Processes for producing very high purity 1,1,1,2,3-pentachloropropane

Abstract

Disclosed is a process for preparing a highly pure 1,1,1,2,3-pentachloropropane product, comprising 1-a) providing a reaction mixture comprising ethylene, carbon tetrachloride and a catalyst in a principal alkylation zone to produce 1,1,1,3-tetrachloropropane in the reaction mixture, and 1-btreating the reaction mixture obtained in step 1-a) to obtain a 1,1,1,3-tetrachloropropane feedstock; 2-a) contacting the 1,1,1,3-tetrachloropropane feedstock with a catalyst in a dehydrochlorination zone to produce a reaction mixture comprising 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene, and 2-b) treating the reaction mixture obtained in step 2-a) to obtain a 1,1,3-trichloropropene feedstock; 3-a) contacting the 1,1,3-trichloropropene feedstock with chlorine in a reaction zone to produce a reaction mixture containing 1,1,1,2,3-pentachloropropane and 1,1,3-trichloropropene, the reaction zone being different from the dehydrochlorination zone, and 3-b) treating the reaction mixture obtained in step 3-a) to obtain the highly pure 1,1,1,2,3-pentachloropropane product.

Claims

1. A process for preparing a highly pure 1,1,1,2,3-pentachloropropane product comprising: 1-a) providing a reaction mixture comprising ethylene, carbon tetrachloride and a catalyst in a principal alkylation zone to produce 1,1,1,3-tetrachloropropane in the reaction mixture, and, 1-b) treating the reaction mixture obtained in step 1-a) to obtain a 1,1,1,3-tetrachloropropane feedstock; 2-a) contacting the 1,1,1,3-tetrachloropropane feedstock with a catalyst in a dehydrochlorination zone to produce a reaction mixture comprising 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene, and 2-b) treating the reaction mixture obtained in step 2-a) to obtain a 1,1,3-trichloropropene feedstock; 3-a) contacting the 1,1,3-trichloropropene feedstock with chlorine in a reaction zone to produce a reaction mixture containing 1,1,1,2,3-pentachloropropane and 1,1,3-trichloropropene, the reaction zone being different from the dehydrochlorination zone, and 3-b) treating the reaction mixture obtained in step 3-a) to obtain the highly pure 1,1,1,2,3-pentachloropropane product wherein, in step 1-a), the concentration of the 1,1,1,3-tetrachloropropane in the reaction mixture in the principal alkylation zone is maintained at a level such that the molar ratio of 1,1,1,3-tetrachloropropane:carbon tetrachloride in the reaction mixture does not exceed: 95:5 where the principal alkylation zone is in continuous operation, or 99:1 where the principal alkylation zone is in batchwise operation.

2. The process of claim 1, wherein treatment steps 1-b), 2-b) and/or 3-b) comprise a distillation step.

3. The process of claim 1, wherein treatment steps 1-b), 2-b) and/or 3-b) comprise contacting compositions comprising 1,1,1,3-tetrachloropropane (in the case of step 1-b), 1,1,3-trichloropropene (in the case of step 2-b), and/or 1,1,1,2,3-pentachloropropane (in the case of step 3-b) with an aqueous medium.

4. The process of claim 1, wherein the reaction mixture produced in step 1-a) is extracted from the principal alkylation zone and is subjected to an aqueous treatment step in step 1-b), in which the reaction mixture is contacted with an aqueous medium in an aqueous treatment zone, a biphasic mixture is formed and an organic phase comprising catalyst is extracted from the biphasic mixture.

5. The process of claim 1, wherein the catalyst used in step 1-a) is a metallic catalyst, optionally further comprising an organic ligand.

6. The process of claim 5, wherein the organic ligand is an alkylphosphate.

7. The process of claim 1, wherein the reaction mixture produced in step 1-a) is extracted from a primary alkylation zone and fed into the principal alkylation zone, wherein the ratio of 1,1,1,3-tetrachloropropane:carbon tetrachloride present in the reaction mixture extracted from the principal alkylation zone is greater than the ratio of 1,1,1,3-tetrachloropropane:carbon tetrachloride present in the reaction mixture taken from the primary alkylation zone.

8. The process of claim 1, wherein the amount of unreacted ethylene in the reaction mixture leaving the principal alkylation zone is less than 0.6%.

9. The process of claim 1, wherein any unreacted gaseous ethylene is directly recycled back to the alkylation reaction zone/s operating at elevated pressure.

10. The process of claim 1, wherein any unreacted gaseous ethylene is recycled back to the reaction zone/s operating at elevated pressure by absorbing ethylene into the cold liquid carbon tetrachloride feedstock.

11. The process of claim 1, wherein step 2-b) comprises contacting a mixture comprising 1,1,3-trichloropropene, catalyst and 1,1,1,3-tetrachloropropane with an aqueous medium in an aqueous treatment zone.

12. The process of claim 11, wherein a biphasic mixture is formed in the aqueous treatment zone and an organic phase comprising 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene is extracted from the biphasic mixture.

13. The process of claim 1, wherein all parts of the dehydrochlorination zone which come into contact with the reaction mixture in step 2-a) have an iron content of about 20% or less and/or are formed from non-metallic materials.

14. The process according to claim 13, wherein the non-metallic materials are selected from the group consisting of enamel, glass, impregnated graphite, silicium carbide, plastics materials and any combination thereof.

15. The process according to claim 14, wherein the impregnated graphite is impregnated with phenolic resin.

16. The process according to claim 14, wherein the plastic materials are selected from the group consisting of polytetrafluoroethylene, perfluoroalkoxy, polyvinylidene fluoride, and any combination thereof.

17. The process of claim 1, wherein at least some parts of the dehydrochlorination zone which come into contact with the reaction mixture in step 2-a) are formed of a nickel-based alloy.

18. The process according to claim 17, wherein the nickel-based alloy comprises nickel, chromium, molybdenum, iron, and tungsten.

19. The process of claim 1, wherein reaction mixture produced in step 3-a) is extracted from the primary reaction zone and is then subjected to a principal conversion step in a principal reaction zone to produce a 1,1,1,2,3-pentachloropropane rich product, which is extracted from the principal reaction zone.

20. The process of claim 19, wherein, in step 3-a), the principal conversion step comprises a reduced temperature conversion step in which the reaction mixture extracted from the primary reaction zone is fed into a principal reaction zone operated at a reduced temperature and the 1,1,1,2,3-pentachloropropane rich product is extracted from the principal reaction zone.

21. The process of claim 19, wherein the primary and/or the principal reaction zone is exposed to visible light and/or ultraviolet light.

22. The process according to claim 19, wherein the 1,1,1,2,3-pentachloropropane rich product produced in step 3-a) is subjected to an aqueous treatment and/or hydrolysis step.

23. The process according to claim 22, wherein the aqueous treatment and/or hydrolysis step comprises contacting the 1,1,1,2,3-pentachloropropane rich product with an aqueous medium in an aqueous treatment zone.

24. The process according to claim 19, wherein step 3-b) comprises one or more distillation steps, carried out on the 1,1,1,2,3-pentachloropropane rich product produced in step 3-a).

25. The process according to claim 19, wherein step 3-b) comprises one or more distillation steps, carried out on an organic phase extracted from the mixture formed in an aqueous treatment zone.

26. The process of claim 1, wherein step 3-b) comprises one or more distillation steps, carried out on the reaction mixture produced in step 3-a).

27. A process for preparing a highly pure 1,1,1,2,3-pentachloropropane product comprising: 1-a) providing a reaction mixture comprising ethylene, carbon tetrachloride and a catalyst in a principal alkylation zone to produce 1,1,1,3-tetrachloropropane in the reaction mixture, and 1-b) treating the reaction mixture obtained in step 1-a) to obtain a 1,1,1,3-tetrachloropropane feedstock; 2-a) contacting the 1,1,1,3-tetrachloropropane feedstock with a metal catalyst, a metal salt catalyst or any combination thereof, in a dehydrochlorination zone to produce a reaction mixture comprising 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene, and 2-b) treating the reaction mixture obtained in step 2-a) to obtain a 1,1,3-trichloropropene feedstock; 3-a) contacting the 1,1,3-trichloropropene feedstock with chlorine in a reaction zone to produce a reaction mixture containing 1,1,1,2,3-pentachloropropane and 1,1,3-trichloropropene, the reaction zone being different from the dehydrochlorination zone, and 3-b) treating the reaction mixture obtained in step 3-a) to obtain the highly pure 1,1,1,2,3-pentachloropropane product, wherein the concentration of the 1,1,3-trichloropropene in the reaction mixture produced in step 2-a) in the dehydrochlorination zone is controlled such that the molar ratio of 1,1,3-trichloropropene:1,1,1,3-tetrachloropropane is from 1:99 to 50:50.

28. A process for preparing a highly pure 1,1,1,2,3-pentachloropropane product comprising: 1-a) providing a reaction mixture comprising ethylene, carbon tetrachloride and a catalyst in a principal alkylation zone to produce 1,1,1,3-tetrachloropropane in the reaction mixture, and 1-b) treating the reaction mixture obtained in step 1-a) to obtain a 1,1,1,3-tetrachloropropane feedstock; 2-a) contacting the 1,1,1,3-tetrachloropropane feedstock with a metal catalyst, a metal salt catalyst or any combination thereof, in a dehydrochlorination zone to produce a reaction mixture comprising 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene, and 2-b) treating the reaction mixture obtained in step 2-a) to obtain a 1,1,3-trichloropropene feedstock; 3-a) contacting the 1,1,3-trichloropropene feedstock with chlorine in a reaction zone to produce a reaction mixture containing 1,1,1,2,3-pentachloropropane and 1,1,3-trichloropropene, the reaction zone being different from the dehydrochlorination zone, and 3-b) treating the reaction mixture obtained in step 3-a) to obtain the highly pure 1,1,1,2,3-pentachloropropane product, wherein, in step 3-a), the degree of conversion of the 1,1,3-trichloropropene starting material to the 1,1,1,2,3-pentachlorpropane product is controlled such that the molar ratio of 1,1,1,2,3-pentachloropropane:1,1,3-trichloropropene in the reaction mixture produced in step 3-a) does not exceed 95:5.

