CORE Metadata, citation and similar papers at core.ac.uk Provided by University of Kentucky University of Kentucky UKnowledge Chemical and Materials Engineering Faculty Patents Chemical and Materials Engineering 12-21-1982 Production of Anhydrous 1,4-Dioxane Jean Yamanis University of Kentucky Right click to open a feedback form in a new tab to let us know how this document benefits oy u. Follow this and additional works at: https://uknowledge.uky.edu/cme_patents Part of the Chemical Engineering Commons, and the Materials Science and Engineering Commons Recommended Citation Yamanis, Jean, "Production of Anhydrous 1,4-Dioxane" (1982). Chemical and Materials Engineering Faculty Patents. 30. https://uknowledge.uky.edu/cme_patents/30 This Patent is brought to you for free and open access by the Chemical and Materials Engineering at UKnowledge. It has been accepted for inclusion in Chemical and Materials Engineering Faculty Patents by an authorized administrator of UKnowledge. For more information, please contact [email protected]. United States Patent [191 [11] 436mm Yamanis [45] Dec, 21, 1982 [54] OF ANHYDROUS OTHER PUBLICATIONS 9 . _ Beilsteins Handbuch Organ. Chem. 19/1, p. 9, (1977). [75] Inventor: Jean Yamams’ Lexmgton» Ky‘ The Canadian Journal of Chemical Engineering, vol. [73] Assignee: The University of Kentucky Research 57’ Jun’ 1979’ pp’ 297404’ J‘ Yamams ‘21nd 13' D‘ Patton‘ Foundation’ Lexington’ Ky_ Chem. Abstracts 71:124349f, 76:14449J. Primary Examiner-—Ethel G. Love [21] Appl' No‘: 151’593 Attorney, Agent, or Firm-Birch, Stewart, Kolasch & [22] Filed: May 20, 11980 Blrch [51] llnt. Cl.3 .......................................... .. C0711) 3119/04 [57'] _ ABSTRACT [52] US. Cl. .................................... .. 549/377 Thls lnvemion relates to the Production of anhydrous [58] Field Of Search .................... .. 260/340.6; 549/377 1,4-dioxane by the dimerization of ethylene oxide in the presence of an acidic type of cation exchanger, prefera [56] References Cited bly an acidic cation exchanger resin having sulfonic U_S_ PATENT DOCUMENTS acid groups associated therewith. The 1,4-dioxane is formed by contacting ethylene oxide in the liquid phase 12/ gvébel ', """" """"""""" " with an acidic-type cation exchanger at a ?rst tempera 2’O35’386 351936 sglzrgélrug et a‘ 54/9/37'7 ture and for a time sufficient to yield a reaction product 3’825’568 7/1974 scheckfr'é't'gi "" " 549/377 of the ethylene oxide and the cation exchanger, and 3:998:843 12/1976 Stapp _________ n ' 549/377 thereafter heating the reaction product at a second tem 4,124,541 11/1978 Conrad 61 a1, 549/377 perature higher than the ?rst temperature and for a time 4,146,736 3/1979 Scheffel et al. ................ .. 260/340.6 period sufficient to dissociate the reaction product and thereby yield 1,4-dioxane. FOREIGN PATENT DOCUMENTS ' 740423 11/1955 United Kingdom ........... .. 260/340.6 13 Claims, 1 Drawing Figure Stirring Eihylene Oxide MOT“ Potentiometer Bomb / / / Sampllng- / ’ ’ m Temperature Controller Valve / // Relay ' _ _ _ "" ____"l I l i.\ l [I f P um p l ,._ __ ... J ._ .a _ _ :1"; Cold Temperature -—- Reactor 1 I I 01’ G a s Chromatograph Furnace Schematic of Experimental Set-up 4,365,071 11 2 lation and cause contamination of the desired product. PRODUCTION OF ANHYDROUS 1,4-DIOXAN1E Besides the inconveniences mentioned, executing the reactions in the presence of acid catalysts results in BACKGROUND OF THE INVENTION material losses and contaminated products due to the This invention relates to a process for the production occurrence of side reactions. Thus, for example, when of anhydrous l,4-dioxane. More particularly, the inven sulfuric acid is employed as the catalyst, there is always tion is concerned with a process wherein ethylene oxide produced, due to side reactions, a greateror lesser is dimerized in the presence of an acidic cation ex change resin, preferably one having sulfonic acid amount of tars which are only difficultly separably from groups associated therewith, said dimerization yielding the reaction mixture. 1,4-dioxane which is a valuable solvent. SUMMARY OF THE INVENTION THE PRIOR ART Therefore, the primary object of the present inven Various techniques have been disclosed in the prior tion is to provide a practical and] economical process art for the preparation of dioxane. For example, the which is adapted to the technical scale production of dimerization of an alkylene oxide to dioxane in the pres 1,4-dioxane by dimerizing ethylene oxide in the pres ence of a sulfuric acid catalyst is disclosed in US. Pat. ence of an acidic cation exchange resin. Another objec No. 2,293,868 of Toussaint. US. Pat. No. 1,921,378 to tive of the invention is to provide an ef?cient process Webel, issued on Aug. 8, 1933, discloses contacting for producing anhydrous 1,4-dioxane. ethylene oxide with an aluminum sulfate catalyst, result ing in the production of dioxane. The process of the present invention makes it possible More recent disclosures include