 to 80 ⁰ C. Preferably, substantially stoichiometric molar ratios of chlorine to be used, for example ethylene _s Mo! Ratios of Cl to CH ^. in the range of ₁ Oj 9: 1 to 1.1 ϊ 1 "The reaction may be in the absence of a catalyst or in the presence of a catalyst such as _s ,. of a metal chloride, for example iron (III) chloride, can be carried out »High conversions of ethylene and chlorine with a very high degree of selectivity for 1 _s 2-dichloropethane

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keep. A physical separation of the nitrogen oxyres in one «.InsIgen stage ο is also effected.

When the process of the eri'indungagemfißen nicht' unreacted Silckoxyd from the chlorinator may be oxidized eu NO ₂ ", the latter may be reacted with an inorganic metal chloride, such as K'31 or · NIkCl wherein Nltrosylchlorid and potassium or ammonium nitrate is produced, which are valuable fertilizers. The nitrosyl chloride provides the source for nitrogen oxide and cilor. In this way an extremely valuable integrated process is achieved ₃ which chlorinated hydrocarbons such as zJ3. IJA DIchlorofithanj) returns from a non-electrolytic source Γ Ji chlorine "The 1,2-Dichloroßthan _s can be easily and zweckm'ißlg cracked with vinyl chloride and hydrogen chloride eitsteht"

The following examples illustrate the invention.

nelsplel 1

32 l / st nitrosyl chloride were introduced into an empty, heat-resistant glass tube of 20 cm length and 0.32 cm in inner diameter, wherein the Fohr was placed in a maintained at 500 ⁰ C oven. The hot AusfcrlttsgaEj which nitric oxide and C'ilor contained was passed through a water-cooled condenser, to cool the Oas to approximately 2'3 ⁰ C.

Dis Gaf? was mixed with ethylene (12.6 l / st; the wood ratio of CL .; au C ₂ K ₁ J was approximately 1: 1) and placed in the bottom of an unpacked reactor 75 cm long and 3.5 cm r -mar.durchmeseer · introduced The reactor contained 700 ml of 1,2-diohloroethane. the anhydrous Elsen (III) ". Chlcrid overall li -ittigt was * Di '* Temperature thieves; 3 medium was 65 ⁰ C, and *: 1,2-Dichlo z: ·:"ätii;*; vnarde formed n , it flowed over the reactor aid Kurds: The outlet gases from the reactor were caught

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BATH ORIGINAL

• by cooler "hlndurungeführt organic product © ent of f er ·" nen ₀

The IJS Dichloroäthanprodukc contained only traces of other organic materials as l _a 2- »Dlohloroäthän _s wherein the conversion of ethylene au i _s 2" = DichlotOllthan was 96% ,, analysis of exhaust gases showing © ₉ that nitric oxide is the only nitrogen-containing or sauer3toffhaltige byproduct the reaction was.

Example 2

A mixture of chlorine _a Stlekostyd and Ätliylen was introduced at a rate of 10 1 / et Ci ₂₂ 20 l / st NO and 10 l / st C ₂ Hj, into the reactor described in Example i. The reactor contained 400 ral i _s 2 _»s dichloroethane was with iron (III) chloride saturated" ax ^ and the medium was on bO ° C maintained _a The experiment ended after 6 hours _s and the liquid medium (599 ml) was analyzing _s and it was found _s that 9 $% LJ2 ~ Dlchloro & than and 0 _s 86% 1 ₉ 1 ₉ 2-Trlohlorofithan ent would consider the conversion of ethylene to i _s 2-dichloroethane was 97% o the nitric oxide was unchanged through the reactor _a

A mixture of chlorine, _{nitrogen oxide 9,} ethylene and nitrogen dioxide (MO ₂ ) was produced at a rate of 10 l / h Cl ₃₅ 20 l / h NO ₉ 10 1 / at C ₂ Hi ₁ and 2 .1 / et NO ₃ during a period of time _o introduced by 6 hours in the liquid phase under the beschrie in example 2 surrounded conditions the experiment was then discontinued, j and the liquid medium {600 ml) was analyzed, it was found that _s ea approximately 99 ₉ ^J l 1,2% Dlchloroäthan and O _1, 54% l ₉ l _s 2 ~ Triehloroäthan contained. The conversion of ethylene in ₉ l 2 ° dichloroethane was 97 '£ 0 There was no nitrogen-containing organic by-product found in the liquid medium "The nitric oxide was unchanged by aen reactor ₀ The nitrogen