29. A process for preparing a highly pure 1,1,1,2,3-pentachloropropane product comprising: 1-a) providing a reaction mixture comprising ethylene, carbon tetrachloride and a catalyst in a principal alkylation zone to produce 1,1,1,3-tetrachloropropane in the reaction mixture, and 1-b) treating the reaction mixture obtained in step 1-a) to obtain a 1,1,1,3-tetrachloropropane feedstock; 2-a) contacting the 1,1,1,3-tetrachloropropane feedstock with a metal catalyst, a metal salt catalyst or any combination thereof, in a dehydrochlorination zone to produce a reaction mixture comprising 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene, and 2-b) treating the reaction mixture obtained in step 2-a) to obtain a 1,1,3-trichloropropene feedstock; 3-a) contacting the 1,1,3-trichloropropene feedstock with chlorine in a reaction zone to produce a reaction mixture containing 1,1,1,2,3-pentachloropropane and 1,1,3-trichloropropene, the reaction zone being different from the dehydrochlorination zone, and 3-b) treating the reaction mixture obtained in step 3-a) to obtain the highly pure 1,1,1,2,3-pentachloropropane product, wherein the reaction mixture produced in step 3-a) is subjected to an aqueous treatment and/or hydrolysis step.

30. The process according to claim 29, wherein the aqueous treatment and/or hydrolysis step comprises contacting the reaction mixture with an aqueous medium in an aqueous treatment zone.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1—Alkylation Step

(2) TABLE-US-00001 1 ethene feed stream 2 particulate iron feed stream 3 continuously stirred tank reactor (primary alkylation zone) 4 plug/flow reactor (principal alkylation zone) 5 reaction mixture stream 6 flash evaporation vessel 7 1,1,1,3-tetrachloropropane-rich mixture stream 8 evaporated ethene stream 9 condenser 10 ethene stream 11 absorption column 12 carbon tetrachloride and tributyl phosphate/ferric chloride catalyst feed stream 13 stream of recovered catalyst (tributyl phosphate/ferric chloride), fresh catalyst and carbon tetrachloride 14 cooler 15 cooled stream of recovered catalyst (tributyl phosphate/ferric chloride), fresh catalyst and carbon tetrachloride 16 off-gas

(3) FIG. 2—First Distillation Step

(4) TABLE-US-00002 101 1,1,1,3-tetrachloropropane-rich mixture stream (stream with reference numeral 7 in FIG. 1) 102 batch distillation boiler 103 stream of 1,1,1,3-tetrachloropropane-rich mixture comprising catalyst 104 vacuum distillation column 105 distillate stream 106 condenser 107 intermediate line 108 reflux divider 109 reflux stream 110.1 light ends stream 110.2 carbon tetrachloride stream 110.3 tetrachloroethene stream 110.4 purified 1,1,1,3-tetrachloropropane product stream

(5) FIG. 3—Aqueous Catalyst Recovery Step

(6) TABLE-US-00003 201 weak hydrochloric acid solution stream 202 1,1,1,3-tetrachloropropane-rich mixture feed stream comprising catalyst 203 haloalkane extraction agent feed stream (1,1,1,3- tetrachloropropane) 204 batch distillation boiler 205 batch distillation boiler outlet 206 filtration 207 filter cake removal 208 organic phase stream (part of feed stream 13 in FIG. 1) 209 aqueous phase stream 210 column for steam distillation of crude 1,1,1,3-tetrachloropropane 211 crude 1,1,1,3-tetrachloropropane stream 212 condenser 213 condensed crude 1,1,1,3-tetrachloropropane stream 214 reflux liquid-liquid separator 215 reflux stream 216 crude 1,1,1,3-tetrachloropropane stream for further distillation

(7) FIG. 4—Second Distillation Step

(8) TABLE-US-00004 301 crude 1,1,1,3-tetrachloropropane product feed stream 302 distillation boiler 303 heavy ends residue 304 distillation column 306 condenser 308 reflux divider 310.1 purified 1,1,1,3-tetrachloropropane product stream 310.2 chlorinated pentane/pentene stream

(9) FIG. 5—Dehydrochlorination Step (1,1,1,3-tetrachloropropane Conversion to 1,1,3-trichloropropene)

(10) TABLE-US-00005 401 1,1,1,3-tetrachloropropane feed stream 402 ferric chloride feed stream 403 continuously stirred tank reactor 404 reaction residue 405 filter 406 filter cake 407 filtrate 408 distillation column 409 1,1,3-trichloropropene rich stream 410 partial condenser 411 gaseous hydrogen chloride stream 412 1,1,3-trichloropropene rich stream 413 reflux divider 414 reflux stream 415 purified 1,1,3-trichloropropene product stream

(11) FIG. 6—Aqueous Treatment Step

(12) TABLE-US-00006 501 aqueous hydrochloric acid feed stream 502 residue feed stream (from the reactor in FIG. 1, stream 4) 503 haloalkane extraction agent feed stream 504 505 washing tank 506 washing tank outlet 507 filter 508 filter cake 509 organic phase stream 510 aqueous phase stream 511 distillation column 512 chlorinated alkanes stream 513 condenser 514 intermediate line 515 reflux liquid-liquid separator 516 aqueous phase (reflux) stream 517 organic phase (1,1,1,3-tetrachloropropane) stream

(13) FIG. 7—Distillation Step

(14) TABLE-US-00007 601 organic phase (1,1,1,3-tetrachloropropane) feed stream 602 distillation boiler 603 heavy ends residue stream 604 filter 605 filter cake 606 liquid residue 607 distillation column 609 condenser 611 reflux divider 613.1 1,1,3-trichloropropene product stream 613.2 1,1,1,3-tetrachloropropane stream

(15) FIG. 8—Primary Conversion and Principal Conversion Steps (1,1,3-trichloropropene Conversion to 1,1,1,2,3-pentachloropropane)

(16) TABLE-US-00008 701 gaseous chlorine feed stream 702 gas-liquid reactor column 703 external circulation loop 704 external cooler 705 external circulation loop 706 1,1,3-trichloropropene feed stream 707 external circulation loop 708 1,1,1,2,3-pentachloropropane-rich stream 709 cooler 710 1,1,1,2,3-pentachloropropane-rich stream (feed to hydrolysis step, FIG. 2) 711 off-gas

(17) FIG. 9—Hydrolysis Step

(18) TABLE-US-00009 801 water stream 802 1,1,1,2,3-pentachloropropane-rich feed stream 803 washing tank 804 washing tank outlet 805 filter 806 filter cake 807 1,1,1,2,3-pentachloropropane-rich product stream 808 wastewater stream

(19) FIG. 10—Distillation Step

(20) TABLE-US-00010 901 1,1,1,2,3-pentachloropropane-rich feed stream (product stream 107, FIG. 2) 902 distillation boiler 903 distillation residue stream 904 filter 905 filter cake 906 heavies stream 907 vacuum distillation column 908 distillate stream 909 condenser 910 intermediate line 911 liquid divider 912 reflux stream 913.1 1,1,3-trichloropropene stream 913.2 1,1,1,3-tetrachloropropane stream 913.3 purified 1,1,1,2,3-pentachloropropane stream

EXAMPLES

(21) The present invention is now further illustrated in the following examples. For the avoidance of doubt, where reference is made to units of pressure (kPa) herein it is the absolute value which is identified. Where values are presented as percentages herein, they are percentages by weight unless otherwise stated. Where the purity of a composition or material is presented by percentage or ppm herein, unless otherwise stated, this is a percentage/ppm by weight.

(22) For clarity, Examples 1 to 7 exemplify or relate to the telomerisation reaction (and subsequent treatment steps) of step 1) of the process of the present invention. Examples 8 to 12 exemplify or relate to the dehydrochlorination reaction (and subsequent treatment steps) of step 2) of the process of the present invention. Examples 13 to 19 exemplify or relate to the chlorination reaction (and subsequent treatment steps) of step 3) of the process of the present invention.

(23) Abbreviations used: TeCPa=1,1,1,3-tetrachloropropane TCPe=1,1,3-trichloropropene PCPa=1,1,1,2,3-pentachloropropane TeCM: tetrachloromethane TeCPna: tetrachloropentane HCE=hexachloroethane DCPC=dichloropropanoylchloride Bu.sub.3PO.sub.4: Tributylphosphate

Example 1

Demonstration of Catalytic Ability of Recovered Catalyst Using an Aqueous Treatment

(24) Ethylene and carbon tetrachloride were reacted to produce 1,1,1,3-Tetrachloropropane in the presence of catalyst which was either i) recovered from a reaction mixture using conventional distillation techniques, or ii) recovered from a reaction mixture using the inventive aqueous treatment step for catalyst described herein. The reaction mixture additionally comprised 1,1,1,3-Tetrachloropropane (present in the recycle stream) and tetrachloropentane (a chlorinated alkane impurity commonly formed as a byproduct in the presence of telomerisation reactions between carbon tetrachloride and ethylene).

(25) These test examples show that using the aqueous treatment step to recover catalyst, the performance of the catalyst is significantly higher as compared to catalyst recovered using conventional distillation techniques.

(26) Gas chromatography was used to monitor the progress of the reaction.