US. Pat. No. to eliminate the drawbacks and inconveniences of the 3,825,568 to Schecker et al, issued on July 23, 1974, known processes for effecting the dimerization of ethyl- , which teaches the dimerization of ethylene oxide to ene oxide to produce 1,4-dioxane. This process is based dioxane in the presence of various Lewis acid catalysts, 25 on the use of an acidic cation exchange resin which e.g., ZnClg, SnCl4, SiF4, and BF3. Canadian Patent No. accelerates the rate of reaction to at least as great an 540,278 to Astle et al, issued on Apr. 30, 1957, shows the extent as any of the catalysts previously employed. preparation of dioxane by contacting various polyethyl Therefore, although the cation exchange resins are not ene glycols with various acidic type cation exchangers, catalysts in accordance with the precise meaning of the e. g., sulfonated polystyrene type resins, sulfonated phe nol-formaldehyde type resins, etc. British Patent No. term as such, these materials are referred to as “cata 785,229 to Petrochemicals, Ltd., published Oct. 23, lysts” herein for the sake of convenience. The catalysts 1957, teaches the dimerization of ethylene oxide to diox employed in this invention are readily available and can ane in the presence of a metal alkyl catalyst, e.g., alumi be easily and completely removed after completion of num triethyl. 35 the dimerization reaction without any destruction of the A process is also known for preparing dioxane by reaction product. As a result, the process of the inven contacting diethylene glycol with sulfo-acid cationites, tion provides excellent yields of the desired reaction i.e., cation exchanger resins containing sulfonic acid product, with the reaction proceeding smoothly and groups. rapidly at considerably lower temperatures and under However, all of these techniques suffer from one or lower pressures than are necessary when operating in more disadvantages which has prevented an effective the presence of the known acidic catalysts. Although commercialization of this process to date. the catalysts employed in the invention can be dis The dimerization of ethylene oxide for the produc carded after the dimerization is ‘completed, they can tion of l,4~dioxane is a known reaction, and, as noted also be easily regenerated by a simple procedure as above, various proposals have been advanced in the 45 prior art in an attempt to bring this reaction within the described below. ?eld of practical utility by executing it in the presence DESCRIPTION OF THE DRAWING of catalysts. Several catalysts for this purpose are of an acidic nature, particularly sulfuric acid and salts thereof Other objects and advantages of the present invention such as aluminum sulfate, and also various Lewis acids will become apparent from a study of the following such as ZnClg, SnCl4, etc. description and the accompanying drawing in which While the processes which depend upon the employ the FIGURE is a schematic representation of the exper ment of acidic catalysts have the advantage of permit imental set-up used in the invention. ting the use of simple apparatus, they are still quite undesirable from the commercial standpoint. Under the DETAILED DESCRIPTION OF THE reaction conditions employed in the prior art, the acidic INVENTION reaction mixtures have a strongly corrosive action on These objectives are accomplished by the process of the reaction equipment, making necessary the use of costly non-corrosive apparatus or requiring periodic the present invention which comprises dimerizing eth ylene oxide in the presence of an acidic cation exchange replacement of the initially less costly apparatus. Many 60 processes of this kind make use of sulfuric acid as the resin, preferably one having sulfonic acid groups associ catalyst and involve elimination of the acid, after the ated therewith. The reaction mechanism involved in dimerizing reaction is terminated, e.g., by precipitating conducting this process is believed to be as follows: it from the reaction mixture in the form of its barium or calcium salts. Such separation is, however, always in STAGE I complete, and substantial amounts of non-precipitatable In this stage, a reaction is carried out between the salts of organic sulfuric acid compounds remain in the ethylene oxide and the cation exchange resin containing reaction mixture which are only separated during distil sulfonic acid groups to form an ester: 4,365,071 4 In this second stage, the dioxane formation is effected by the back-biting of the chain to product oxonium 0 || species which liberate 1,4-dioxane and an H+. Other P01 mer Substrate —s-on + (mcm-cnz —9 reactions are possible during this stage of the process. g \o/ THE CATALYST EMPLOYED It has been found that the dimerization of the ethyl ene oxide to form 1,4-dioxane proceeds at a practical, rapid rate with resultant high yields of the desired prod uct if it is conducted in the liquid phase in the presence of an acidic cation exchange resin, preferably one hav wherein n; l.