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Patented Aug. 20, 1946 2,406,195 UNITED STATES‘ PATENT‘ OFFICE 2,406,195 MANUFACTURE OF THE HIGHER CHLORIDES OF METHANE Oliver W; Cass,.Niagara Falls, N. Y., assignor ‘to E. I. du Pont de Nemours & Company, Wilming ton, Del‘., a corporation of Delaware N'o Drawing. Application February 17, 1944, Serial No. 522,799 2 Claims. (Cl. 260—65'7') 2 This invention relates to a new and improved process for preparing halogenated organic com pounds. More particularly, it relates to a new and improved method for preparing the higher chlorides of methane, such as methylene chlo ride, CI-IzC‘lz; chloroform, CHCl3-; and carbon tetrachloride, CC14. ‘ In previous attempts to overcome this inherent difficulty in the chlorination process, it has been proposed to admix the entire reaction mixture resulting from such a chlorination with an amount of methanol essentially equivalent to the hydrogen chloride content of the reaction mix ture. The mixed gases were then passed through My invention is primarily concerned with a' a reaction chamber containing catalytic mate new and improved procedure for the. chlorina rial, for example alumina gel or fused zinc chlotion of methane, methyl chloride, or mixtures 10 ride, in whichv chamber a reaction between the of these two compounds in varying, proportions, whereby mixtures of the desired higher halide derivatives of methane result. By the utiliza vaporized methanol and hydrogen, chloride oc curred, this reaction resulting in the formation of further amounts of methyl chloride and water, tion of my improved process for producing these the latter being formed as a icy-product. In this higher chlorides of methane, it is possible to 15 previously suggested processv the ?nal reaction secure yields of chlorinated products that are product was then separated into the following much higher, from the viewpoint of the amount constituents: (1.) the water, containing unre of available chlorine utilized to form valuable acted hydrogen chloride and methanol; (2): the products, than previously possible. higher halides of methane, including methylene t is well understood in the art that the higher 20 chloride, chloroform, and carbon tetrachloride; halides of methane, particularly methylene chloride, chloroform, and carbon tetrachloride, may be readily prepared by chlorinating meth and (3) the methane or methyl chloride, or mix-- - ture of the, two. In utilizing this process it. was then necessary to dry both the higher halides ane, a lower chlorinated methane halide such of methane component, as well as the gaseous as methyl chloride, or by the chlorination of 25 mixture of methane, methyl chloride, or, mixture mixtures of these compounds. This chlorina tion. reaction has been carried out in a number of ways, such as by reacting the starting mate rials at an elevated temperature in the absence of any catalytic or activating agent; by reacting the starting materials at a moderately elevated temperture in the presence of catalytic agents possessing large surface areas such as activated carbon; or by carrying out the reaction at still lower temperatures in the presence of actinic radiation as an activating agent. , Regardlessof the particular procedure adopted, the funda of methane and » methyl chloride. The dried higher halides of methane could then be Worked up by known methods, While the gaseous mixture was again recycled to the chlorination process. By;utilizing this procedure it was possible to recover at least a portion of the hydrogen chlo ride formed as by-product in the substitution chlorination reaction in the form of methyl chlo-_ ride, which could then be utilized in subsequent chlorinations. However, in the practical operation of such a process, particularly on ‘the industrial scale, a mental reaction involves a substitution of chlo large number of dif?culties are encountered. .In rine for hydrogen atoms in methane or methyl the original chlorination reaction, especially chloride with the formation of the higher chlo 40 when the chlorination is conducted, at relatively rides of methane and the simultaneous 'pro high temperatures, or With relatively high ratios duction of hydrogen chloride as a by-product. of chlorine to. the amount of the other reactants, In practice the chlorination reaction is ordinarily small quantities of carbon as'well as high boil incomplete, as, in order to controlthe heat of the ing condensation products are formed. These reaction, only a portion of the starting mate 45 materials tend to accumulate upon or in the cat rial, whether that material be methane, methyl alyst mass which is utilized after the vaporized methanol has been added to the reaction prod uct in order to bring about reaction between the methanol and the by-product hydrogen chloride evident,,however, that an inherent defect in the economical operation of this process by any of 50 to form further amounts of methyl chloride. As the procedures speci?ed is the production of the a consequence the catalyst mass becomes fouled relatively worthless compound, hydrogen chlo and rapidly loses its activity, necessitating fre ride,» as a Icy-product, this product being produced quent and uneconomical replacement of the cat in amount equivalent to half of the chlorine sup alyst body. Moreover, the hydrogen chloride is plied to the process. diluted by the entire reaction mixture so that it