(27) Batchwise Arrangement

(28) A stainless steel autoclave with a volume of 405 ml, equipped with a stirrer, a thermowell for temperature measurement and a sampling tube (with valve) was filled with the reaction mixture described below and closed. Heating was provided by means of an oil bath placed on a magnetic (heating) stirrer. Ethylene was fed by a copper capillary tube from 10 l cylinder placed on weighing scale. The gaseous atmosphere in the autoclave was replaced by ethylene flushing. After pressurizing with ethylene to 5 bar, the autoclave was heated up to 105° C., then the ethylene supply to the autoclave was opened. Ethylene supply was controlled manually for a first ten minutes (to maintain the reaction temperature to 112° C.), and later was maintained at a constant pressure of 9 bar. The reaction was allowed to react defined time period. Than the reactor was cooled and reaction mixture was withdrawn after opening of depressurised reactor.

Comparative Examples 1-1 and 1-3 and Examples 1-2, 1-4 and 1-5

(29) In the first example, the distillation residue was directly used as a recycled catalyst (Comparative Example 1-1). In the second example, the distillation residue was extracted with 5% hydrochloric acid and a filtered organic fraction was used as a catalyst (Example 1-2).

Comparative Example 1-1

(30) 90.1 g of a distillation residue comprising 63.7% TeCPa, 22.8% TeCPna and 7.49% Bu.sub.3PO.sub.4 was mixed with 400 g of TeCM. The mixture was then introduced into the autoclave where 5.0 g of iron was added. After flushing with ethylene, the mixture was heated in the autoclave up to 110° C. At this temperature and at a pressure of 9 bar of ethylene, the reaction mixture was allowed to react for 4.5 hours. The first sample was taken after 3 hours. The concentration of residual TeCM at the end of the experiment was 19.7% (33.0% after 3 hours).

Example 1-2

(31) 90.1 g of a distillation residue comprising 63.7% TeCPa, 22.8% TeCPna and 7.49% Bu.sub.3PO.sub.4 was extracted with 370 g of 5% HCl. A bottom organic layer was filtered and mixed with 400 g TeCM. The mixture was then introduced into the autoclave where 5.0 g of iron was added. After flushing with ethylene, the mixture was heated in the autoclave up to 110° C. At this temperature and at a pressure of 9 bar of ethylene, the reaction mixture was allowed to react for 4.5 hours. The first sample was taken after 3 hours. The concentration of residual TeCM at the end of the experiment was 5.5% (24.6% after 3 hours).

Comparative Example 1-3

(32) Comparative Example 1-3 was carried out using identical conditions as those employed in Comparative Example 1-1, except that differing concentrations of tetrachloromethane and tributylphosphate were used.

Example 1-4 and 1-5

(33) Examples 1-4 and 1-5 were carried out using identical conditions as those employed in Example 1-2, except that differing concentrations of tetrachloromethane and tributylphosphate were used.

(34) The results of Comparative Example 1-1 and Example 1-2, and Comparative Example 1-3 and Examples 1-4 and 1-5 are shown in the following table. As can be seen, the percentage of tetrachloromethane which was converted to 1,1,1,3-Tetrachloropropane is significantly higher in Examples 1-2, 1-4 and 1-5 than in Comparative Examples 1-1 and 1-3 demonstrating that the performance of an aqueous treatment step when recovering the catalyst has a profound positive effect on the system. This is due to the high viability of the catalyst recovered from the distillate residue and also potentially due to the removal of impurities (e.g. oxygenated impurities) from the reaction mixture which otherwise may retard the reaction.

(35) TABLE-US-00011 % TeCM in % of reacted TeCM Example Bu.sub.3PO.sub.4 the feedstock 3 hrs. 4.5 hrs. Comparative 1.37% 84.7% 57.4% 73.8% Example 1-1 Example 1-2 1.35% 83.7% 67.3% 92.4% Comparative 1.77% 78.7% 60.0% 78.1% Example 1-3 Example 1-4 1.64% 81.2% 87.7% 99.4% Example 1-5 1.64% 70.6% 78.7% 99.4%
Continuous Arrangement:

(36) The same stainless steel autoclave as described above for the batch experiments was used as a stirred flow continuous reactor. The reactor was initially filled with approximately 455 g of reaction mixture. After pressurizing with ethene to 5 bar, the autoclave was heated up to 105° C., then the ethylene supply to the autoclave was opened, with continuous feed of the raw material and continuous withdrawal of the reaction mixture started.

(37) Feedstock solution with dissolved catalyst was fed into the autoclave from a stainless steel tank. The tank was placed above the reactor, and thus, a pump was not used for feeding the reactor. Reactor and tank were under an atmosphere of ethene distributed by copper capillaries from the cylinder, with conditions in the cylinder selected to prevent commencement of the reaction. Sampling of the reaction mixture was carried out by sampling tube every five minutes. To monitor the course of the reaction, the container with the feedstock and dissolved catalyst, cylinder of ethene and the withdrawn reaction mixture were weighed. The reaction mixture was always collected for an hour and after that, the collecting vessel is replaced.

Comparative Example 1-6 and 1-8 and Examples 1-7 and 1-9

(38) Continuous experiments comparing the activity of recycled catalyst (i.e. a distillation residue were conducted with and without performance of an aqueous treatment step. In the first case, the distillation residue was directly used as a recycled catalyst (Comparative Example 1-6). In the latter cases, the reaction mixture, after aqueous treatment of the distillation residue with 5% HCl, was used as a raw material containing recycled catalyst (Examples 1-4 and 1-5).

Comparative Example 1-6

(39) 587.5 g of the distillation residue comprising 63.7% TeCPa, 22.8% TeCPna and 7.49% Bu3PO4 was mixed with 2200 g of TeCM. This mixture comprised 78.7% TeCM, 11.8% TeCPa, 5.8% TeCPna and was used as a feed stream for the continuous arrangement. The reaction vessel constituted an autoclave was filled with reaction mixture and 8 g of fresh iron. The reaction was carried out at 110° C. with a pressure of ethylene of 9 bar. The residence time was 2.7 hours. During the reaction, the amount of reacted TeCM ranged between 75-76%.

Example 1-7

(40) 587.5 g of the distillation residue comprising 63.7% TeCPa, 22.8% TeCPna 7.49% Bu3PO4 was added dropwise over 1.5 hour into 1001.5 g of boiling 5% HCl. This mixture was then stripped. From the overhead product, an organic phase was collected and an aqueous phase was returned as a reflux. Distillation was terminated after an hour when all of the distillation residue was added. The residue, after stripping, was diluted with 200 g of TeCM and then separated in a separatory funnel. A bottom organic phase was filtered and together with distilled residue was mixed with 2000 g of TeCM. This mixture comprised 81.2% TeCM, 10.8% TeCPa and 5.3% TeCPna. It was used as a feed stream for the continuous arrangement of the experiment. The reaction vessel (autoclave) was filled with the older reaction mixture and 8 g of fresh iron. The reaction was carried out at 110° C. and a pressure of ethene of 9 bar. Residence time was 2.7 hours/flow rate. During the time of the reaction the amount of reacted TeCM ranged between 83-85%.

Comparative Example 1-8

(41) Comparative Example 1-8 was carried out using identical conditions as those employed in Comparative Example 1-6, except that differing concentrations of tetrachloromethane and tributylphosphate were used.

Example 1-9

(42) Example 1-9 was carried out using identical conditions as those employed in Example 1-7, except that differing concentrations of tetrachloromethane and tributylphosphate were used.

(43) TABLE-US-00012 Example % TeCM in % reacted (recycled catalyst) Bu.sub.3PO.sub.4 the feedstock TeCM Comparative 1.67% 78.7% 75.0%.sup.  Example 1-6 Example 1-7 1.64% 81.2% 84% Comparative 1.83% 76.8% 60% Example 1-8 Example 1-9 1.89% 78.0% 89%

Example 2

Preparation of High Purity 1,1,1,3-tetrachloropropane

(44) High purity 1,1,1,3-Tetrachloropropane may be obtained according to step 1) of the process of the present invention involving an alkylation step (FIG. 1), a first distillation step (FIG. 2), an aqueous catalyst recovery step (FIG. 3) and a second distillation step (FIG. 4). However, it will be appreciated that not all of these steps are necessary to obtain high purity C.sub.3-6 alkane according to step 1) of the process of the present invention.

(45) In the alkylation step shown in FIG. 1, ethene and particulate iron are fed via lines 1 and 2 into a continuously stirred tank reactor 3. The ethene is introduced into the continuously stirred tank reactor 3 in gaseous form via a dip tube provided with a nozzle. A controlled feed of particulate iron is fed into the continuously stirred tank reactor 3.

(46) Particulate iron is intermittently fed into the continuously stirred tank reactor 3 using a controlled feed. The ongoing addition of particulate iron is employed because, as the alkylation reaction proceeds, particulate iron dissolves into the reaction mixture. It has been found that optimal results are obtained by maintaining the presence of particulate iron in the reaction mixture, in this example with the addition of 1 to 2% by weight of the reaction mixture in the primary alkylation zone. This results in the reaction mixture extracted from the primary alkylation zone having a dissolved iron content of 0.2 to 0.3% by weight of the reaction mixture.

(47) Carbon tetrachloride is fed into the continuously stirred tank reactor 3 via line 12 in liquid form. In the illustrated embodiment, the carbon tetrachloride stream is used to trap gaseous ethene extracted from the reaction mixture. However, the use of carbon tetrachloride in this way is not essential to the present invention; a feed of fresh carbon tetrachloride as the sole or main source of carbon tetrachloride could be fed into the reactor 3.

