The way of transformation of chlorinated alkane in less chlorinated alkene

 

(57) Abstract:

Describes how the transformation of chlorinated alkane in less chlorinated alkene by reacting chlorinated alkane in the presence of a catalyst containing palladium and a metal M on the media. The metal M is chosen in the group consisting of silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth and mixtures thereof. The technical result increased selectivity, high conversion without rapid deactivation of the catalyst over time. 13 C.p. f-crystals, 4 PL.

The invention relates to a method of transformation of chlorinated alkane (paraffin) less chlorinated alkene (olefin) by reacting a chlorinated alkane with hydrogen in the presence of a catalyst consisting of a metal of group VIII and other metal, medium.

In international applications 94/07828, 94/07827, 94/07823, 94/07821, 94/07820, 94/07819 and 94/07818 describes how the transformation of various chlorinated alkanes in less chlorinated alkenes using hydrogen in the presence of a bimetallic catalyst comprising a metal of group VIII and a metal of group IB, supported on a carrier. In European patent application 0640574 describes the conversion of hlorirovanii metal, such as lanthanum, titanium, vanadium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, indium, tin or bismuth, on the media. In the known methods the best degree of transformation of chlorinated alkanes and the best selectivity in respect of the receipt of alkenes reach using bimetallic catalyst of platinum-copper at the active angle. In the international application 94/07819 and European patent application 0640574, in particular, describes how the transformation of 1,2-dichloropropane in propylene. From this it follows that the above bimetallic catalysts do not allow to achieve simultaneously a high degree of conversion of 1,2-dichloropropane and high selectivity in respect of propylene. In addition, these catalysts are initially low selective towards the formation of propylene, and produce large amounts of propane. In this regard, these known catalysts are unsuitable for obtaining propylene, directly used for the production of allylchloride by chlorination of propylene. In fact, during the recirculation stage production allylchloride, in a mixture containing propylene and propane, by chlorination of propane formed 1-chloropropane and/or 2-chloropropane, products, hard Otdelenia necessary pre-processing of these catalysts by florodora to improve their initial selectivity and stability.

In U.S. patent 3892818 describes how dechlorination of 1,2-dichloropropane using hydrogen in the presence of a bimetallic catalyst rhodium-gold supported on alumina. This catalyst has good activity and long life, however, the reaction product is mainly propane.

Currently found a way, which does not have the above disadvantages and which allows to transform chlorinated alkanes in less chlorinated ethylenes with good selectivity and, preferably, with a high degree of conversion, without rapid deactivation of the catalyst over time, and this catalyst does not require pre-treatment with chlorocarbon.

Thus, the invention relates to a method of transformation of chlorinated alkane in less chlorinated alkene by reacting chlorinated alkane with hydrogen in the presence of a catalyst comprising a metal of group VIII and a metal M, on the media, which differs in that the metal of group VIII is palladium and the metal M is chosen in the group consisting of silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth and mixtures thereof.

Chlorinated alkane rosy results are achieved when using chlorinated acyclic alkanes and in particular, chlorinated acyclic alkanes General formula CnH2n+2-xClxwhere "n" denotes an integer from 2 to 6, and x represents an integer from 1 to (2n+2). Particularly preferred chloropropane and, in particular, dichloropropane and trichlorpropane. The preferred 1,2-dichloropropan.

Under less chlorinated alkene understand alkene, the number of carbon atoms corresponding to the number of carbon atoms used chlorinated alkane and which contains at least one chlorine atom less than the chlorinated alkane. Less chlorinated alkene, such as indicated in accordance with the present invention, therefore, may not contain any chlorine atoms. In the case of chlorinated alkane of General formula CnH2n+2-xClxwhere "x" = 1-(2n+2) formed in the method according to the invention alkene, therefore, satisfies the General formula CnH2n-yClyin which y varies from 0 to 2n, but never exceeds (x-1). In the method according to the invention, the interaction of chlorinated alkane with hydrogen can lead to one less chlorinated alkene, as specified above, or a mixture of several less chlorinated alkenones the metal M, selected in the group consisting of silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, on the media. The metal M is preferably chosen from among silver, tin, lead, thallium and bismuth. Good results are achieved in the case when the metal M is tin. Excellent results are achieved when the metal M is silver. Preferably, the catalyst consists mainly of palladium and a metal M on the media. Palladium and the metal M can be in the elemental state or in the form of compounds, such as salt or oxide. The catalyst preferably comprises palladium and the metal M in the elementary state.

