United States Patent tis) Schussler et al, (1) Patent Number {45]__Date of Paten 4,814,528 Mar, 21, 1989 [54] REMOVING WATER FROM CRUDE 1,2-DICHLOROETHANE COMPOSITIONS CONTAINING CHLORAL HYDRATE, Henry W. Schussler, North Canton, Ohio; W. Eugene Wimer, McMurray, (75] Inventors: (73] Assignee: PPG Industries, Ine, Pitsburgh, Pa. [21] Appl. No. 780,154 (22] Filed: Sep, 26, 1988 [51] Im ci. 107 17/38, [2] US.c, 570/262 (58] Field of Scareh 570/262 (56) References Cited U.S. PATENT DOCUMENTS. 2,584,036 1/1952. Mahoney etal von 2OR/, 2,146,912 5/1956 Park etal, ren, 202/82 31055.955 9/1962 Hodges SS aeor6s6 3.378597 4/1968 Dehn et al, non 260/652 34271389. 2/1969 Rectenwald eta. “260/659 3,488,398 1/1970. Harpring etal. 280/659 3,679,373 7/1972 Vancamp etal. 23/288 L 3,996,300 12/1976 Ahlstrom 260/682 B 4151212 4/1979. Rideout .. 0/282 4263269 4/1981 Little et al. 23/488 4513152 4/1985 Schllawski 568/492 FOREIGN PATENT DOCUMENTS 1129982 5/1962. Fed. Rep. of Germany OTHER PUBLICATIONS L. F. Albright, “Manufacture of Vinyl Chloride’ Chemical Engineering, Apr. 10, 1967, pp. 219-224 and 226. R. W. McPherson, C. W. Starks, and G. J. Fryar, “Vinyl Chloride Monomer . . . What You Should Know," Hydrocarbon Processing, Mar. 1979, pp. 75-88, Primary Examiner—Howard T. Mars Attorney, Agent, or Firm—George D. Mortis bn ABSTRACT ‘The water content of crude 1,2-dichloroethane compo- sitions containing chloral hydrate is reduced by strip- ping under superatmospheric pressure, 410 Claims, 1 Drawing SheetUS. Patent Mar. 21, 1989 4,814,5284,814,528 1 REMOVING WATER FROM CRUDE 1,2-,DICHLOROETHANE COMPOSITIONS CONTAINING CHLORAL HYDRATE 5 1,2-Dichloroethane is frequently produced in a reac- tor ‘system from which at least one stream of crude 1,2-dichloroethane comprising contaminating amounts of various impurities including chloral hydrate. Typical sources of such crude 1,2-dichioroethane include pro- 10 cesses in which ethylene is oxychlorinated in packed bed, fluidized bed, or liquid phase reactors and pro- cesses in which ethane is oxychlorinated. See, for exam- ple, L. F. Albright, “Manufacture of Vinyl Chloride”, Chemical Engineering, Apr. 10, 1967, pages 219-224 and 15 226, R. W. McPherson, C. M. Starks, and G. J. Fryar, ‘Vinyl Chloride Monomer. ... What You ‘Should Know", Hydrocarbon Processing, March 1979, pages 75-88, and U.S. Pat. Nos. 3,055,955, 3,427,359; and 3,679,373, the entire disclosures of which are incorpo- rated hherein by reference, directed to oxychlorination. Using the oxychlorination of ethylene as an example, ethylene, hydrogen chloride, and an oxygen containing gas (usually commercial oxygen, ait, or oxygen- enriched air) are reacted to form a gas stream whic! removed from the reactor and condensed to form two liguid phases, nne organic and the other aqueous. The liquid organic phase is substantially separated from the liquid aqueous phase and is forwarded as a crude 1,2- dichloroethane composition for further purification. The crude 1,2-dichloroethane composition comprises 1,2-dichloroethane as the principal constituent and con- taminating amounts of impurities including chloral hy- date. In most cases the composition is saturated with water as it leaves the phase separator and also contains 35 some hydrogen chloride. Inasmuch as chloral hydrate ‘may be prepared by simpiy admixing anhydrous chloral and water, the chloral is principally present as chloral hydrate. The crude 1,2-dichloroethane composition is typi- cally forwarded to a purification system where the ‘various components are separated using primarily sev- eral distillation operations. There are many systems that can be used, each differing from the others in the ar- rangement, numbers, identities, and functions of partic ular types’ of equipment. One factor common to all, however, is that 1,2-dichloroethane having a purity acceptabie for the purposes of the manufacturer is pro- duced. See, as examples, the article by McPherson, Starks, and Fryar and U.S. Pat, No, 3,055,955, both of 0 which are referenced above. It has been found that if the chloral hydrate is allowed to remain in the crude 1,2-dichloroethane composition, its presence eventually gives cise to corrosive conditions that can damage equipment. Although itis not desired to be bound by any theory, it is believed that chloral hydrate decom- ‘poses to form anhydrous chloral and water and that the water then associates with small amounts of acidic ma- terials such as the small amount of hydrogen chloride present, to form acid which is responsible