(48) Tributyl phosphate/ferric chloride catalyst is also fed into the continuously stirred tank reactor 3 via line 12. The tributyl phosphate present in that stream is partly obtained from the aqueous treatment process illustrated in FIG. 3 (and discussed below in more detail), with the balance being provided as fresh tributyl phosphate added into the system. The stream in line 12 additionally comprises a haloalkane extraction agent.

(49) In the illustrated embodiment, a single primary alkylation zone is employed, located in the continuously stirred tank reactor 3. Of course, if required, a plurality of primary alkylation zones could be employed, for example in one or more continuously stirred tank reactors, that could be operated in parallel and/or in series.

(50) The primary alkylation zone is operated under superatmospheric pressure (5 to 8 bar gauge) and elevated temperature (105° C. to 110° C.) and for a residence time of 100-120 minutes. These conditions are selected to cause the carbon tetrachloride and ethene to form 1,1,1,3-Tetrachloropropane in an alkylation reaction. However, it has been found that the total conversion of carbon tetrachloride to 1,1,1,3-Tetrachloropropane is undesirable as this also results in the formation of unwanted impurities. Thus the level of conversion of the carbon tetrachloride to the chlorinated C.sub.3-6 alkane of interest is controlled and, in this embodiment of the invention, is not permitted to proceed beyond 95% Control of the progress of the alkylation reaction is achieved partly through use of reaction conditions which do not favour the total conversion of carbon tetrachloride to 1,1,1,3-Tetrachloropropane, through control of the residence time of the reaction mixture in the continuously stirred tank reactor.

(51) Reaction mixture comprising i) unreacted carbon tetrachloride and ethene, ii) 1,1,1,3-Tetrachloropropane (the chlorinated C.sub.3-6 alkane of interest in this embodiment) and iii) tributyl phosphate/iron chloride catalyst is extracted from the primary alkylation zone (the continuously stirred tank reactor 3) and fed into a plug/flow reactor 4 (in which the principal alkylation zone is located).

(52) The reaction mixture is extracted such that particulate iron catalyst present in the primary alkylation zone 3 is not extracted and thus the reaction mixture is substantially free of particulate material. Further, in the illustrated embodiment, no additional catalyst is added into the plug/flow reactor 4, although the plug/flow reactor 4 may provided with a catalyst bed. Additionally, no further ethene is added into the plug/flow reactor 4.

(53) In the illustrated embodiment, the operating pressure in the principal alkylation zone 4 is the same as that in the primary alkylation zone 3. The residence time of the reaction mixture is about 30 minutes, which in the illustrated embodiment was sufficient to result in substantially all of the ethene present being used up in the reaction. Of course, it will be understood that for different reactor types and operating conditions, different resident times may be optimal.

(54) When the determined optimal residence time of the reaction mixture in the principal alkylation zone has been reached, reaction mixture is extracted therefrom via line 5, while being maintained at elevated pressure and temperature, and fed into flash evaporation vessel 6. In this vessel, the extracted reaction mixture is subjected to depressurisation, to atmospheric pressure. This pressure drop causes evaporation of the ethene present in the reaction mixture. The 1,1,1,3-Tetrachloropropane-rich mixture, now with substantially no ethene present, is extracted from the flash vessel via line 7 and subjected to the distillation step shown in FIG. 2, and discussed below in more detail.

(55) The evaporated ethene is extracted from the flash vessel 6 via line 8 and fed through a condenser 9. The ethene is then fed via line 10 into absorption column 11 where it is contacted with a stream of carbon tetrachloride and tributyl phosphate/iron chloride catalyst, recovered from the reaction mixture in the aqueous treatment step shown in FIG. 3, and discussed below in more detail. The stream of recovered catalyst/carbon tetrachloride 13 is passed through a cooler 14 and then fed via line 15 into the absorption column 11.

(56) The flow of cooled carbon tetrachloride/catalyst through the absorption column 11 has the effect of trapping the ethene therein. The obtained liquid flow of carbon tetrachloride/catalyst/ethene is then fed back into the continuously stirred tank reactor 3.

(57) As is apparent from FIG. 1, the illustrated embodiment includes an ethene recycling loop which is advantageous for several reasons. First, almost total utilisation of the ethene is achieved and thus the amount of ethene lost from the system is very low. Additionally, the energy requirements of the components of the ethene recycling system are also low. Further, the amount of ethene lost from the system is also very low, meaning that the environmental burden is reduced.

(58) Turning now to FIG. 2, the 1,1,1,3-Tetrachloropropane-rich mixture extracted from the flash vessel shown with reference numeral 7 in FIG. 1, is fed via line 101 into a batch distillation boiler 102 which is operated in communication with a vacuum distillation column 104. The distillation boiler is operated at a temperature of 90° C. to 95° C. Chloroalkanes present in the mixture fed into the boiler 102 are evaporated and separated using distillation column 104 (and the downstream condenser 106 and reflux divider 108) into light ends stream 110.1, carbon tetrachloride stream 110.2, tetrachloroethene stream 110.3 and purified 1,1,1,3-Tetrachloropropane product stream 110.4.

(59) The light ends and tetrachloroethene streams 110.1, 110.3 may be used in the production of carbon tetrachloride, advantageously minimising the production of waste products. This can be achieved through use of a high temperature chlorinolysis process.

(60) The carbon tetrachloride stream 110.2 is recycled back into the continuously stirred tank reactor shown with reference numeral 3 in FIG. 1. The purified 1,1,1,3-Tetrachloropropane product stream 110.4 is extracted from the system and may be stored for shipment or employed in downstream processes requiring pure 1,1,1,3-Tetrachloropropane as a starting material.

(61) A 1,1,1,3-Tetrachloropropane-rich mixture which also comprises catalyst is extracted as a residue from boiler 102 via line 103 and is subjected to the catalyst recovery step shown in FIG. 3.

(62) In that step, the 1,1,1,3-Tetrachloropropane-rich mixture is fed into a batch distillation boiler 204 via line 202, along with a weak (1-5%) hydrochloric acid solution via line 201.

(63) Advantageously, the water present in the acid solution deactivates the catalyst system and protects it from thermal damage. This enables the catalyst system, to be recovered from the 1,1,1,3-Tetrachloropropane-rich mixture, and it can be easily reactivated, post-recovery, and reused in the alkylation process without any significant loss in catalytic activity.

(64) The batch distillation boiler is operated at a temperature of about 100° C., to create a gaseous mixture comprising 1,1,1,3-Tetrachloropropane and water vapour.

(65) The gaseous mixture produced in the boiler 204, is then subjected to steam distillation (or steam stripping) of crude 1,1,1,3-Tetrachloropropane in column 210, which is coupled to the boiler 204. The crude 1,1,1,3-Tetrachloropropane is extracted from the distillation column 210 via line 211, condensed with a condenser 212, fed via line 213 to a reflux liquid-liquid separator 214. Water from the gaseous mixture is fed back to the distillation column 210 via line 215, and a portion is taken off via line 216 for a further distillation step, shown in more detail in FIG. 4 and discussed below in more detail.

(66) The operating temperature of the boiler 204 is then reduced to stop steam stripping, resulting in the condensation of the water vapour present therein. This results in the formation of a biphasic mixture containing an aqueous phase and an organic phase containing the catalyst system, which has not be subjected to steam stripping. To facilitate extraction of the organic phase, a haloalkane extraction agent (in this case, 1,1,1,3-Tetrachloropropane) is added to the boiler 204 via line 203 to increase the volume of that phase.

(67) Extraction of the organic phase from the biphasic mixture is achieved by the sequential extraction of the phases from the boiler 204 via line 205. The organic phase is extracted from the boiler 204 via line 205 and is filtered 206. A filter cake is removed from the filter 206 via line 207. The organic phase is extracted via line 208 and, in this embodiment, fed back to the primary alkylation zone, as shown in FIG. 1, specifically via line 13 in FIG. 1. The aqueous phase is extracted via line 205, filtered 206 and disposed of via line 209.

(68) The stripped crude 1,1,1,3-Tetrachloropropane product is subjected to a further distillation step shown in FIG. 4. In that step, the crude product is fed into a distillation boiler 302 via line 301. The boiler 302 is in communication with distillation column 304. Evaporated chlorinated organic compounds present in the crude 1,1,1,3-Tetrachloropropane are separated in the distillation column 304 (and related downstream apparatus, condenser 306 and reflux divider 308) into a purified 1,1,1,3-Tetrachloropropane product stream 310.1 and chlorinated pentane/pentene stream 310.2.

(69) The chlorinated pentane/pentene stream 310.2 may be used in the production of carbon tetrachloride, advantageously minimising the production of waste products. This can be achieved through use of a high temperature chlorinolysis process.

(70) The purified 1,1,1,3-Tetrachloropropane product stream 310.1 is extracted from the system and may be combined with the major product stream (identified with reference numeral 110.4 in FIG. 2. The product may be stored for shipment or employed in downstream processes requiring pure 1,1,1,3-Tetrachloropropane as a starting material.

(71) The heavy ends residue extracted from the boiler 302 via line 303 is either disposed of or further processed.

(72) Using the apparatus and process conditions outlined above, 2635 kg of carbon tetrachloride (CTC, 99.97% purity) was continuously processed with an average hourly loading 78.2 kg/h to produce 1,1,1,3-Tetrachlorpropene (1113TeCPa). Basic parameters of disclosed process carried out according to Example 2 are as following.

(73) TABLE-US-00013 Basic parameters First reactor mean residence time (min) 118 First reactor temperature range (° C.) 100-110 First reactor pressure (kPa) 800 Second reactor mean residence time (min) 25 Second reactor temperature range (° C.) 100-110 Second reactor pressure (kPa) 800 Overall reaction CTC conversion (%) 91.0 Overall 1113TeCpa reaction yield (mol 95.5 TeCPa/mol CTC converted, in %) Overall 1113TeCpa yield including the 94.0 all process steps described in Example 2

(74) The full impurity profile of the purified product of the above-described embodiment is presented in the following table. Please note that the figures are given as a weighted average of the profiles for the product obtained in line 110.4 in FIG. 2 and line 310.1 in FIG. 4.

