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UNITED STATES PATENT OFFICE 2,529,671 PURFICATION of THONY CHLORIDE William E

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UNITED STATES PATENT OFFICE 2,529,671 PURFICATION of THONY CHLORIDE William E Patented Nov. 14, 195 2,529,671 UNITED STATES PATENT OFFICE 2,529,671 PURFICATION OF THONY CHLORIDE William E. Bissinger, Akron, Ohio, assignor to Pittsburgh Plate Glass Company, Allegheny County, Pa., a corporation of Pennsylvania, No Drawing. Application August 4, 1948, Serial No. 42,539 8 Clains. (C. 23-203) 2 This invention relates to the purification of hydrocarbon or halogenated hydrocarbon. The thionyl chloride, SOC2, and more particularly to nature of the reaction is such that the reaction a process for removing Sulfuryl chloride from products which are formed are high boiling and thionyl chloride which is contaminated with this may easily be separated from the thionyl chloride compound. by renoviing the lower boiling thionyl chloride Thionyl chloride is a well-known material preferably through simple distillation, leaving a which in pure form is a water-white liquid having residue which is readily renovable from the re a specific gravity of 1.638, and a boiling point of action vessel. 75.9°C. at 760 millimeters of mercury. Its utiliza It has been found that many hydrocarbons are tion in commercial operations has been restricted 10 Suitable for this purification process. Of especial somewhat because of the high cost of producing value are the predominantly aromatic hydrocar a relatively pure material which is low as to bons, that is those hydrocarbons having a greater other chlorides which almost invariably are pres number of carbon atoms in the ring structure ent as by-products of the main reaction by which than the number of carbon atoms in the Sub the thionyl chloride is formed. 5 stituent groups if any be present. Typical com While certain methods for producing thionyl pounds are the mono- and polycyclic aromatic chloride yield a material which has a relatively hydrocarbons and their partially halogenated de low Sulfuryl chloride content, none is known to rivatives such as the toluenes, xylenes, mesitylene, yield an absolutely pure product. In U. S. Patent naphthalene, anthracene, phenanthrene, pyrene 2,431,823, granted to Alphonse Pechukas, Decem 20 and picene. While benzene itself may be used, ber 2, 1947, there is disclosed a process by which its boiling point closely approaches that of thionyl thionyl chloride is prepared by reacting a sulfur chloride and it is difficult to separate the two chloride with sulfur dioxide and chloride at tem compounds by distillation. Other hydrocarbons peratures in excess of 100° C. While the thionyl may be used as will appear more fully hereinafter. chloride thus produced is relatively pure, never 2325 The process may be performed by adding to the theless it contains a small amount of sulfuryl contaminated thionyl chloride an amount of a chloride which is considered undesirable for cer hydrocarbon which is capable of reacting with tain purposes. Thionyl chloride prepared by Sulfuryl chloride to form a chlorinated reaction other processes also contains Sulfuryl chloride product in the presence of a Friedel-Crafts cata in objectionable concentration which frequently 30 lyst, if necessary, and heating the mixture. is much higher than that produced by the above Usually this is effected by refluxing the resultant mentioned process. mixture to insure complete reaction, followed by Sulfuryl chloride is a colorless liquid which removal of the purified thionyl chloride by dis boils at 69° C. Since the boiling point of thionyl tillation, solvent extraction, crystallization or chloride is about 76°C., effective separation of the other convenient method. two chlorides by fractional distillation is in The nature of the reaction which tends to occur practicable in conventional distillation apparatus. is dependent upon the type of hydrocarbon used According to this invention it has been found and has not been fully determined. Usually the that sulfuryl chloride may be largely removed reaction products are halogenated hydrocarbon from thionyl chloride by treatment of the thionyl 40 or sulphochlorinated hydrocarbons. For ex chloride with a hydrocarbon or partially halo ample, when naphthalene is reacted with Sul genated hydrocarbon which is capable of under furyl chloride 1-chloronaphthalene, which has a going reaction with sulfuryl chloride. It has been boiling point of 263° C. at 760 millimeters of found that such compounds preferentially react mercury, is produced. Some of the other chloro with sulfuryl chloride even when sulfuryl chloride substituted naphthalenes which may be produced, is present in Small amount, for example less than such as 2-chloronaphthalene or the poly Sub 5 percent by weight of thionyl chloride. stituted chloronaphthalenes, have boiling points Thionyl chloride contaminated with sulfuryl which are of a similar order of magnitude. Since chloride may be treated with a wide variety of the boiling point of the thionyl chloride is ap hydrocarbons and partially halogenated hydro 50 preciably lower than 100° C. separation of thionyl carbons. These agents preferentially react with chloride from the hydrocarbon chloride by dis sulfuryl chloride but do not react excessively with tillation presents no problem. Although most of thionyl chloride. Consequently the mixture thus the hydrocarbons suitable for the purification produced comprises unreacted thionyl chloride process are compounds having high boiling points, and the product of reaction produced by the 55 it does not necessarily follow that the process is 2,529,671. 