The way to obtain 1-chloro-1,3-butadiene


(57) Abstract:

Describes how to obtain 1-chloro-1,3-butadiene by dehydrochlorination of dichlorobutenes selected from 3,4-dichlorobutene-1, 1,4-dichlorobutene-2 or mixtures thereof, and the process is conducted in the gas phase in the presence of a catalyst selected from lanthanum phosphate or phosphate of lanthanum, additive comprising an alkaline or alkaline-earth metal, or mixtures of these phosphates. The proposed method is simpler and cheaper than known. 2 C.p. f-crystals, 2 tab.

The present invention relates to a method for producing 1-chloro-3,4-butadiene by the dehydrochlorination of 3,4-dichlorobutene-1, 1,4-dichlorobutene-2 or mixtures thereof.

It is known that 1-chloro-1,3-butadiene, also called "alpha chloroprene, you can polimerizuet or copolymerizate preferably, chloroprene 2-chloro-1,3-butadiene.

A method of obtaining 1-chloro-1,3-butadiene degidrirovanie 1,4-dichlorobutene-2 by the action of sodium amide in liquid paraffin - see Methods elementool. chemistry, Ed. by A. N. PL, M: Nauka, 1973, S. 460.

Alpha chloroprene usually obtained as a by-product in most of the reactions that receive a 2-chlorobutadiene. In fact, a small amount of al is ropren stands, the quantity which can vary from the conditions of reaction formed during the chlorination reactions of butadiene, or isomerization of 1,4-chloro-2-butene to obtain 3,4-sodium dichloro-1-butene, or also dehydrochlorinating 3,4-sodium dichloro-1-butene.

High level output alpha chloroprene can be obtained by dehydrochlorination of 1,4-sodium dichloro-2 butene, obtained in turn from butandiol with amidon of sodium in mineral oil. This method is very expensive, as it requires at least stoichiometric quantities of sodium amide.

The purpose of the present invention is an improved way to obtain 1-chloro-1,3-butadiona, which is free from the above disadvantages.

In accordance with the foregoing, the present invention relates to a method for producing 1-chloro-1,3-butadiene, wherein dichlorobutene is selected from 3,4-sodium dichloro-1-butene, 1,4-di-sodium dichloro-2-butene and mixtures thereof, and dehydrochlorinated in the gas phase in the presence of a catalyst selected from lanthanum phosphate, lanthanum phosphate with an additive of at least one alkali or alkaline earth metal, and mixtures of these phosphates.

The catalyst preferably is selected from phosphate and lanthanum phosphate landata La" refers to the connection, which is defined in EP-A-440555, i.e. a compound with the General formula on the basis of dry material/: LaPO4/Imp/p/1/.

In connection with the General formula /1/ "Imp" refers to the primary treatment composition, which comprises a metal selected from alkali metal or alkaline earth metal, preferably alkaline earth metals, and these metals are associated with the counter-ion as to ensure the neutrality of the compounds of General formula /1/. In the above formula, /1/, the ratio "R" is in the range from 10-2up to 1/3 , preferably from 0.05 to 0.2.

The phosphate landata can be well-known technology, for example, by reaction of phosphoric acid and salts of lanthanum, for example, lanthanum carbonate.

Receiving lanthanum phosphate with an additive of alkaline metal or alkaline earth metal is disclosed in EP-A-440555.

Before using the catalyst in the method degidro-chlorination according to the present invention, the catalyst is subjected to conventional procedures calcination, preferably at temperatures in the range from 420 to 480oC.

The catalyst can be used in the method of the present invention as such, or as lump is particularly suitable oxides such as alumina, silica, titanium oxide, magnesium oxide, zirconium dioxide, taken separately or combined with each other.

The catalyst and binder can be mixed in a weight ratio of 30: 70, preferably in a ratio of from 50:50 to 70:30. The mixture can be shaped in a desired form, for example, extruded bodies or granules.