(75) TABLE-US-00014 Compound (% wt) Trichloromethane 0 1,2-Dichloroethane 0 1-chlorobutane 0.023 Tetrachloromethane 0.008 1,1,1-Trichloropropane 0.001 Tetrachloroethene 0.006 1,1,3-Trichlororoprop-1-ene 0.014 1,1,1,3-Tetrachloropropane 99.925 1,1,1,3,3-Pentachloropropane 0.004 hexachloroethane 0.012 1,1,1,2,3-Pentachloropropane 0.005 1,1,1,5-Tetrachloropentane 0 1,3,3,5-Tetrachloropentane 0 Tributylphosphate 0 Unknown 0.007

Example 3

Effect on Selectivity of Molar Ratio of Starting Material:Product in Reaction Mixture

(76) These examples were carried out using the equipment and techniques outlined above in the ‘Continuous Arrangement’ in Example 1, except where otherwise stated. The molar ratio of the chlorinated C.sub.3-6 alkane product (in this case, 1,1,1,3-Tetrachloropropane):carbon tetrachloride in the reaction mixture was controlled to differing levels, principally by the residence time of reaction mixture in the alkylation zone. Temperature was maintained at 110° C. and pressure was maintained at 9 Bar. The selectivities towards product of interest are reported in the following table:

(77) TABLE-US-00015 mol. ratio Selectivity of 1113TeCPa:Tetra- Tetrachloromethane Trial No. chloromethane towards 1113TeCPa 3-1 79.0:21.0 96.6 3-2 84.4:15.6 95.2 3-3 89.8:10.2 95.5 3-4 93.9:6.1  94.1 3-5 98.0:2.0  90.3

(78) As can be seen from this example, when the molar ratio of product:starting material exceeds 95:5 when the process is operated on a continuous basis, there is a notable reduction in selectivity towards the product of interest.

Example 4

Effect on Selectivity of Molar Ratio of Starting Material:Product in Reaction Mixture

(79) These examples were carried out using the equipment and techniques as illustrated in FIG. 1, with reference to the accompanying text in Example 2 above, except where otherwise stated. The molar ratio of the chlorinated C.sub.3-6 alkane product (in this case, 1,1,1,3-Tetrachloropropane):carbon tetrachloride in the reaction mixture was controlled to differing levels, principally by control of the feed rate of the ethylene starting material. Temperature was constantly 110° C. The selectivities towards the product of interest are reported in the following table:

(80) TABLE-US-00016 mol. ratio Selectivity of 1113TeCPa:Tetra- Tetrachloromethane Trial No. chloromethane towards 1113TeCPa 4-1 91.5:8.5 95.6 4-2 95.3:4.7 94.8 4-3 96.4:3.6 93.3 4-4 97.0:3.0 92.9

(81) As can be seen from this example, when the molar ratio of product:starting material exceeds 95:5 when the process is operated on a continuous basis, there is a notable reduction in selectivity towards the product of interest.

Example 5

Effects of Feedstock Purity

(82) These examples were carried out using the equipment and techniques as illustrated in FIG. 2, with reference to the accompanying text in Example 2 above, except where otherwise stated. Trial 5-1 is the stream obtained from stream 110.4 in FIG. 2. Trials 5-2-5-5 are alternative examples, obtained using the same apparatus and techniques, but employing feedstocks of differing purity. The data below demonstrates that although lower purity feedstock was used in trials 5-2 to 5-5, this advantageously does not significantly impact product purity when obtained from step 1) of the process of the present invention.

(83) TABLE-US-00017 Trial No. Compounds 5-1 5-2 5-3 5-4 5-5 1-chlorobutane 0.004 0.028 0.032 0.011 0.002 TeCM 0.0004 0.007 0.004 0.014 0.006 1,1,1- 0 0 0.0005 0.004 0.009 trichloropropane Tetrachloroethene 0.002 0.001 0.002 0.02 0.052 1,1,3- 0.01 0.025 0.017 0.013 0.065 trichloropropene 1,1,1,3- 99.96 99.81 99.92 99.89 99.836  tetrachloropropane 1,1,1,3,3- 0.0002 0.017 ND ND ND pentachloropropane Hexachlorethane 0.002 0.079 0.002 0.013 0.001 1,1,1,2,3- 0.0004 0.003 0 0.004 ND pentachloropropane Others 0.023 0.033 0.022 0.031 0.028

Example 6

CSTR and Plug Flow Combination

(84) These examples were carried out using the equipment and techniques as illustrated in FIG. 1, with reference to the accompanying text in Example 2 above, except where otherwise stated. The efficiency of reaction in the second plug-flow reactor (reference numeral 4 in FIG. 1) was evaluated. Two trials were conducted with differing amount of dissolved ethylene at the inlet of the plug-flow reactor which was operated at the same temperature, 110° C., as the main CSTR reactor (reference numeral 3 in FIG. 1). The results are shown in the following table:

(85) TABLE-US-00018 Ethylene TeCM Ethylene TeCM content at content at content at content at plug-flow plug-flow plug-flow plug-flow reactor reactor reactor reactor Trial No. inlet (%) intlet (%) outlet (%) outlet (%) 6-1 1.19 12.5 0.087 6.58 6-2 0.36 9.17 0.089 6.99

(86) As can be seen from this example, there is a conversion of ethylene between 75-93% in the plug-flow reactor. Thus if plug-flow reactor is employed there is more efficient ethylene utilization in the reaction section. The serial plug-flow reactor allows the CSTR reactor to be operated at an optimal pressure, without needing complex and uneconomical ethylene recovery processes. The serial plug reactor therefore controls the ethylene use in an efficient closed loop.

Example 7

Problematic Degradation of Catalyst Ligand During Conventional Distillation

(87) Fractional distillation equipment consisting of a 2-litre glass distillation four-neck flask equipped with condenser, thermometer, heating bath and vacuum pump system was set up. The distillation flask was initially filled with 1976 grams of reaction mixture obtained using the apparatus and techniques illustrated in FIG. 1 and explained in the accompanying text in Example 2 above.

(88) During distillation, pressure was gradually reduced from an initial pressure of 100 mmHg to a final pressure of 6 mmHg. During this period, 1792 grams of distillate (in different fractions) were extracted. During distillation, there was visible HCl gas formation and furthermore chlorobutane (the breakdown product from tributylphosphate ligand) was also formed in significant amounts namely between 1 to 19% for the distillate fractions. Upon these observations being made, the distillation was interrupted, distillation residue was weighed and analyzed and was found to have a Tetrachloropropane content of 16%. It was no longer possible to continue distillation without significant degradation of the Tributylphosphate ligand.

Example 8

Production of 1,1,3-trichloropropene from 1,1,1,3-tetrachloropropane

(89) FIG. 5 shows a schematic drawing of a system which can be used to operate processes of step 2) of the present invention. 1,1,1,3-tetrachloropropane and ferric chloride are added into the continuously stirred tank reactor 403 via lines 401 and 402. The addition of ferric chloride is conducted using a controlled feed. The continuously stirred tank reactor is operated at a temperature of 140° C. to 145° C. and at atmospheric pressure.

(90) The 1,1,1,3-tetrachloropropane is converted to 1,1,3-trichloropropene in the continuously stirred tank reactor 403, which fulfils the role of the dehydrochlorination zone. The residence time of the reaction mixture in the reactor 403 is limited to prevent the excessive conversion of 1,1,1,3-tetrachloropropane to 1,1,3-trichloropropene and thus, the molar ratio of 1,1,3-trichloropropene:1,1,1,3-tetrachloropropane does not exceed 50:50.

(91) A proportion of 1,1,3-trichloropropene is extracted from the reaction mixture through the use of distillation column 408. Reaction mixture is fed into the bottom of the distillation column 408 and a 1,1,3-trichloropropene rich stream is withdrawn as overhead vapours via line 409. A partial condenser 410 functions to extract gaseous hydrogen chloride from the 1,1,3-trichloropropene rich stream via line 411. The 1,1,3-trichloropropene rich stream is then fed via line 412 to a reflux divider 413, and a stream of purified 1,1,3-trichloropropene is taken off via line 415. A proportion of the 1,1,3-trichloropropene rich stream is fed back as a reflux to distillation column 408 via line 414.

(92) A mixture comprising catalyst, unreacted 1,1,1,3-tetrachloropropane and a limited amount of 1,1,3-trichloropropene is extracted via line 404 from the reactor 403 to a filter 405. The obtained filter cake is extracted via line 406 and the filtrate is passed via line 407 for aqueous treatment, as shown in FIG. 6.

(93) In FIG. 6, the mixture from the reactor in FIG. 5 is fed via line 502 into a washing tank 505 including a stripping boiler. For better liquid phase separation efficiency, 1,1,1,3 tetrachloropropane or another haloalkane extraction agent is fed into the washing tank via line 503. Aqueous hydrochloric acid is fed into the washing tank 505 via line 501.

(94) A biphasic mixture is formed in the tank 505 and the organic phase is extracted from the tank 505 via line 506, filtered 507 and taken via line 509 for further treatment, as shown in FIG. 7. The remaining aqueous phase is extracted via line 510 for further treatment. The filter cake is extracted (508) 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene dissolved in the aqueous layer present in the washing tank 505 are extracted therefrom by means of a steam distillation column 511. Stripped chlorinated alkanes are passed via line 512 from the distillation column 511 to a condenser 513 and then via line 514 to a reflux liquid-liquid separator 515 where two layers are formed. The stripped 1,1,1,3-tetrachloropropane is then taken off as an organic phase via line 517 and an aqueous phase is refluxed back to the distillation column via line 516.