for much of 60 the corrosion. Corrosion can be reduced by construct ing the equipment of corrosion resistant materials such as tantalum or glass, but the capital expenditures for such equipment are very high. In many eases the purifi- cation equipment is constructed of mild steel which is less expensive, and chloral hydrate is removed as an early step in the purification process. One such method of chloral hydrate removal isthe treatment of the crude 2 3 30 ey 4 38 6 2 1,2-dichloroethane composition with aqueous alkali metal hydroxide to produce alkali metal formate, chlo- roform and water, as shown in U.S. Pat. No. 3,378,597, the entire disclosure of which is incorporated herein by reference. In that method the effluent from the contact- ing tower is phase separated into organic and aqueous phases and the organic phase is forwarded to a distlla- tion column where the crude 1,2-dichloroethane is es- sentially dehydrated. This procedure has been used successfully, but itis disadvantageous in that the alkali metal formate and chloroform by-products must even- tually be disposed of or recovered. Experience has shown that in the stripping of water from crude 1,2-dichloroethane compositions containing, chloral hydrate by distillation conducted at or near ambient atmospheric pressure, (1) most of the chloral accompanies the 1,2-dichloroethane-containing bot toms product, and (2) the crude composition cannot ordinarily be dehydrated such that the 1,2-dichloroe- thane-containing bottoms product contains less than about 170 parts of water per million parts of the bottoms composition by weight. In this connection, the mean- ings of “chloral”, “water”, and their quantitative values should be clarified. The ‘usual method for analyzing. crude 1,2-dichloroethane compositions and other com- positions which are predominately 1,2-dichloroethane, for water, is the Karl Fischer method. This method of analysis does not distinguish between free water and ‘water combined with chloral as chloral hydrate. There- fore, the quantitative value of water given by this method includes both forms of water. Similarly, the usual method for analyzing crude 1,2-dichloroethane compositions and other compositions which are pre- dominately 1,2-dichloroethane, for chloral is gas cheo- matography. This method does not distinguish between anhydrous chloral and chioral hydrate, and the quanti- tative value of chloral determined includes both the anhydrous chloral and the chloral of the chloral hy- drate expressed on an anhydrous basis. As used throughout the present specification and claims, the terms “chloral” and “water” and their quantitative val- ues will, when used in connection with the composition of crude 1,2-dichloroethane compositions and other compositions which are predominately 1,2-dichloroe- thane, be expressed on these bases, unless otherwise indicated or obvious from the context. Itis believed that in the gas chromatographic method of analysis, the chloral hydrate is essentially decomposed into anhy- drous chloral and water before the stream reaches the detector. ‘Although it is not desired to be bound by any theory, it is believed that the difficulty in dehydrating crude 1,2-dichloroethane compositions containing chloral hydrate by distillation at or near ambient pressure is because some of the chloral accompanying the 1,2- dichloroethane effluent is in the form of chloral hy- rate. Irrespective of theory, it has now been found that conducting the distillation of crude 1,2-dichloroethane ‘compositions containing chloral hydrate under condi- tions of elevated pressure (and hence elevated tempera- tare) can produce products having very low water contents. Accordingly, the invention is a method com- rising (@) countercurrently contacting in a distillation apparatus a crude 1,2-dichloroethane composition which comprises 1,2-dichloroethane as the principal constituent and a contaminating amount of chloral hy- rate, with reboiled vapors of 1,2-dichloroethane and4,814,528 3 cchloral under superatmospheric pressure conditions of at least $5 kilopascals gauge, thereby substantially dehy- rating the chloral hydrate, (b) removing from the ap- paratus at least one by-product composition which comprises water, and (c) removing from the apparatus at least one product composition which comprises 1, dichloroethane as the principal constituent and chloral, the product composition containing less than about $0 parts of water, whether free or combined with chloral as chloral hydrate, per million parts of