As a catalyst carrier typically use a porous media, such as media, usually used with the catalysts used in hydrogenation reactions. Examples of such carriers are active carbon, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, zirconium oxide, lithium aluminate, a mixture of silicon dioxide with aluminum oxide. The preferred carrier is an activated carbon.

The amount of palladium on the carrier preferably has a value of at least 0.05 percent, preferably, p is the mass media. Preferably it does not exceed 5%.

The amount of metal M on the carrier is preferably at least 0.05 percent, preferably at least about 0.15 wt.%, in the calculation of the mass media. Usually the amount of the metal M does not exceed 10 wt.%, in the calculation of the mass media. Preferably it does not exceed 5%.

The mass ratio of palladium to the metal M is preferably at least 0,05. Especially it is preferable that the mass ratio is at least 0,1; it is most preferable that the mass ratio has a value of at least 0.25 in. Preferably, the mass ratio of palladium to the metal M does not exceed 20. Especially preferably, this ratio does not exceed 10; most preferably, this ratio does not exceed 4.

In the private embodiment of the method according to the invention, where the metal M is silver, the mass ratio of palladium to silver in particular is preferably a value of at least 0.4. In this embodiment of the invention, the mass ratio of palladium to silver is preferably not more than 2.5.

The catalyst also optionally can contain is the being or in the form of a compound of the metal (group call according to the nomenclature CAS as shown in the CDS "Handbook of chemistry and physics 75th edition, 1994-1995, D. R. Lide). If necessary, the amount of this additional metal does not exceed 50 wt.% from the total mass of palladium and a metal M

Included in the composition used in the method according to the invention the catalyst metals can be deposited on the carrier by impregnation of the latter with a solution or several solutions containing metal components of the catalyst. Solutions for impregnation are preferably aqueous salt solutions. Used for this purpose salts are especially the chlorides, nitrates, acetates or ammonium complexes. According to a preferred variant proposed in the invention method uses a catalyst that is obtained by two successive impregnations. In this case, the first media permeate containing palladium solution, dried, and then impregnated with a solution containing the metal M, and again dried. Normally soaked and dried carrier is subjected to heat treatment in a reducing atmosphere, such as, for example, hydrogen, at a temperature of at least 100oC and preferably less than or equal to 400oC. Termoobrezan Is, the hen is used chlorinated alkane and hydrogen in the way.

In the method according to the invention the molar ratio of hydrogen/chlorinated alkane is preferably at least 0.1 and more preferably at least 0.5. This ratio is preferably not more than 40, most preferably it does not exceed 20.

In the method according to the invention, the hydrogen reacts with chlorinated alkanol, giving at least one less chlorinated alkene, as mentioned above. If necessary, the hydrogen may be mixed with another gas which is inert under the reaction conditions of transformation of chlorinated alkane in less chlorinated alkene. As another gas can be used gas actually from a group of inert gases, such as helium or a gas which does not participate in the above reaction, such as chlorodrol or alkene. In the case where the selected inert gas is alkene, it preferably represents an alkene or alkenes formed by the reaction of a chlorinated alkane with hydrogen. The volume fraction of hydrogen is preferably at least 5% of the total volume of hydrogen and another gas. Most preferably, the proportion of hydrogen Sidhi phase or in the gas phase. The method according to the invention is preferably carried out in the gas phase. The method preferably is carried out at a temperature of at least 150oC, more preferably at least 200oC. the Temperature usually does not exceed 450oC, even more preferably it does not exceed 400oC. the Pressure at which carry out the method in itself is not critical. Typically operate at a pressure at least 1 bar. Typically, the pressure does not exceed 30 bar, preferably it does not exceed 10 bar.