3 4 restricted to such materials. If the reaction tion containing 2.27 percent by weight of Sulfuryl product of sulfuryl chloride and the purifying chloride was added 2.2 grams of anthracene, agent is one from which thionyl chloride may C14H10. This represents a 100 percent exceSS be readily separated, hydrocarbons boiling at over the theoretical amount of anthracene needed relatively low temperatures may be used. to combine with sulfuryl chloride according to It has further been found that certain olefinic the equation: and cyclo-olefinic hydrocarbons and their partial ly halogenated derivatives are effective when re acted with the contaminated thionyl chloride An immediate reaction between the hydrocar without resorting to the use of a catalyst. When 10 bon and the stock Solution took place with a aromatic hydrocarbons and partially halogenated darkening of the Solution. 0.8 gram of anhydrous aromatic hydrocarbons are used as purifying aluminum chloride was added to the mixture and agents they are only slightly effective unless a it was boiled under reflux for two hours. An Friedel-Crafts catalyst is present. Anhydrous 86.8 percent recovery of thionyl chloride con 15 taining 0.12 percent by weight of Sulfuryl chloride aluminum chloride is a Friedel-Crafts type of was obtained. catalyst which may be used according to this This experiment shows that this particular invention, and it has been employed in most of hydrocarbon may be used effectively even in the the experimental purification tests which have absence of aluminum chloride, as evidenced by been performed. However, other Friedel-Crafts the immediate reaction at room temperature. type catalysts such as ferric chloride, zinc chlo 20 The lowered thionyl chloride recovery points to ride, and boron fluoride etherate are suitable. When saturated hydrocarbons and partially a partial reaction between the hydrocarbon and halogenated saturated hydrocarbons are utilized, thionyl chloride. Such reaction can be mini a catalyst capable of promoting free radical mized by the use of a smaller amount of formation is required. This reaction is activated 25 anthracene and/or refluxing for a shorter period by actinic light through the use of a mercury arc of time. lamp or by a peroxide catalyst Such as benzoyl Eacample IV peroxide. To 50 cubic centimeters (81.3 grams) of thionyl The invention will be more clearly understood chloride containing 2.27 percent by weight of by reference to the following examples which 30 Sulfuryl chloride was added 1.3 grams of a mix are illustrative of the preferred embodiments ture of Ortho, meta, and para xylene. This of the invention. represents a 100 percent excess over the theo retical amount of the mixed xylene needed to Eacample I combine With Sulfuryl chloride according to the A thionyl chloride-sulfuryl chloride mixture 35 equation: containing 2.07 percent of sulfuryl chloride by weight based upon the weight of the total mix ture was prepared. A 75 cubic centimeter por 0.8 gram of anhydrous aluminum chloride was tion of this mixture was placed in a round-bottom added through a reflux condenser. The mixture flask and 5 grams of naphthalene was added. 40 was heated at refux temperature for 2 hours and The fiask was fitted with a water-cooled reflux the thionyl chloride was removed by distillation. condenser and the mixture was heated at reflux A recovery of 94.7 percent thionyl chloride con temperature for three hours. After refluxing taining 0.76 percent by weight of sulfuryl chlo was completed the thionyl chloride was removed ride was obtained. by distillation at 72-75° C. The distilled thionyl 45 chloride contained 1.93 percent by weight of Eacample V Sulfuryl chloride. To determine the effectiveness of a non-aro natic hydrocarbon, 2.0 grams of kerosene com Eacample II prising aliphatic hydrocarbons and having a boil To a mixture of 81.3 grams of thionyl chloride 50 ing range of 160 to 220° C. and 81.4 grams (50 containing 2.07 percent by Weight of sulfuryl cubic centimeters) of thionyl chloride contain chloride was added 0.1 gram of anhydrous ing 2.08 percent by weight of sulfuryl chloride aluminum chloride and 0.8 gram of naphthalene. were placed in a round bottom flask and boiled at This quantity of naphthalene was 100 percent reflux for 2 hours. 79.4 grams of thionyl chloride in excess of the weight theoretically required to 55 containing 1.97 percent by weight of sulfuryl react with sulfuryl chloride to form tetrachloro chloride was recovered by distillation.
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