the product ‘composition by weight. Fora better understanding of the invention, reference may be made to the drawing which shows diagrammati- cally an embodiment of the invention. ‘The particular form of the distillation apparatus may vary widely. Examples of various distillation columns that may be used include bubble cap columns, sieve plate columns, packed columns, and similar devices In many cases the countercurrent contacting is con- ducted under superatmospheric pressure conditions of at least about 275 kilopascals gauge. Often the superat- mospheric pressure is in the range of from about 55 to about 1725 kilopascals gauge. Preferably the superat- ‘mospheric pressure is in the range of from about 275 to about 560 kilopascals gauge. In most cases the by-product composition also com- prises 1,2-dichloroethane. Hence itis preferable to cool the by-product composition to produce a liquid organic phase and a liquid aqueous phase, to substantially sepa- rate the liquid organic phase from the liquid aqueous phase, and to introduce at least a portion of the sepa rated liquid organic phase to the distillation apparatus as, reflux. Preferably, substantially all of the separated liquid organic phase is introduced to the distillation apparatus as reflux. The crude 1,2-dichloroethane composition which contains a contaminating amount of chloral hydrate and Which is treated in accordance with the present inven- tion ordinarily comprises at least about 90 percent by ‘weight 1,2-dichloroethane. Often it comprises at least about 92 percent by weight 1,2-dichloroethane. By a contaminating amount of chloral hydrate is ‘meant more than a mere trace. The crude 1,2-dichloroe- thane composition usually comprises at least about 0.1 percent by weight chloral hydrate. Often the crude composition comprises at least about 0.2 percent by weight chloral hydrate. In many cases the chloral hy- drate concentration isin the range of from about 0.1 to about 2 percent by weight. Frequently the chloral hy- drate concentration is in the range of from about 0.2 to about 0.8 percent by weight. The crude composition may, and often does, include minor amounts of organic materials in addition to the chloral hydrate. Frequently the crude 1,2-dichloroethane composition ‘comprises water not combined with chloral as chloral hydrate (hereinafter “free water”) as well as water com- bined with chloral as choral hydrate. In such cases the crude 1,2-dichloroethane composition usually, but not necessarily, comprises at least about 0.01 percent by weight free water. Often the crude composition com- prises from about 0.05 to about 0.3 percent by weight free water. ‘The crude 1,2-dichloroethane composition may origi- ‘ate from substantially any source which gives rise to chloral hydrate contamination, but in most cases it has originated at least in part from the oxychlorination of ethylene. 2» 25 30 38 40 4s 55 65 4 Preferably, the product composition contains less than about 35 parts of water, whether free or combined with chloral as chloral hydrate, per million parts of the product composition by weight ‘After the product composition has been removed from the distlltion apparatus, it may be introduced to fone or more purification systems where the purity of the I,2-dichloroethane is increased by removal of other materials. Usually at least a portion of the chloral is removed from the product composition. Distillation is most often used for this purpose. Referring now in detail to the drawing, there is, shown diagrammatically @ reactor 1 in which ethylene is oxychlorinated to produce 1,2-dichloroethane. Ethyl- ‘ene from line 2is admixed with hydrogen chloride from Tine 4 and the mixture passed through line 6 imo reactor 1. Onygen is passed through line 8 into reactor 1. The {gaseous effluent from reactor 1 passes through line 10 to Cooling system 12 where most of the effluent is con- densed by coolant passing through line 13 to a liguid comprising an organic phase and an aqueous phase. The effluent is transferred through line 14 to phase separator 16 where the liquid phases are allowed to substantially separate into layers. Uncondensed gases may be re ‘moved through line 18. The upper liquid aqueous phase is removed through line 20 and may be dealt with as, desired; for example, it may be processed to recover any of its components such as hydrogen chloride, and then discharged to an effluent treatment system. The lower liquid organic phase, which is a crude 1,2-dichloroe- thane composition comprising 1,2-dichloroethane