In the case where the method according to the invention is carried out in the gas phase, the average time of contact between the gases and the catalyst, i.e., the ratio between the volume occupied by the catalyst, and the total consumption of the load, measured at the temperature and pressure during the reaction is preferably at least 0.5 seconds, more preferably at least 1 second. Preferably, the contact time does not exceed 30 seconds. Particularly preferably, the contact time does not exceed 20 seconds.

The method according to the invention allows to achieve a high degree of transformation of chlorinated alkane and very significant selektivnosti selectivity in relation to less chlorinated alkenes without appreciable formation of alkanes and chlorinated alkanes, moreover, this is achieved with the use of a catalyst and without pre-treatment of the catalyst with florodora. The method according to the invention has the advantage that the deactivation of the catalyst over time is particularly slow compared to the deactivation of the known catalysts of the prior art.

In the particular case where chlorinated alkanol used in the method according to the invention is 1,2-dichloropropane, propylene get with good selectivity and high conversion. The invention thus relates, in particular, to a method for producing propylene by reacting 1,2-dichloropropane with hydrogen in the presence of a catalyst containing palladium and a metal M selected in the group consisting of silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth and mixtures thereof, on the media.

The method according to the invention finds an application in the conversion of chloropropanol and more specifically chloropropanol formed as byproducts in the production of allylchloride by chlorination of propylene and/or in the production of epichlorohydrin by hypochloraemia alishar ochropus and 1,2,3-trichlorpropane. Chloropropane, which is used in this application of the method according to the invention may contain a minor amount, usually less than 5 wt. %, other products, in particular products involved in obtaining allylchloride and/or epichlorohydrin, and mostly chloropropylene, such as 1,3-dichloropropene, 2-chloropropylene and allylchloride. This is a special application of the method according to the invention is particularly preferred, as a result, it is possible to obtain a propylene containing only very small amounts of propane, usually below 3%, often below 1%, which thus can be directly recycled in the production phase of allylchloride by chlorination of propylene. Use in the production stage of allylchloride depleted propane propylene allows you to restrict the number of 1-chloropropane and/or 2-chloropropane, which are formed by chlorination of propane and are difficult to separate from allylchloride.

The invention is illustrated in more detail by the following examples.

Example 1 (according to the invention)

In this example, using a catalyst of palladium-silver on the carrier of activated carbon.

a) Preparation of catalyst ml/g, injected into the flask containing 3.5 ml of water and 1.5 ml of a solution containing 0.10 g of palladium/ml (solution of palladium chloride in 6 N. hydrochloric acid). After incubation for 15 minutes at room temperature, the impregnated activated carbon is dried in vacuum at 80oC. After cooling to room temperature in the flask was injected 6 ml of a solution containing 0.05 g of silver (AgCl in aqueous ammonia solution with an ammonia content of 25 wt. %). After incubation for 15 minutes at room temperature, the impregnated activated carbon is dried first in vacuum at 80oC, then in the helium atmosphere for 1 hour at 120oC and for 1 hour at 280oC. the Impregnated and dried active carbon is then treated for 4 hours at 280oC hydrogen.

The thus obtained catalyst contains 1.5 wt.% palladium and 3 wt.% silver, based on the weight of active carbon. X-ray analysis of the catalyst shows that the metals are present partly in the form of alloys containing from 20 to 50 at.% silver, and the grain size is from 3 to 10 nm.

b) the Conversion of 1,2-dichloropropane

of 3.43 g (7,50 cm3) Catalyst, such as described above, is introduced into a tubular reactor (internal dia standards. l/h of hydrogen at 345oC, at a pressure of 1.5 bar and within a few hours. The time is 1,39 seconds.

At various intervals, a sample is taken of the product, continuously emerging from the reactor and analyzed by chromatography in gas phase and determine the degree of conversion of 1,2-dichloropropane in propylene and the selectivity (defined as the molar fraction of unreacted 1,2-dichloropropane turned propylene).