(95) Turning to FIG. 7, the organic phase is fed via line 601 into distillation boiler 602. 1,1,1,3-tetrachloropropane and 1,1,3-trichloropropene are extracted from the formed mixture using distillation column 607, condenser 609 and reflux divider 611 to produce fractions of 1,1,3-trichloropropene 613.1 and 1,1,1,3-tetrachloropropane 613.2. The fraction of 1,1,1,3-tetrachloropropane is recycled back to the dehydrochlorination zone while the fraction of 1,1,3-trichloropropene is stored or transported for use in downstream reactions employing that chlorinated alkene as a starting material.

(96) A heavy ends residue is extracted from boiler 602 via line 603 and filtered 604. The obtained filter cake and liquid residue are extracted via lines 605 and 606 respectively and recycled or treated.

(97) Using the apparatus and process conditions outlined above, 3563 kg of 1,1,1,3-Tetrachloropropane (1113TeCPa, 99.925% purity) was continuously processed with an average hourly loading 63.1 kg/h to produce 1,1,3-Trichloropropene (113TCPe). Basic parameters of disclosed process carried out according to Example 8 are as following.

(98) TABLE-US-00019 Basic parameters Reactor mean residence time (min) 174 Reactor temperature (° C.) 141 Reactor pressure (kPa) 101 Overall reaction 1113TeCPa conversion (%) 91.7 Overall 113TCpe reaction yield (mol TCPe/mol TeCPa 97.4 converted, in %) Overall 113TCpe yield including the all process steps 96.5 described in Example 8

(99) The full impurity profile of the purified product of the above-described embodiment is presented in the following table. The figures are given as a weighted average of the profiles for the product obtained in line 415 in FIG. 5 and line 613.1 in FIG. 7.

(100) TABLE-US-00020 Pilot plant Wt % Perchloroethylene 0.011 1,1,3-Trichloropropene 97.093 2,3-dichloropropanoyl chloride 0.028 1,1,3,3-Tetrachloropropene 0.019 1,1,1,3-Tetrachloropropane 2.573 unknown 0.276

(101) As can be seen, step 2) of the process of the present invention can be operated to produce highly pure chlorinated alkene material.

Example 9

Production of 1,1,3-trichloropropane from 1,1,1,3-tetrachloropropane

(102) This example was conducted using the apparatus and techniques employed in Example 8 above, except where otherwise stated. The continuously stirred tank reactor was operated at a temperature of 149° C. and at atmospheric pressure. The molar ratio of 1,1,3-trichloropropene:1,1,1,3-tetrachloropropane in the reactor was controlled such that it did not exceed 30:70. Using the apparatus and process conditions outlined in Example 8 above, 1543.8 kg of 1,1,1,3-Tetrachloropropane (1113TeCPa, 99.901% purity) was continuously processed with an average hourly loading 47.5 kg/h to produce 1,1,3-Trichloropropene (113TCPe). Catalyst was added in the form of FeCl.sub.3 aqueous solution to provide a catalyst content of 66 ppm, based on feedstock 1113TeCPa. Basic parameters of disclosed process carried out according to Example 8 are as following.

(103) TABLE-US-00021 Basic parameters Reactor mean residence time (min) 287 Reactor temperature (° C.) 149 Reactor pressure (kPa) 101 Overall reaction 1113TeCPa conversion (%) 91.4 Overall 113TCPe reaction yield (mol TCPe/mol TeCPa 98.7 converted, in %) Overall 113TCPe yield in % including the all process steps 97.8 described in Example 9

(104) The full impurity profile of the product of the above-described embodiment is presented in the following table. The figures are given as a weighted average of the profiles for the product obtained in line 415 in FIG. 5 and line 613.1 in FIG. 7.

(105) TABLE-US-00022 Compound Wt % Perchloroethylene 0.006 3,3,3-Trichloropropene 0.038 1,1,3-Trichloropropene 99.347 2,3-dichloropropanoyl chloride 0.045 1,1,3,3-Tetrachloropropene 0.004 1,1,1,3-Tetrachloropropane 0.322 unknown 0.238

(106) As can be seen, when the dehydrochlorination reaction is controlled such that the molar ratio of 1,1,3-trichloropropene:1,1,1,3-tetrachloropropane does not exceed 30:70, the process of step 2) the present invention can be operated to produce highly pure chlorinated alkene material with the very high selectivity and in high yield. Of note is that 3,3,3-trichloropropene is only formed in trace amounts. This is particularly advantageous as 3,3,3-trichloropropene is a very reactive olefin contaminant with a free induced (activated) double bond and can be a precursor of highly problematic oxygenated impurities.

Example 10

Alkene:Alkane Ratio in Reaction Mixture

(107) These examples were conducted using the apparatus and techniques employed in Example 8 above, except where otherwise stated. In each of these trials, the reaction progress was controlled such that there was a different ratio between 1,1,3-Trichloropropene:1,1,1,3-Tetrachloropropane in the reaction mixture present in the reactor (403, FIG. 5) reaction mixture (407, FIG. 5) in each trial. The amount of dosed catalyst FeCl.sub.3 was controlled to maintain the reaction conversion rate at about 90%. The influence of different levels of 113TCPe in reaction mixture on the heavy oligomers formation and catalyst deactivation is shown in the following tables:

(108) TABLE-US-00023 Heavy Oligomer Formation 10-1 10-2 10-3 10-4 10-5 10-6 Calculated 23:77 22:78 34:66 43:57 46:54 43:57 TCPe:TeCPa molar ratio in reac. mix TCPe (%) in 18.95 18.25 27.6 34.54 32.01 34.31 reaction mixture Heavy 0.36% 0.40% 1.05% 1.57% 2.87% 2.54% oligomers/TCPe 10-7 10-8 10-9 10-10 10-11 10-12 Calculated 39:61 37:63 40:60 39:61 38:62 39:31 TCPe:TeCPa molar ratio in reac. mix TCPe (%) in 32.1 29.94 32.84 31.46 30.56 31.83 reaction mixture Heavy 1.56% 1.79% 1.65% 1.01% 1.47% 1.55% oligomers/TCPe

(109) TABLE-US-00024 Catalyst Deactivation 10-1 10-2 10-3 10-4 10-5 10-6 TCPe (%) in 18.95 22.36 27.6 34.54 32.01 34,313 − 1 reaction mixture Calculated 23:77 22:78 34:66 43:57 46:54 43:57 TCPe:TeCPa molar ratio in reac. mix Required 26.5 26.5 66 101 116 78 conc. of FeCl3 in feedstock 10-7 10-8 10-9 10-10 10-11 10-12 TCPe (%) in 32.1 29.94 32.84 31.46 30.56 31.83 reaction mixture Calculated 39:61 37:63 40:60 39:61 38:62 39:61 TCPe:TeCPa molar ratio in reac. mix Required 132 132 105 177 106 74 conc. of FeCl3 in feedstock

(110) As can be seen from this example, when the specific apparatus and techniques employed, an increase in the molar ratio of the product to starting material (increased amount of the product in the reaction mixture) in step 2) of the process of the present invention, this corresponds to an increase in the formation of heavy oligomers. Further, if the 1,1,3-Trichloropropene concentration is high, catalyst deactivation was also observed.

Example 11

Compatibility of the Product Fluid with Various Materials

(111) An Erlenmeyer glass flask was filled with pure distilled 1,1,3-Trichloropropene with purity of >99%. The test construction material sample was immersed in the liquid and the system was closed with a plastic plug.

(112) Samples of the Trichloropropene were regularly taken from the flask. The construction material samples were weighed before and after trail. The temperature of the liquid was ambient laboratory conditions, around 25° C.

(113) The major changes in the quality of the Trichloropropene are shown in the following table, as a % change in purity:

(114) TABLE-US-00025 Feedstock 11-1 11-2 11-3 11-4 Trial duration 0 day 29 days 29 days 30 days 30 days Construction Material CS SS Ti C-276 1.4541 1,1,3- 0 −53.75 −3.70 −3.27 −0.67 Trichloropropene - relative change (%) Sum of oligomers (%) 0 42.68 0.20 0.32 0.01
CS=carbon steel, SS=stainless steel, Ti=Titanium, C-276=Hastelloy C-276

(115) In a second set of trials, an Erlenmeyer glass flask equipped with a back cooler and oil heating bath with controlled temperature was filled with pure distilled 1,1,3-Trichlorpropene with a purity of >99%. The test material sample was immersed in the liquid and the system was partially closed using a plastic plug. Samples of Trichloropropene were regularly taken from the flask. The material samples were weighed before and after trail. The temperature of the liquid was controlled at 100° C. The major changes in the liquid Trichloropropene are shown in the following table:

(116) TABLE-US-00026 feedstock 11-5 11-6 11-7 11-8 Trial duration 0 day 5 hours 48 hours 5 hours 48 hours Construction Glass as material of Impregnated Material flask graphite 1,1,3-Trichloro- 0 −0.32 −2.31 −0.30 −2.00 propene - relative change (%) Sum of 0 0.05 0.28 0.05 0.34 oligomers (%) feedstock 11-9 11-10 11-11 11-12 Trial duration 0 hours 5 hours 48 hours 5 hours 48 hours Construction SS 1.4341 SS 1.4541 Material 1,1,3-Trichloro- 0 −0.54 −3.08 −0.51 −2.80 propene - relative change (%) Sum of 0 0.27 1.01 0.29 1.29 oligomers (%)

(117) As can be seen from this example, the use of carbon steel appears to be challenging as it is not compatible with the process fluid consisting of 1,1,3-Trichloropropene. Stainless steel and titanium have also poor performance, resulting in the formation of significant amounts of oligomers are formed. From the tested metal materials, the Ni-alloy Hastelloy C-276 has excellent results. It can be seen also that glass (or enamel) and other non-metallic material, such as phenolic resin impregnated graphite, are also more suitable.