as the Principal constituent and a contaminating amount of cchloral hydrate, is passed through line 22 to distillation column 24 containing packing material 26. In distilla- tion column 24, and especially within the channels pro- vvided by packing material 26, 1,2-dichloroethane com- position is countercurrently ‘contacted with reboiled ‘vapors of 1,2dichloroethane and chloral under superat- mospheric pressure conditions of at least 55 kilopascals gauge. Bottoms liquid is passed through line 28 to re- boiler 30 heated by steam or other hot heat transfer fuid introduced to line 32. In reboiler 30 the bottoms liquid is boiled thereby producing the reboiled vapors which return to distillation column 24 through line 34. A por- tion of the bottoms liquid, which comprises 1,2- dichloroethane as the principal constituent and chloral, is removed through line 36 as a product composition, The product composition contains less than about 50 parts of water, whether free or combined with chloral 45 chloral hydrate, per million parts of the product composition by weight. A stream of gaseous by-product composition comprising water and 1,2-dichloroethane is removed from distillation column 24 through line 38 and introduced to condenser 40 cooled by coolant pass- ing through line 41. In condenser 40 most of the by-pro- duct composition is condensed to a liquid comprising an organic phase and an aqueous phase. The material is transferred through line 42 to phase separator 44 where the liquid phases are allowed to substantially separate into layers. Uncondensed gases may be removed through line 46. The upper liquid aqueous phase is re- moved through line 48 and may be discarded or pro- cessed to recover any of its components. The lower liquid organic phase is passed through line $0 and intro- ‘duced to distillation column 24 as reflux. For the sake of clarity in setting forth the nature of the system, parts of the apparatus such as valves, pumps, flow indicators, pressure indicators, pressure4,814,528 5 reducers, temperature indicators, hold-up tanks, storage tanks, and the like, not essential to a complete under- standing of the invention have been omitted from the drawing, It will be appreciated that various modifications can 5 bbe made to the system of the drawing without departing from the spirit of the invention. For example, the distil- lation column may be a bubble cap column, sieve plate column, or similar device. Sources of heat other than steam or hot heat transfer fluid may be used. Single condensers may be replaced with a plurality of condens- ers operating in series and/or parallel. Condensers may bbe vented to permit removal of uncondensed gases. Although distillation column 24 is shown operating as a stripping column, a rectifying section may be added above the feed point, if desired. Other modifications will be apparent to those skilled in the art. The invention is further described in conjunction with the following example, which is to be considered illustrative rather than limiting. EXAMPLE, Feed material was charged to a 41iter holding vessel which was connected via polytetrafluoroethylene tub- ing to a variable flow feed pump. (Unless otherwise noted, all tubing used in the construction of the appara tus was 6.35 millimeter outside diameter polytetrafluo- roethylene tubing having a wall thickness of 1.1938 millimeter.) The pump was equipped with a ceramic shaft and plastic head. A bypass was fitted to the pump discharge to provide added flow rate flexibility. The feed passed through a steam heated preheater consisting, of 7.62 meters of tubing contained in a 0.61 meter sec- tion of 25.4 centimeter schedule 40 steel pipe. Steam was supplied to the preheater from a 965 kilopascal steam header and controlled with a needle vaive. The heated feed material traveled from the preheater t0 one of the horizontal branches of a 2.54 centimeter borosii- cate glass pipe cross attached to the top of the column. ‘The column was constructed of 2.54 centimeter inside diameter borosilicate giass pipe, packed with 6.35 milli- ‘meter Berl Saddles. The packed height was 1.37 meters. The overhead material exited through the vertical branch of the cross into a tee to which nitrogen was added. The nitrogen, metered via a two stage regulator 45 from cylinders through a needle valve, served to pro- vide smooth pressure control and keep any organic ‘material from the pressure transmitter. A rupture disk set at 690 kilopascals was attached to the nitrogen line to prevent overpressurization