The results of the measurements are presented in table 1.

From table 1 it follows that after the operation for a time more than 150 hours, the catalyst was still as active and selective as the original. After 8 days of operation, the catalyst allows you to still reach the degree of conversion above about 95%. At this point, turn around 711 kg 1,2-dichloropropane per kg of catalyst.

Example 2 (not according to invention)

The conversion of 1,2-dichloropropane carried out in the same conditions as those described in example 1, but using 3,67 g (7,50 cm3) catalyst containing 2.7 wt.% platinum and 1.8 wt.% copper, based on the weight of active carbon. This catalyst is applied on the same medium and under the same operating conditions, that is asnie intervals, determine the degree of conversion of 1,2-dichloropropane in propylene and selectivity, as in example 1.

The results of these changes are presented in table 1.

Comparing the obtained results reveal that in the same operating conditions and using catalysts containing the same atomic number metals of groups VIII and IB, respectively, used in example 1 (according to the invention) the catalyst containing palladium and silver, originally clearly more selective than catalyst based on platinum and copper, used in example 2 (not according to the invention). In addition, the catalyst based on platinum and copper requires more than 40 hours of operation, before the selectivity to propylene reaches 90%, while using a catalyst based on palladium with silver selectivity of 90% is achieved after only 3.50 hours.

Comparison of degrees of transformation, moreover, shows that used in example 1, a catalyst based on palladium, silver is more stable in time than the catalyst based on platinum with copper of example 2.

Example 3 (according to the invention)

The catalyst containing 0.5 mA is of the same carrier and mode of operation, similar to that described in example 1.

3,61 g (7,50 cm3This catalyst is introduced into a tubular reactor (inner diameter = 0.8 cm). Into the reactor containing the catalyst, and then upload 2.6 standards.l/h 1,2-dichloropropane and 10.3 standards.l/h of hydrogen at 350oC and a pressure of 1.5 bar. The time of contact is 1.4 seconds.

After different time intervals to determine the degree of transformation of 1,2-dichloropropane in propylene and propane and selectivity (defined as the molar fraction unreacted 1,2-dichloropropane, which are respectively turned into propylene and propane).

The results of these measurements are presented in table II.

Example 4 (not according to invention)

The conversion of 1,2-dichloropropane carried out in the same working conditions as the conditions described in example 3, but using of 3.53 g (7,50 cm3) a catalyst containing 1 wt.% platinum and 0.5 wt.% silver, based on the weight of active carbon. This catalyst is applied on the same medium and under the same operating conditions as in example 1 using an aqueous solution of H2PtCl26H2O.

After different time intervals, determine the degree of conversion of 1,2-dichloropropane in the PCC is not according to the invention)

The conversion of 1,2-dichloropropane carried out in the same conditions as described in example 3, but using a catalyst containing 1 wt.% platinum and 0.3 wt.% copper, based on the weight of active carbon. This catalyst is applied on the same medium and under the same operating conditions as in example 1 using an aqueous solution of H2PtCl66H2O and CuCl22H2O.

After different time intervals, determine the degree of conversion of 1,2-dichloropropane in propylene and propane and selectivity.

The results of these measurements are also presented in table II.

Comparing the results obtained under the same operating conditions and using catalysts containing the same atomic number metals of groups VIII and IB, respectively, reveal that the catalyst containing palladium and silver, originally clearly more selective in respect of propylene than catalysts based on platinum and silver or copper. When the above operating conditions, using a catalyst based on platinum and copper, you have over 70 hours operation before the selectivity for propylene will reach 95%. At this point, the amount of propane is always sustaini propylene of about 95% is achieved after barely 1.55 hours. The amount of propane is very minor since the beginning of the reaction and after the operation for a time less than 20 hours becomes void.

Example 6 (according to the invention)

The catalyst containing 0.5 wt.% palladium and 0.5 wt.% silver, based on the mass of the carrier, receive according to the method similar to that described in example 1, but using as a carrier of titanium dioxide (quality HARSHAW N Ti-T 1/8").