Example 12

Problematic Chlorinated Alkene Impurities

(118) In many downstream reactions in which chlorinated alkenes are used as starting materials, the presence of oxygenated organic impurities is problematic. This example demonstrates that certain impurities have a surprising propensity to form such compounds.

(119) A four neck glass flask equipped with a stirrer, thermometer, back cooler, feed and discharge neck and cooling bath was filled with water and chlorine gas was bubbled into the water to produce a weak solution of hypochlorous acid. When an appropriate amount of chlorine had been introduced into the water, a feedstock consisting obtained from the process of Example 8 comprising 1,1,3-Trichloropropene with a purity of 98.9% was slowly dropped into the prepared solution of hypochlorous acid for a period of 90 min and cooled. The pressure was atmospheric and the operating temperature was close to 20° C. The same procedure was repeated with 3,3,3-Trichloropropene having a purity of 68.1%. After reaction completion the systems formed bi-phasic mixtures. The organic phase (product) was extracted and then analyzed by gas chromatography. The results are shown in the following table:

(120) TABLE-US-00027 12-1 12-2 Hypochlorination of Feedstock Product Feedstock Product Trichloropropenes (%) (%) (%) (%) 3,3,3-Trichloropropene 68.063 33.544 0.024 0.023 1,1,3-Trichloropropene 21.772 16.651 98.922 91.374 1,1,1,2,3-Pentachloropropane 20.942 6.800 1,1,1,3-Tetrachloropropan- 12.792 0.018 2-ol

(121) As can be seen from this example, 1,1,3-Trichlorpropene reacts with chlorine in water to produce 1,1,1,2,3-Pentachloropropane, while 3,3,3-Trichloropropene reacts significantly to produce corresponding tetrachlorohydrines, especially 1,1,1,3-Tetrachloropropan-2-ol.

(122) In other words, 1,1,3-Trichlorpropene reacts to produce a product of commercial interest, while 3,3,3-Trichloropropene reacts to the produce an oxygenated impurity which cannot be easily removed from the 1,1,1,2,3-Pentachloropropane. As is apparent from Examples 8 and 9 above, the processes of step 2) of the present invention can be advantageously employed to produce 1,1,3-trichloropropene resulting in the formation of only trace amounts of 3,3,3-trichloropropene.

Example 13

Continuous Production of 1,1,1,2,3-pentachloropropane

(123) A schematic diagram of the equipment used to perform the primary conversion step and principal conversion step in step 3-a) of the process of the present invention is provided as FIG. 8. A liquid stream of 1,1,3-trichloropropene is fed via line 706 into an external circulation loop 703, 705, 707 connected to a column gas-liquid reactor 702. Gaseous chlorine is fed in the reactor 702 via line 701. The reactor 702 is includes a single primary reaction zone, namely circulation loop 703, 705, 707 and lower part of the reactor 702. The circulation loop 703, 705, 707 is provided with an external cooler 704 to control the temperature of the reaction mixture. Thorough mixing of 1,1,3-trichloropropene and chlorine is achieved within the primary reaction zone. The primary conversion step could equally be conducted in one or more other types of reactor, such as continuously stirred tank reactor/s.

(124) The operating temperature within the primary reaction zone is 0° C. to 20° C. Operating the reactor within this range was found to minimise the formation of pentachloropropane isomers, which are difficult to separate from the target product, 1,1,1,2,3-pentachloropropane. Thorough mixing of the reaction mixture and mild temperatures, but also controlling the proportion of 1,1,1,2,3-pentachloropropane present in the reaction mixture, was found to minimise serial reactions of 1,1,3-trichloropropene and the formation of 1,1,1,3,3-pentachloropropane (which is difficult to separate from 1,1,1,2,3-pentachloropropane). To increase the rate of reaction at the low temperatures, the reaction mixture is exposed to visible light.

(125) The reaction mixture is then passed up through the reactor 702 for the principal conversion step, which is performed as a reduced temperature conversion step. Cooling of the reaction mixture is achieved using cooling tubes, and the reaction mixture is passed through a series of upstream and downstream principal reaction zones (not shown), resulting in zonal chlorination of 1,1,3-trichloropropene. To drive the reaction towards completion, the reaction mixture in the downstream principal reaction zone is exposed to ultraviolet light. Advantageously, this fully utilizes the chlorine starting material such that the obtained reaction mixture which is extracted from the downstream-most principal reaction zone has very low levels of dissolved chlorine.

(126) Operating the principal reaction zones at such temperatures has been found to minimise the serial reactions of 1,1,3-trichloropropene, which result in the formation of unwanted and problematic impurities, such as hexachloropropane.

(127) A 1,1,1,2,3-pentachloropropane rich stream is extracted from reactor 702 via line 708. Off-gas is extracted from the reactor 702 via line 711. The 1,1,1,2,3-pentachloropropane rich stream is subjected to cooling using a product cooler 709 and passed via line 710 for a hydrolysis step. A schematic diagram illustrating the equipment used to conduct this step is presented as FIG. 9.

(128) In that equipment, the 1,1,1,2,3-pentachloropropane rich stream is fed into washing tank 803 via line 802. Water is fed into the washing tank via line 801 to form a biphasic mixture. The organic phase (containing the 1,1,1,2,3-pentachloropropane rich product) can easily be separated from the aqueous phase by the sequential removal of those phases via line 804. The extracted phases are filtered 805 with the filter cake being removed 806. The 1,1,1,2,3-pentachloropropane rich product is then fed via line 807 for further processing while wastewater is removed via line 808.

(129) The hydrolysis step is especially effective at removing oxygenated organic compounds, such as chlorinated propionyl chloride and their corresponding acids and alcohols, which may be formed during upstream steps in the process of the present invention. While the formation of such compounds can be avoided by excluding the presence of oxygen from the upstream stages of the synthesis, doing so increases the cost of production. Thus, the hydrolysis step assists with the economic and straightforward removal of such otherwise problematic (owing to the difficulty of removing them, e.g. by distillation) impurities.

(130) To maximise the purity of the obtained 1,1,1,2,3-pentachloropropane, a vacuum distillation step was performed, using the apparatus shown in FIG. 10, namely a distillation boiler 902 and vacuum distillation column 907. Advantageously, the components of the distillation apparatus which come into contact with the process liquid and distillate are formed of non-metallic materials which prevents the formation of degradation products of the 1,1,1,2,3-pentachloropropane.

(131) The vacuum distillation column 907 is provided with a liquid side stream withdrawal which can be used to prevent contamination of the product stream with light molecular weight compounds which may be formed in the boiler.

(132) The 1,1,1,2,3-pentachloropropane rich product from the apparatus shown in FIG. 9 is fed into boiler 902 via line 901. A residue is extracted from the distillation boiler 902 via line 903, subjected to filtering using a filter 904. The filter cake is extracted from the system 905 and a heavies stream is extracted via line 906 and subjected to further processing.

(133) Distillate is taken from the distillation column 907 via line 908, fed via condenser 909, intermediate line 910 and liquid divider 911 to yield a streams of i) 1,1,3-trichloropropene via line 913.1 which is recycled to the primary reaction zone, ii) 1,1,1,3-tetrachloropropane via line 913.2 and purified 1,1,1,2,3-pentachloropropane via line 913.3. A reflux stream 912 from divider 911 is fed back into the vacuum distillation column 907.

(134) Using the apparatus and process conditions outlined above, 3062 kg of 1,1,3-Trichloropropene (113TCPe, purity 97.577%) was continuously processed with an average hourly loading 44.9 kg/h to produce 1,1,1,2,3-Pentachloropropane (11123PCPa). Basic parameters of the process are as follows:

(135) TABLE-US-00028 Basic parameters Reactor overall mean residence time (min) 375 Reactor temperature range (° C.) 1-30 Reactor pressure (kPa) 101 Overall reaction 113TCPe conversion (%) 91.3 Overall 11123PCPa reaction yield (mol PCPa/mol TCPe 97.9 converted, in %) Overall 11123PCPa yield including the all process steps 97.4 described in Example 13

(136) The full impurity profile of the purified product obtained in line 913.3. in FIG. 10 of the above-described embodiment is presented in the following table

(137) TABLE-US-00029 Compound (% wt) Phosgene ND 1,1,3-Trichloroprop-1-ene 0.007 2,3-Dichloropropanoylchloride ND 1,2.3-Trichloropropane ND 2,3,3,3-Tetrachloroprop-1-ene 0.001 1,1,3,3-Tetrachloroprop-1-ene 0.003 1,1,1,3-Tetrachloropropane 0.002 1,1,2,3-Tetrachloroprop-1-ene 0.003 1,1,3,3,3-Pentachloroprop-1-ene 0.001 1,1,1,3,3-Pentachloropropane 0.004 hexachloroethane ND 2,3-Dichloropropanoic acid ND 1,1,1,2,3-Pentachloropropane 99.967  1,1,2,2,3-Pentachloropropane 0.001 1,1,1,3-Tetrachloropropane-2-ol 0.001 1-Bromo-1,1,2,3-Tetrachloropropane ND 2-Bromo-1,1,1,3-Tetrachloropropane ND 1,1,1,3,3,3-Hexachloropropane ND 1,1,1,2,3,3-Hexachloropropane 0.002 1,1,1,2,2,3-Hexachloropropane 0.001 1,2-Dibromo-1,1,3-Trichloropropane ND HCl as Cl— ND H.sub.2O 0.005 ND means below 0.001% wt.