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d.ioxyd dissolved in the liquid medium until it was "saturated with NO ₃ whereupon the NO _{2 passed} unchanged through the reactor"

Example fr

A mixture of chlorine (2fr l / st) and nitrogen oxide (fr8 l / st) was introduced into a reactor which contained 200 ml vinylidene chloride, which was saturated with anhydrous El3en (III) chloride and was at room temperature. The introduction took 2 liters / 2 hours = the experiment was then terminated, the liquid medium was then analyzed. Ea contained 93% by weight? l, l, lj, 2 »tetrachloroethane and 7 Gev /» »? Vinylidene chloride, The conversion of vinylidene chloride in 1 ₅ L, 1,2-Tetrachloroäthan therefore was 93% - The nitric oxide was unchanged through the reactor.

PATENT CLAIMS

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8AD

Claims (1)

2 O 1 2 8 PA T E HT.AMS'PHOCH E Process for the production of chlorinated hydrocarbons, in which chlorine is reacted with an unsaturated aliphatic hydrocarbon, an aromatic hydrocarbon or a halogenated derivative of these hydrocarbons in a liquid phase _s characterized _s that the source of chlorine is a gaseous mixture of chlorine and nitrogen oxide is used, which is brought into contact with the liquid phase » 2 * Method according to claim I _1, characterized in that the mixture of nitrogen oxide and chlorine contains at least 0 _f J. moles of nitrogen oxide per mole of chlorine « 3c method according to claim 1 or 2 _t characterized in that the mixture of nitrous oxide and chlorine is produced by thermal or catalytic decomposition of nitrosyl chloride. ty * Process according to one of the preceding claims, characterized in that the liquid phase used is one in which the nitrogen oxide is practically insoluble under the reaction conditions » 5. "Method according to one of the preceding claims, characterized in that the liquid phase is such is used, the opposite of one present in the gas mixture Nitrosyl chloride is inert. 6 ο α θ traversing according to any one of the preceding claims, 'characterized in that _a liquid organic phase that is used " 0098 ^ 0/22 ^ 5. 7 * Process according to claim β ₉ characterized * that the liquid organic phase is an aliphatic hydrocarbon or aromatic hydrocarbon or a halogenodei? The citrus derivative thereof is _e 8 ο method according to claim 7 _S characterized in that the liquid organic phase consists of 1,2-dichloroethane, a tetrachloroSthari or a diehloroethylene » 9 ο A method according to any preceding claim _s characterized in that the chlorine desselbeiij _s in a mixture with an olefinic hydrocarbon or a Chlorotlerivat which is introduced in liquid medium AEAs ₉ responded 10ο method according to any of the preceding claims, characterized _s that a liquid chlorohydrocarbon "* is used stofX'phase _s is introduced into the liquid medium by reaction of chlorine in said gas mixture with the hydrocarbon or chlorinated hydrocarbons, formed 11 »A method according to any one of claims l _s 3, 4, 5 _S 6" 7, 8 _S 9 or 10, for the preparation of _£ 1, 2-dichloroethane, characterized in that a gaseous ,, _s ßemisch which nitric oxide and chlorine and has been obtained by thermal or catalytic decomposition of nitrosyl chloride, brings it into contact with a "liquid phase which contains 1,2-chloro-thane, in which chlorine reacts with ethylene which is introduced into the liquid phase" 12ο method according to claim 11, characterized in that the reaction is carried out at a temperature in the range of Ilo to 80 ⁰ C and at virtually atmospheric pressure " 0 098A0 / 22A5 SAD ORIGINAL 13 ο Method according to claim 11 or »12 ₄ characterized in that the molar ratio of Cl ₂ to C ₂ H _{if is} in the range from 0.9 ϊ 1 to I ₉ I: 1 * 1*". A method according to any one of claims 11 _s 12 or 13 characterized _9, wherein the chlorination reaction is carried out in Oegenwart a catalyst. " 15 = Process according to Claims 14 _9, characterized in that Ssen (III) chloride is used as the catalyst l6o method according to any one of claims 1 or 3 in up to 15 "in the _S is the nitric _oxide's exiting the chlorination oxidized to nitrogen dioxide to produce, which in turn is reacted with an inorganic metal chloride or with Amraoniumchlorid to Hitrosylchlorid produce, through which thermal or catalytic decomposition the gas mixture of nitrogen oxide and chlorine can deliver _o 009840/2245