2.16 g (2.5 cm3This catalyst is introduced into a tubular reactor (inner diameter = 1.0 cm). In containing the catalyst, the reactor can then load 0.4 norms. l/h 1,2-dichloropropane, 0.8 norms.l/h of hydrogen and 2.7 norms. l/h of helium at 350oC and a pressure of 1.5 bar. The time of contact is 1.5 seconds.

The degree of transformation of 1,2-dichloropropane is 100%, the selectivity for propylene is 82% and the selectivity in respect of chloropropylene (sum of fractions 1-, 2 - and 3-chloropropylene) is 18%.

Example 7 (according to the invention)

For the conversion of 1,2,3-trichloropropane use a catalyst containing 1.5 wt.% palladium and 3 wt.% silver, based on the weight of activated carbon, which is obtained as described in example 1.

containing a series of catalyst, then upload 0,78 standards.l/h 1,2,3-trichlorpropane, 3.12 norms.l/h of hydrogen and 3.9 norms.l/h of helium at 300oC and a pressure of 3 bars.

The time of contact is 1.7 seconds.

The degree of conversion of 1,2,3-trichloropropane is 93% and the selectivity for propylene reaches 99%.

Example 8 (according to the invention)

In this example, using a catalyst based on palladium and tin on the active angle.

a) Preparation of catalyst on the carrier

50.0 g of Active charcoal (quality NC 35; issued in a sale by the company CECA), having a pore volume of 0.5 ml/g, is introduced into the flask with 18,0 ml of water and 17.0 ml of a solution containing 0,0147 g of palladium per ml (solution of palladium chloride in 6 M hydrochloric acid). After incubation for 60 minutes at room temperature, the impregnated activated carbon is dried in vacuum at 80oC, then at 100oC. After cooling to room temperature in the flask enter 16,08 ml of a solution containing 0,0171 g tin/ml (solution of SnCl45H2O). After keeping at room temperature for 60 minutes, the impregnated activated carbon is dried in vacuum at 80oC, then at 100oC. the Impregnated and dried active carbon 0.5. % (4.7 mmol) of palladium and 0.55 wt.% (4.6 mmol) of tin, calculated on the weight of activated carbon.

b) the Conversion of 1,2-dichloropropane

4.5 g (10 cm3) Videolounge catalyst is introduced into a tubular reactor (inner diameter = 0.8 cm). Into the reactor containing the catalyst, and then download the 3.0 rules.l/h 1,2-dichloropropane, 21,0 standards.l/h of helium and 6 standards. l/h of hydrogen at 300oC and a pressure of 3 bars within a few hours. The time of contact is 1.7 seconds.

After functioning for 8.5 hours and 14.5 hours away samples of products coming from the reactor and analyzed by chromatography in gas phase and determine the degree of conversion of 1,2-dichloropropane and selectivity to propylene.

The results of the measurements are presented in table III.

From this table it follows that the degree of conversion is higher or equal to 95% and the selectivity for propylene is 96%, and, after functioning for a 14.5 hours, the catalyst is still active and has a high selectivity, and after 8.5 hours of time functioning.

Examples 9 and 10 (not according to invention)

The conversion of 1,2-dichloropropane carried out in the same working is 9) and 0.5 wt.% platinum and 0.3 wt.% tin (example 10), moreover, quantities are expressed per mass of active carbon. These catalysts applied on the same medium and under the same operating conditions as in example 8, using aqueous solutions of H2PtCl66H2O, CuCl22H2O and SnCl45H2O.

After intervals of 8.5 hours and 14.5 hours to determine the degree of conversion of 1,2-dichloropropane and the selectivity for propylene as in example 8. The results of these measurements are also presented in table III.

Examples II, 12 and 13 (according to the invention)

The conversion of 1,2-dichloropropane carried out under the same operating conditions as described in example 8, but using a catalyst containing 0.5 wt.% palladium and 0.97 wt.% lead (example 11); 0.5 wt.% palladium and 0.96 wt.% thallium (example 12); and 0.5 wt.% palladium and 0.98 wt.% bismuth (example 13), and the quantities are expressed per mass of active carbon. These catalysts applied on the same medium and under the same operating conditions as in example 8, using aqueous solutions of Pb(CH3CO2)23H2O, Tl(CH3CO2)3and Bi(NO3)35H2O.