chloride, or a mixture of the two, is chlorinated per pass through the reaction system. It is 2,406,195 3 4 . is impossible to secure even fairly complete uti lization of the hydrogen chloride without in . ceiver is maintained at a temperature su?iciently high to insure the removal of substantially all the hydrogen chloride present, as well as a major portion of the unreacted methyl chloride. The condensation of the, major portion of ther disadvantage, under the conditions main— higher halides of methane at the top of the frac tained in the reaction between the methanol tionation column, and the separation out of the and by-product hydrogen chloride, the higher reaction product of substantially all the gaseous halides of methane present, i. e. methylene chlo constituents thereof, 1. e. the hydrogen chloride ride, chloroform, and carbon tetrachloride, react‘ with the steam produced as by-product vin the“10 vand the'major portion of the methane or methyl chloride,'I readily accomplish by maintaining a hydrogen chloride-methanol reaction.” " The net‘ temperature gradient throughout the column. effect is a decrease in the yield ofnthese higher The actual temperature to which the top of the halogenated methane derivatives, which, to some column must be cooled in order to effect substan extent, o?sets the advantages resulting from uti tially complete removal of the higher chlorides lizing the by-pro-duct hydrogen chloride to form of methane will depend on the nature of the further amounts of methyl chloride. ' ' chlorination. For example, if the reaction in-' II have now found that the advantages incident volves the chlorination of methyl chloride alone, to the utilization of by-product hydrogen chloride troducing economically excessive quantities of methanol into the reaction mixture. As a fur wherein it is reacted with methanol to form fur ther amounts of chlorinated products may be retained, at the same ‘time avoiding the disad with the use of some l‘to 3 mols chlorine per 5 vantages inherent in previously available proce-v mols methyl chloride, temperatures of —18°. C. to _—24° C. are suitable to, insure removal of 90-95 per cent of the higher halides of methane from dures. This is accomplished by a new and line theoff-gas issuing from-the fractionating column. proved process for handling the reaction products of the chlorination system and for converting the by—product hydrogen chloride by reaction with On the other hand, if methane-methyl chloride mixtures are being chlorinated, temperaturesiof methanol to methyl chloride. 7 ' , Accordingly, it is one object of my invention‘ to provide an improved process for thepreparation ' of the 5 higher'chlorides of methane; namely, 30 methylene chloride, chloroform, and carbon tet rachloride, which will‘ permit the utilization of —50° to .-70°‘ C. may be required; or, if desired, . the fractionation column may be operated under pressure at somewhat higher temperatures. ' The actual temperature under any,v given set of. conditions should be such that 90-95v per cent of the higherhalides of methane are removed from the o?-gas from thetop of the column. ‘At the bottom of 'the fractionation column a temperature sufficient to ensure saparation of the 35 hydrogen chloride and av major portion of the methyl chloride constituent is satisfactory, a attempts to utilize the byeproduct hydrogen temperature of approximately 40° to 50°. C., for chloride. .Another object of my invention’ is‘ to example, giving very e?icient results. provide a new andimproved method for the man~ It is thus possible to withdraw from the're- ' ufacture of the higher halides of methane wherein ceiver an anhydrous, essentially acid-free mix the by-product hydrogen chloride is economically ture of the higher halides of methane which, f utilized to form valuable products in a cyclic proc fromv that point on, may be handled in ordinary ess under circumstances wherein fouling and in steel equipment under substantially atmospheric activation of the catalytic massis avoided. Still pressure. At the sametime there is secured from another object of my invention is the provision V the top of the fractionation column a mixture of a method wherein this by-product hydrogen consisting essentially of hydrogen chloride to chloride can‘ be utilized under circumstances by-product ‘hydrogen chloride inthe formation of furtheramountsof chlorinated hydrocarbon without thedisadvantages incident to previous ' wherein dilution of the hydrogen chloride content of the reaction mixture is avoided and objection able side, reactions between the higher chlorinated halides of methane and by-product steam do not " occur. These and still other objects of my proc ess will be apparent from the ensuing disclosure of certain illustrative preferred embodiments thereof. In carrying out my improved procedure, meth ane, methyl chloride,v or mixtures of these two compounds in various proportions, are reacted withchlorine in the usual manner, utilizing the high temperature noncatalytic method, the mod erately elevated temperature catalytic method, or. ‘ the reaction as carried out atrelatively low tem peraturesrin the presence of actinic radiation. The manner of carrying out all these‘ chlorina tions isrfully understood in the’art, and'no de tailed explanation thereof is necessary.’ The re action gases coming from. the chlorination cham her are, in accordance with my improved method, passed directly into a fractionation column. At gether with the unchlorinated starting materials, whether those starting materials bef methane, methyl chloride, or a mixture of the two. This gaseous mixture from the top of the fractiona tion column is then admixed with methanol in quantity approximately equivalent to the hydro gen chloride present therein, and thecombined gaseous mixture then passed into a suitable re action zone‘ where the methanol and hydrogen chloride react to form methyl chloride and water. The water, together withtraces of unreacted methanol, may then be removed from the gas stream by an appropriate means, the major por tion of the unreacted hydrogen chloride beingrdis ‘solved therein and removed therewith. It is not, however, necessary to remove the'unreacted hydrogen chloride. The gaseous mixture, now en riched by the newly formed methyl chloride is recycled to the chlorination unit. ' ' i It is apparent from the process as described that each of the difficulties inherent in previous attempts to utilize byejproduct hydrogen chloride in the formation of further, amountsof. chlori the top of this column the gas mixture is subjected to a temperature low enough to cause condensa 70 nated products has been overcome by the scrub tion of the major, portion of the desired product, bing, action occurring in the fractionation'col umn. The particles of free carbon present, to the higher halides'of methane, present therein. gether with highboiling condensation products The condensate is allowed to ?ow back through and tars, are scrubbed‘ from the mixture which, is the column and iscollected in the receiver at the base of the fractionation column. This re 75 to'be fed to the catalyst mass employed. inpthe ‘2,406,195 6 5 preparation of additional methyl chloride. As a result the catalyst mass retains its activity in de?nitely. Furthermore, a considerable concen tration of the hydrogen chloride present in the gaseous mixture has been effected by the removal from the mixture of the higher halides of meth ane, thus permitting greater utilization of the by-product hydrogen chloride. It will also be evident that the higher halides of methane are never subjected to the action of steam at high temperatures, and, as a result, they are not de composed by reaction therewith, there being thus obtained an improved yield of these higher hal ides. Other and additional advantages reside in the separation of these higher halides of meth ane in a form in which they may be readily han dled in steel equipment at atmospheric pressure, due to the substantially complete removal there from in the process of the hydrogen chloride and low boiling raw materials, such as methane or methyl chloride, initially present therein. In the appendedclaims the term higher chlo rides of methane is to be understood as includ ing all chlorides of methane containing a per remove high boiling products, carbon and tars from said uncondensed portion while maintain ing the hydrogen chloride and a major portion of the methyl chloride in the gaseous phase; adding methanol to said gaseous portion and passing the resulting gaseous mixture in contact with a catalytic mass promoting reaction between meth anol and hydrogen chloride at an elevated tem perature, thus forming methyl chloride and wa ter; removing water and unreacted methanol from the resulting gaseous reaction product; and returning said puri?ed gaseous reaction product to prepare further amounts of the chlorides of - methane. 2. The process for preparing the chlorides of methane which comprises reacting a material se lected from the group which consists of methyl chloride and mixtures of methane and methyl chloride with chlorine; cooling the resultant gas eous reaction product, condensing the higher chlorides of methane, scrubbing the uncon densed portion of said reaction product with the condensed portion so as to substantially complete 1y remove high boiling products, carbon and tars; centage of chlorine higher than that present in 1 separating out said condensed portion, high boil methyl chloride. ing products, carbon andvtars from said uncon 7 The above description is intended to be illus trative only. Any modi?cations of or variations therefrom which conform to the spirit of the in vention are intended to be included within the scope of the appended claims. I claim: 1 1. The process of preparing the chlorides of methane which comprises reacting a material se ‘lected from the group which consists of methyl ‘ densed portion while maintaining the hydrogen chloride and a major portion of the methyl chloride in the gaseous phase; adding methanol to ‘said unco-ndensed portion and passing the re sulting gaseous mixture in contact with a cata lyst mass promoting reaction between methanol and hydrogen chloride at an elevated tempera ture, thus forming methyl chloride and water; and removing water and unreacted methanol from the ‘resulting gaseous product, and return- ' chloride and mixtures of methyl chloride and ing the puri?ed gaseous reaction product to pre methane with chlorine; cooling the resultant pare further amounts of the chlorides of meth gaseous reaction product, condensing the higher chlorides of methane, scrubbing the uncondensed portion of said reaction product with the con 40 OLIVER w. oAss, densed portion so as to substantially completely ane. 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