The reaction dihydrochloride, which is based on the method of the present invention, is as follows:

the isomerization of 3,4-sodium dichloro-1-butene /3,4-DCB/, obtaining 1,4-sodium dichloro-1-butene /1,4-DCB/;

the dehydrochlorination of 1,4-DCB to obtain 1-chloro-1,3-butadiene /1-SW/.

It follows from the above that the method according to the present invention is equally effective as of 3,4-DCB and 1,4-DCB as starting compounds.

The method of the present invention provides a process in which 3,4-DCB or 1,4-DCB or mixtures thereof are skipped over a specified catalyst.

In accordance with a variant of the invention it is possible to use a carrier gas, which consists of one or more inert gases, preferably is nitrogen.

The contact time is in the range of 5 to 0.5 seconds, better than 2 to 1 second.

The method of the invention mainly provoditj examples to further illustrate the invention.

Example 1. Getting LaPO4< / BR>
57 g of H3PO4/85% Prolabo/, and 150 ml of deionized water are loaded into the reactor. The resulting mixture was stirred at a speed of 500 to 700 rpm In a cold state with strong stirring is added 166.6 g of La2/CO3/312H2O. the Reaction medium is heated for 60 minutes and then cooled with bringing to room temperature for 30 minutes. The suspension is filtered on a filter with a porous glass plate N 3 until then, until you leave the mother liquor.

The pressed residue is immersed in 1000 ml of water with strong stirring and maintained in suspension for 30 minutes while stirring. Stage washing is repeated twice. The product is filtered, then dried at 110oC.

Example 2. Getting LaPO4with the cesium additive.

4,7 ml 6M CsOH is added to 14.12 ml 1M H3PO4. The addition of water, the volume of the mixture is brought to 50 ml.of

To 50 g LaPO4prepared in accordance with the previous example, is added dropwise 20 ml of the indicated solution.

The product is brewed for 60 minutes, dried overnight at 110oC, and then fired at 500oC for 120 minutes.
In a tubular quartz reactor equipped with a channel for a thermometer, two pipes for the fluid /nitrogen environment supply by type of syringe/, and a cylindrical oven, on a partition of porous glass was loaded in sequence a layer of powder glass Pyrex /1 cm, a layer of a mixture of catalyst /2 ml/ powder of Pyrex /8 g/, the layer of beads from Pyrex /2 cm/.

The catalyst was air in the following way:

the calcination: 120 minutes at 400oC;

- air conditioning heat: 120 minutes at 250oC.

The resulting reaction products were separated by trap /being isolated in three traps set by the cascade/ p separation was performed within 1 hour after a period beginning 45 minutes.

Experimental conditions:

- N2: 2.8 l/h

the feed rate of 3,4-dichlorobutene /reduction States "3,4 -, or 1,4-di-sodium dichloro-2 butene: g/h;

- temperature: 250oC.

The results are shown in Table 1, where: RRICBoutput 1-chloroprene,

RR1,4- yield of 1,4-di-sodium dichloro-2-butene,

TT3,4- conversion of 3,4-sodium dichloro-1-butene,

TT1,4- conversion of 1,4-di-sodium dichloro-2-butene.

Example 4.

In this example, /TableA in the presence of CS2NRA4LaPO4obtained as disclosed in example 2 above. Was also calculated yield of chloroprene /RRCP.

The data in table 2 show that the best results in the transformation and exit out at a temperature of approximately 200oC, albeit with 250oC data is also satisfactory.

1. The way to obtain 1-chloro-1,3-butadiene by dehydrochlorination of dichlorobutene in the presence of a catalyst, characterized in that use dichlorobutene selected from 3,4-dichlorobutene-1, 1,4-dichlorobutene-2 or mixtures thereof, and the process is conducted in the gas phase at a temperature of 190 - 280oC, and as a catalyst using a catalyst selected from lanthanum phosphate or phosphate of lanthanum, additive comprising an alkaline or alkaline-earth metal, or mixtures of these phosphates.

2. The method according to p. 1, wherein the used catalyst is selected from phosphate and lanthanum phosphate, lanthanum, including cesium additive.

3. The method according to p. 1, wherein the process is conducted at 200 to 250oC.


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