After intervals of 8.5 hours and 14.5 hours, determine the degree of conversion of 1,2-dichloropropane in propylene and the selectivity, the nnye results find that in the same operating conditions used in examples 8, 11, 12 and 13 (according to the invention) catalysts containing palladium, can achieve very good degree of conversion of 1,2-dichloropropane and they are clearly more selective towards propylene than catalysts based on platinum, used in examples 9 and 10 (not according to the invention).

Example 14 (according to the invention)

In this example, using a catalyst based on palladium and tin on a carrier of alumina. The catalyst was prepared in the same working conditions as in example 8, using a carrier of aluminum oxide (alpha-alumina having a pore volume of 0.43 ml/g and a specific surface area of 3 m2/g).

The conversion of 1,2-dichloropropane carried out in the same working conditions as described in example 8, but using 9,1 g (10 cm3) a catalyst containing 0.5 wt.% palladium and 0.55 wt.% tin, calculated on the weight of alumina.

After intervals of 8.5 hours and 14.5 hours, determine the degree of conversion of 1,2-dichloropropane in propylene and selectivity, as in example 8.

The results of these measurements are presented in table IV.

Example 1 is vannie in example 14, but using a catalyst containing 0.5 wt.% platinum and 0.3 wt.% tin, calculated on the weight of alumina. This catalyst is applied on the same media and by the same method as in example 14, using an aqueous solution of H2PtCl66H2O.

After the same time intervals, determine the degree of conversion of 1,2-dichloropropane in propylene and selectivity, as in example 14.

The results of these measurements are also presented in table IV.

Comparing the obtained results reveal that, in the same operating conditions used in example 14 (according to the invention) comprising palladium catalyst is clearly more selective towards propylene than the catalyst based on platinum, used in example 15 (not according to the invention).

1. The way of transformation of chlorinated alkane in less chlorinated alkene by reacting chlorinated alkane with hydrogen in the presence of a catalyst containing a metal of group VIII and a metal M, on the media, wherein the metal of group VIII is palladium and the metal M is chosen in the group consisting of silver, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth and mixtures thereof.

4. The method according to p. 3, characterized in that the metal M is silver.

5. The method according to any of paragraphs.1 to 4, characterized in that the chlorinated alkane is chosen among chloropropanol.

6. The method according to p. 5, characterized in that chloropropane are by-products generated during the production of allylchloride and/or epichlorohydrin.

7. The method according to p. 5 or 6, characterized in that the chlorinated alkanol is 1,2-dichloropropane.

8. The method according to any of paragraphs.1 to 7, characterized in that the carrier is active carbon.

9. The method according to any of paragraphs.1 to 8, characterized in that the amount of palladium on the carrier is 0.05 - 10 wt.%, in the calculation of the mass media.

10. The method according to any of paragraphs.1 to 9, characterized in that the amount of metal M on the media is 0.05 - 10 wt.%, in the calculation of the mass media.

11. The method according to any of paragraphs.1 to 10, characterized in that the mass ratio of palladium to the metal M is 0.05 - 20.

12. The method according to any of paragraphs.1 - 11, characterized in that the reaction is carried out at a temperature of 150 to 450oC and a pressure of 1 to 30 bar.

13. The method according to SS="ptx2">

14. The method according to any of paragraphs.1 - 13, characterized in that the reaction is carried out in the gas phase with an average contact time between the gas and a catalyst comprising 0.5 to 30 C.

Priority points:

20.09.95 - PP.1 - 3;

24.11.94 - p. 4;

24.11.94 and 20.09.95 - PP.5 - 14.