in case of a control valve failure, The combined overhead stream was introduced into a countercurrent double pipe condenser con- structed of 61 centimeters of 12.7 millimeter outside diameter polytetrafluoroethylene tubing contained in 2.54 centimeter schedule 80 chlorinated poly(vinylchlo- 38 ride) pipe. Tap water circulating in the shell provided the cooling medium. The effluent from the condenser traveled t0 a phase separator mounted above the col- ‘umn. The phase separator was constructed from a 5.08 centimeter rotameter tube fitted with two steel-backed 60 polytetrafluoroethyiene flanges. Threaded rod fastened. between the two flanges provided the means of sealing the rotameter tube to the polytetrafluoroethylene plates. to hold system pressure, The top polytetrafluoroethyl- ‘ene plate was tapped through the side to provide an 65 ‘overflow for the aqueous phase. The condenser effluent ‘was introduced into the phase separator through the top flange via tubing which terminated in the middle of the 18 25 30 35 6 phase separator. The aqueous phase exited the phase separator into a small collector constructed of a 10.16 centimeter piece of 2.54 centimeter inside diameter borosilicate glass pipe. Polytetrafluoroethylene flanges were fitted to each end. A polytetrafluoroethylene valve was connected to the bottom flange to allow for aqueous material drainage at various intervals. In actual operation, this piece of equipment was unnecessary due to the small volume of aqueous material handled. The ‘organic material from the phase separator was metered through a polytetrafluoroethylene needle valve and reintroduced into the second horizontal branch of the borosilicate glass cross. The reflux rate was adjusted to keep a constant organic level in the phase separator. A tee was inserted into the reflux line and connected to a polytetrafluoroethylene valve. This arrangement was ‘used to measure the reflux rate at the end of each mate- rial balance run. In this instance, the reflux line valve ‘was shut, and the purge line valve opened for a speci- fied period of time such that the organic level in the phase separator remained constant. The collected mate- Tal was weighed to determine the reflux rate. A second borosilicate glass cross was attached to the bottom of the column. A polytetrafluoroethylene dis- tributor plate drilled with 3.57 millimeter holes to pro- vide a 75% open area was placed between the cross and the column. This served as a packing support and gas, distributor. A 0.61 meter piece of flanged polytetrafluo- roethylene lined stainless steel hose was fastened to the vertical branch of the cross via a polytetrafluoroethyl- ene plate. This hose was bent in a U shape to provide the return loop for the thermosiphon reboiler. Heat input to the reboiler was provided by a 400 watt quartz electric heater. The polytetrafluoroethylene lined hose ‘was traced with electrical heating tape to allow the desired boil-up to be attained with one heater. Each hheat source was connected to a variable autotrans- former to allow precise heat control. The quartz heater ‘was inserted into the straight run of a borosilicate glass “Y" pipe and secured via a drilled out polytetrafluoro- ethylene fitting. The offset branch of the “Y” pipe was connected to the polytetrafluoroethylene lined stainless steel hose, and the other end of the straight run was connected to a 45° borosilicate glass elbow. This boro- silicate glass elbow was connected to @ horizontal branch of the bottom cross to complete the reboiler loop. The other horizontal branch of the cross provided the means for withdrawing the bottoms material. The bottoms material was cooled by passing through a length of tubing submerged in an ice water bath. The ‘material flow rate was controlled by a level controller. ‘When the liquid level in the column rose above the desired set point, the level controller tripped, opening a 6.35 millimeter polytetrafluoroethylene solenoid valve at the column bottom. The material was further cooled by passing through two water-cooled heat exchangers before being discharged into a collection vessel. Crude 1,2-dichloroethane compositions fed to the column were produced by oxychlorinating ethylene using oxygen and hydrogen chloride to produce a reac- tion product, essentially condensing the reaction prod- uct, and phase separating the condensate to remove the aqueous phase. The feed materials therefore correspond to compositions flowing through line 22 of the drawing. The distillation column was operated