Example 14

Ultra Pure Composition 1,1,1,2,3-pentachloropropane (PCPA)

(138) The process of Example 13 was repeated four times and samples of 1,1,1,2,3-pentachloropropane were obtained following distillation using the apparatus illustrated in FIG. 10. Distillation was conducted at a pressure of around 15 mBar and at a maximum boiler temperature of 105° C. As can be seen in the following table, the process of step 3) of the present invention enables highly pure PCPA, including very low levels of impurities, particularly 1,1,2,2,3-pentachloropropane which is very difficult to separate from 1,1,1,2,3-pentachloropropane using distillation. Note that the figures in this table are provided as percentages by weight of the composition.

(139) TABLE-US-00030 Trial Number Compound 14-1 14-2 14-3 14-4 Phosgene ND ND ND ND 1,1,3-Trichloroprop-1-ene 0.0014 0.0012 0.0006 0.0014 2,3-Dichloropropanoyl chloride ND ND ND ND 1,2.3-Trichloropropane ND ND ND ND 2,3,3,3-Tetrachloroprop-1-ene 0.0005 0.0002 <0.0001 0.0002 1,1,3,3-Tetrachloroprop-1-ene 0.0017 0.0021 0.0008 0.0015 1,1,1,3-Tetrachloropropane 0.0023 0.0013 0.0007 0.0013 1,1,2,3-Tetrachloroprop-1-ene 0.0018 0.0021 0.0008 0.0011 1,1,3,3,3-Pentachloroprop-1- ND ND ND ND ene 1,1,1,3,3-Pentachloropropane 0.002 0.0022 0.0009 0.0016 hexachloroethane ND ND ND <0.0001 2,3-Dichloropropanoic acid ND ND ND ND 1,1,1,2,3-Pentachloropropane 99.984 99.985 99.993 99.989 1,1,2,2,3-Pentachloropropane 0.0006 0.0009 0.0008 0.0009 1,1,1,3-Tetrachlororopropane-2- 0.001 0.0008 0.0006 0.0005 ol 1-Bromo-1,1,2,3- ND ND ND ND Tetrachloropropane 2-Bromo-1,1,1,3- ND ND ND ND Tetrachloropropane 1,1,1,3,3,3-Hexachloropropane ND ND ND ND 1,1,1,2,3,3-Hexachloropropane 0.0006 0.0004 ND 0.0005 1,1,1,2,2,3-Hexachloropropane ND 0.0003 ND ND 1,2-Dibromo-1,1,3- ND ND ND ND Trichloropropane Moisture (mg/kg) 44 23 NP NP Iron (mg/kg) <0.05 0.05 NP NP HCl as Chlorides (mg/kg) 0.51 0.53 NP NP ND = below 1 ppm, NP = not performed

Example 15

Effect of Water Treatment

(140) Crude 1,1,1,2,3-Pentachloropropane compositions were obtained using the apparatus depicted in FIG. 8 and described in Example 13 above, e.g. the compositions were obtained from line 710 in FIG. 8. One stream (Trial 15-1) was not subjected to a hydrolysis step, while the other was (Trial 15-2), using the apparatus shown in FIG. 9 and described in Example 13 above. The resulting crude compositions were then subjected to distillation. The purity of and oxygenated compound contents of the samples, pre- and post-distillation, are shown in the following table:

(141) TABLE-US-00031 Trial Number 15-1 15-2 Pre-distillation 1,1,1,2,3-Pentachloropropane 89.038 91.402 Sum of oxygenated as 0.006 0.001 propanoyl chlorides and their acids Post-distillation 1,1,1,2,3-Pentachloropropane 99.948 99.930 Sum of oxygenated as 0.006 <0.001 propanoyl chlorides and their acids

(142) As is apparent, the washing step can be successfully employed to minimise the content of oxygenated organic impurities in compositions rich in chlorinated alkanes of interest.

Example 16

Influence of Molar Ratio of Chlorinated Alkene:Chlorinated Alkane on Impurity Formation

(143) A batch operated reactor consisting of a four neck glass flask equipped with a stirrer, thermometer, back cooler, feed and discharge neck and cooling bath was set up. The feedstock consisted of 1,1,3-Trichloropropene comprising perchlorethylene and oxygenated impurities in amounts observed in commercially sourced supplies.

(144) Minor amounts of HCl gas were formed and these together with traces of chlorine were cooled down by means of a back cooler/condenser and then absorbed in a caustic soda scrubber. Chlorine was introduced into the liquid reaction mixture via dip pipe in various amounts for a period of 90 minutes. The temperature of reaction was maintained at 26 to 31° C. Pressure was atmospheric. The chlorine was totally consumed during the reaction. The reaction mixture was sampled and analyzed by gas chromatography and the results of this analysis are shown in the following table:

(145) TABLE-US-00032 Trial No. 16-1 16-2 16-3 16-4 16-5 chlorine dosed 20% 40% 60% 80% 100% (mol % of stoichiometry) TCPe:PCPa 90:10 72:28 53:47 33:67 14:86 ratio in reaction mixture (mol %) HCE (w %) 0.015 0.025 0.040 0.064 0.099 DCPC (w %) 0.089 0.067 0.172 0.228 0.322 Other 0.009 0.017 0.030 0.058 oxygenated (w %)

(146) As can be seen, increasing the conversion of the chlorinated alkene starting material to the chlorinated alkane product of interest results in an increase in the formation of impurities in the reaction mixture. These disadvantageous results arise as conversion of the starting material to product approaches total conversion.

Example 17

Influence of Molar Ratio of Chlorinated Alkene:Chlorinated Alkane on Isomeric Selectivity

(147) This example was carried out in as described in Example 16 above. 1,1,3-Trichloropropene (purity 94.6% containing 5% of 1,1,1,3-Tetrachloropropane as an impurity) was used as the feedstock.

(148) 4 trials at different reaction temperature were conducted. The samples of reaction mixture were taken at 80%, 90%, 95% and 100% of stoichiometric quantity of chlorine dosed (based on 113TCPe in the feedstock) and then analyzed by gas chromatography. The results of this analysis are shown in the following table:

(149) TABLE-US-00033 Chlorine dosed (mol % of 113TCPe in feedstock) 80% 90% 95% 100% Reaction 11133PCPA content in Trial No. temp. reaction mixture in % 17-1  6° C. 0.028 0.040 0.053 0.075 17-2 25° C. 0.040 0.055 0.071 0.099 17-3 45° C. 0.049 0.064 0.076 0.095 17-4 63° C. 0.056 0.071 0.086 0.112

(150) These results demonstrate that increasing the conversion of the chlorinated alkene starting material to the chlorinated alkane product of interest results in a decrease in the selectivity of the reaction towards the chlorinated alkane isomer of interest. These disadvantageous results arise as conversion of the starting material to product approaches total conversion.

Example 18

Influence of Molar Ratio of Chlorinated Alkene:Chlorinated Alkane on Impurity Formation

(151) This chlorination step was carried out as described in Example 16 above. 1,1,3-Trichloropropene (purity 99.4%) was used as a feedstock.

(152) Chlorine was introduced into the liquid reaction mixture at 120% of the stoichiometric quantity towards feedstock 1,1,3-Trichloropropene for a period of 90 minutes and was totally consumed during the reaction. The reaction temperature was 80° C. and reactor pressure was atmospheric. The samples of reaction mixture were taken by 80%, 95%, 110% and 120% of stoichiometric quantity of the chlorine dosed was analyzed by gas chromatography. Reaction selectivity is expressed in the table below as a ratio between sum of major impurities (1,1,3,3-Tetrachloropropene, 1,1,1,2,3,3-Hexachloropropane, 1,1,1,2.2.3-Hexachloropropane) to the product 1,1,1,2,3-Pentachloropropane:

(153) TABLE-US-00034 Trial Number 18-1 18-2 18-3 18-4 chlorine dosed (mol % 80 95 110 120 of stoichiometry) TCPe:PCPa ratio in 22:78 11:89 0.6:99.4 0.2:99.8 reaction mixture (mol %) Sum of byproducts/ 3.51 3.59 4.28 6.34 11123PCPa (%)

(154) These results demonstrate that increasing the conversion of the chlorinated alkene starting material to the chlorinated alkane product of interest results in an increase in the formation of unwanted impurities. These disadvantageous results arise as conversion of the starting material to product approaches total conversion. As can be seen, the degree of conversion (and thus the formation of impurities) can advantageously and conveniently be achieved by controlling the amount of chlorine into the reaction zone, such that there is no molar excess of chlorine: chlorinated alkene starting material.

Example 19

Removal of Oxygenated Impurities by Hydrolysis

(155) To demonstrate the effectiveness of the hydrolysis step of step 3-b) of the present invention at removing oxygenated compounds from the chlorinated alkane product of interest, samples of crude reaction mixture were obtained using the apparatus depicted in FIG. 8 and described in Example 13 above, e.g. the composition was obtained from line 710 in FIG. 8. The content of a specific oxygenated compound known to be problematic in downstream reactions was analysed (Feed). The sample was then subjected to a hydrolysis step using the apparatus depicted in FIG. 9 and described above in Example 13, and the organic phase, e.g. the composition obtained from line 807 in FIG. 9 was analysed (After treatment). The results are shown in the following table:

(156) TABLE-US-00035 Content of specific oxygenated compound Trial Number (ppm) 19-1 Feed After treatment 2,3-Dichloropropanoyl 937 23 chloride

(157) As can be seen from this example there is about 97.5% efficiency in the removal of this specific oxygenated impurity.