 

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61 cl, 8 tbl, 32 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to perfluoroolefins production technology, notably to heaxafluorobutadiene CF2=CF-CF=CF2. Process comprises reaction of 1,2,3,4-tetrachlorohexafluorobutane with zinc in aqueous medium at 30 to 90°C. Reaction is carried out by metering 1,2,3,4-tetrachlorohexafluorobutane into reaction vessel containing zinc and water, while simultaneously desired product formed is recovered. Advantageously, process is conducted in presence of promoter selected from acids such as sulfuric acid and hydrochloric acid, soluble weak base salts such as zinc and ammonium halides, interphase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, tetrakis(dialkylamino)phosphonium salts, and N,N',N"-hexaalkyl-substituted guanidinium salts, or mixtures of indicated substances.

EFFECT: increased purity of heaxafluorobutadiene and simplified technology.

4 cl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to oxidative halogenation processes to obtain halogenated products, in particular allyl chloride and optionally propylene. Process comprises interaction of hydrocarbon having between 3 and 10 carbon atoms or halogenated derivative thereof with halogen source and optionally oxygen source in presence of catalyst at temperature above 100°C and below 600°C and pressure above 97 kPa and below 1034 kPa. Resulting olefin containing at least 3 carbon atoms and halogenated hydrocarbon containing at least 3 carbon atoms and larger number of halogen atoms than in reactant. Catalyst contains essentially iron and copper-free rare-earth metal halide or oxyhalide. Atomic ratio of rare-earth metal to iron or copper is superior to 10:1. In case of cerium-containing catalyst, catalyst has at least one more rare-earth element, amount of cerium present being less than 10 atomic % of the total amount of rare-earth elements. Advantageously, process is conducted at volumetric alkane, halogen, and oxygen supply rate above 0.1 and below 1.0 h-1, while diluent selected from group including nitrogen, helium, argon, carbon monoxide or dioxide or mixture thereof is additionally used. Halogenated product is recycled while being converted into supplementary olefin product and olefin product is recycled in order to be converted into halogenated hydrocarbon product. Optionally, allyl chloride and ethylene are obtained via interaction of propane with chlorine source in presence of catalyst.

EFFECT: increased productivity of process and improved economical characteristics.

26 cl, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of chlorinated ethylene derivatives, in particular, vinyl chloride, vinylidene chloride, trichloroethylene by the dehydrochlorination reaction of corresponding chlorinated ethane derivatives. The process is carried out in the presence of sodium hydroxide aqueous solution, catalyst of interphase transfer relating to polyglycols and an extractant-promoter representing mixture of chlorinated hydrocarbons of the general formula: CnH2n +2-xClx wherein n = 10-30; x = 1-7 with molecular mass 250-305 Da and the chlorine content is 24-43% followed by isolation of end substances by the known procedures. As a catalyst of interfase transfer the method uses polyethylene glycols in the amount 0.0001-1% of the mass of the parent chlorinated ethane derivative. Extractant-promoter is used in the amount 1-10% of the mass of the parent ethane derivative. The mole ratio of chlorinated ethane derivative to sodium hydroxide = 1:(1.15-5) at the concentration of sodium hydroxide aqueous solution 5-35 wt.-%. Invention provides the development of the complex method for synthesis of chlorinated ethylene derivatives from chlorinated ethane derivatives, among them, from depleted reagents of the method or waste of corresponding industry, and increasing yield of end products.

EFFECT: improved method of synthesis.

7 cl, 1 tbl, 12 ex

FIELD: chemical industry; methods of production of vinylidene chloride.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of vinylidene chloride by the dehydrochlorination of 1,1,2- trichloroethane with formation of the target product and the quaternary ammonium salts. As the reactant of the dehydrochlorination they use the water-alcoholic solutions of hydroxides - dimethyl-β or γ- chlorodipropenyl of ammonium gained by the electrolysis of the solutions of dimethyl-β or γ- chlorodipropenyl of ammonium chloride in the water at presence of methyl, ethyl or butyl alcohols in the electrolyzers with the ion-exchange membranes. At that the gained hydroxides are sent to the dehydrochlorination. The technical result of the invention is creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.

EFFECT: the invention ensures creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.

3 cl, 3 ex, 1 dwg

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