at both ambient atmospheric pressure and at a superatmospheric pres- sure of 414 kilopascals gauge, both being measured at the top of the column.4,814,528 7 For each run, the crude 1,2-dichloroethane composi- tion fed to the column was analyzed and the analytical results were summed. Each analytical result was then normalized by dividing the analytical result by the sum. ‘Samples of the product composition were taken from $ ‘time to time during each ran. Each sample was analyzed and each analytical result was normalized as described in respect of the feed composition. The normalized analyses were then averaged. The boil-up for each run was ascertained. The boil- up, expressed as percent, is one hundred times the mass flow rate of vapor passing from the top of the column to the condenser divided by the mass flow rate of the crude 1,2-dichloroethane composition fed to the col ‘umn. Expressed in terms of the drawing, itis one hun- dred times the mass flow rate in line 38 divided by the ‘mass flow rate in line 22. ‘The operating conditions and the results are shown in the Table. EDC is an abbreviation for 1,2-dichloroe- thane. A second set of samples was taken during Run 4 and these samples were analyzed at a different analyti- cal laboratory; the results so obtained are shown in the second set of data for Run 4, Although the present invention has been described with reference to specific details of certain embodi- ments thereof, itis not intended that such details should ‘be regarded as limitations upon the scope of the inven- tion except insofar as they are included in the accompa- ying claims, 2» 2s 8 as the principal constituent and chloral, said prod- ‘uct composition containing les than about 50 parts ‘of water, whether ffee or combined with chloral as chloral hydrate, per million parts of said product composition by weight. 2. The method of claim 1 wherein (@ said by-product composition comprises 1,2- dichloroethane; (©) said by-product composition is cooled to produce 8 liquid organic phase and a liquid aqueous phase; (©) said liquid organic phase is substantially separated from said liquid aqueous phase; (@) at least a portion of said separated liquid organic hase is introduced to sid tiation apparatus as 3. The method of claim 2 wherein substantially all of said separated liquid organic phase is introduced to said distillation apparatus as reflux. 4. The method of claim 1 wherein said crude 1,2- dichloroethane composition comprises a contaminating amount of free water. 5. The method of claim 1 wherein said crude 1,2- dichloroethane composition has originated at least in part from the oxychlorinaion of ethylene. 6. The method of claim 1 wherein said crude 1,2- dichloroethane composition comprises atleast about 90, percent by weight 12-dichloroethane and atleast about 0.1 percent by weight chloral hydrate. 7. The method of claim 6 wherein said crude 1,2- TABLE ‘Normalized Fea “Average Normalized Operating Concentrations Weight Percent Prodvct Concentration Mase Pressre, —Boi-Up ‘Other EDC, Chlorsh Organics Water, Recovery Run_kPaGuuge Percent EDC _Chloral Organics Water_Wi% Wess Wi% PPM Tereent Ta 197 982 Os $333 02se 9s 08m 3a79 ssn 2 ° 2 9447 Los 42680261495 LID 3933, TS 3 © 449513 oseT ©3702 S571 ag | 33610 4% a SES wot 0739 roa © oan 98307880955 3217 i455 98a 0s tes 063 98s 09) We claim: 1. A method comprising: G) countercurrently contacting in a distillation appa- ratus a crude 1,2-dichloroethane composition which comprises 1,2-dichloroethane as the princi- pal constituent and a contaminating amount of chloral hydrate, with reboiled vapors of 1,2 dichloroethane and chloral under superatmos- pheric pressure conditions of at least $5 kilopascals, gauge, thereby substantially dehydrating said chlo- ral hydrate, (b) removing from said apparatus atleast one by-pro- duct composition which comprises water, and (©) removing from said apparatus at east one product ‘composition which comprises 1,2-dichloroethane $5 4s dichloroethane composition comprises at least about 0.01 percent by weight free water. 8. The method of claim 1 wherein said superatmos- pheric pressure conditions are of at least about 275 Ielopascals, gauge. 9, The method of claim 1 wherein said product com- position contains less than about 35 parts of water, ‘whether free or combined with chloral as chloral hy” rate, per million parts of said product composition by weight. 10. The method of claim 1 wherein at least # portion of said chloral is subsequently removed from said prod ‘uct composition.