Патент USA US2406631код для вставки
Patented Aug. 27, 1946 - ' 2,406,631 UNITED "STATES PATENT oFncE PRODUCTION OF CYCLO-OIJEFIVNIC HYDRO CARBONS AND AROMA'TIC GHYDROCAR 'BONS Herman Pines and Vladimir N. Ipatieff, r-Cl'licago, 111., assignors to Universal ‘Oil Products Com pany, Chicago, Ill, a corporation of Delaware ‘No‘Drawing. Application‘December 15, 1944, Serial No. 568,391 8 Claims.‘ (01. zco+cesl .1 Glycols, alsoknow-n as dihydric alcohols, uti This invention relates to a process ‘for produc ing cyclic hydrocarbons. More speci?cally, the invention-relates 'toa process forproducing cyclo lizable in our process contain at least 4 carbon atoms :per ‘molecule and have two hydroxyl groups, these groups being preferable in the beta, ole?ns by condensing a glycol of at least 4 carbon atoms iper'molecule with-a ,monohydric alcohol. 5 gamma, and delta positions to each other. Also cyclic glycols ‘such :as 13- Band 1,4-cyclohexane An object of this invention is the condensation diols are utilizable in our process. Ole?nic alco of an aliphatic monohydric alcohol with a gly hols or partially dehydrated glycols such as '2 col containing at least 4 carbon atoms per mole cule. methylpentene-1-o1-4, are also useful raw mate . Another object of this invention is the produc 10 rials for our vcjondensatipn process. Monohydric alcohols utilizable also as starting tion of a cyclohexene hydrocarbon by condensing an 'alkanol with :a glycol vcontaining at least 4 materials in the process of our invention are gen carbon atomsper molecule. erally those :of the aliphatic series and prefer ably are saturated aliphatic carbinols which are A further object of this invention is the pro duction of a cyclohexene hydrocarbon by the con 15 also known as alkanols. Alkanols which do not contain :a quaternary carbon atom are particu densation of a glycol containingat least 4 car larly 'desirablecfor condensationwith a glycol as bon atoms per molecule with an alcohol selected herein set forth as alkanols which contain a from the group consisting of primary and sec quaternary carbon atom sometimes yield a sub A still further object of this invention is the 20 stantial proportion of a teritary‘ ole?n rather than the condensation product desired. production of 1,3,5-trimethylcyclohexene by con Although our IJI'OOESS is sometimes carried out densing 2-methyl-2;4-.p.en;tanediol with a, propyl in the absence of. an added catalyst at suitable alcohol. operating conditions of temperature and pres One speci?c embodiment of this invention re sure, we prefer to utilize catalytic materials to lates to a process for producing a cyclo-ole?n assist in the condensation of a glycol containing which comprises condensing an alkanol and a at least 4 carbon atoms per molecule and an al glycol having at least 4 carbon atoms per mole cohol, preferably an alkanol, and more particu cule in the presence of an acid-acting catalyst at larly an alkanol which does not contain a quater a temperature of from about 150° to about 400° C. nary carbon atom. Catalysts utilizable in our A further embodiment of this invention relates process are acid-acting materials and comprise to a process for producing a benzene hydrocar activated alumina, hydrated silica, acid-treated bon which comprises condensing an alkanol and clays; synthetically prepared composites com a glycol containing at least 4 carbon atoms per prising silica-alumina, silica-alumina-zirconia, molecule to produce a cyclohexene hydrocarbon, ondary alkanols. hydrogenating said cyclohexene hydrocarbon to alumina-zirconia, silica-alumina-thoria; a cyclohexane hydrocarbon, dehydrogenating said cyclohexane hydrocarbon to a benzene hydrocar bon and hydrogen, and utilizing at least a por tion of said hydrogen in the hydrogenation of such as hydrochloric acid, hydrobromic acid, a phosphoric acid, sulfuric acid, a, heteropoly acid as phosphotungstic 0r posphomolybdic acid, etc; and also aqueous solutions of hydrolyzable salts .40 such as ferric chloride, magnesium chloride, zinc said cyclohexene hydrocarbon. chloride, ammonium chloride, magnesium acid Cyclohexene and di?erent alkyl cyclohexene hydrocarbons which are obtainable by the process of our invention may be hydrogenated to cyclo hexane hydrocarbons, or be dehydrogenated to benzene and alkyl benzene hydrocarbons. By the term “condensation” used in this speci ?cation and. in the claims, we mean the chemi cal combination of a dih'ydric alcohol having at phosphate, sodium acid sulfate, etc. process are acid-acting in the sense that an aque ous solution or suspension thereof in Water has a pH below 7. Our process may be carried out using either batch or continuous types of operation, although the latter is preferable. The process is carried hydric alcohol accompanied by thesplitting out i of water. Thus, we have found that 2-methyl 2,4-pentanediol and isopropyl alcohol react at an elevated temperature to produce 1,3,5-tri methylcyclohexene and water as the principal ' These ma terials which we may employ as catalysts in our least 4 carbon atoms per molecule and a mono condensation products. acids 55 out at a temperature of from about 150° to about 400° 0., but preferably at a‘ temperature of from about 175° to about 300° C. The process is pref erably e?ected at a pressure of about 1 atmos phere or higher and is generally not in excess of about 100 atmospheres. 7 7 ‘ _ 2,406,631 3 4 an alkanol at a temperature of from about 150° to about 400° C. and at a pressure of from about character of results obtainable by the process of 1 to about 100 atmospheres. our invention, although the example is not in 4. A process for producing a cyclo-ole?nic hy troduced with the intention of restricting unduly (Fl drocarbon which comprises ‘reacting a glycol the broad scope of the invention. The following example is given to illustrate the 1.3 molecular proportions of isopropyl alcohol having at least 4 carbon atoms per molecule and and 1 molecular proportion of 2-methyl-2,4-pen- . tanediol are commingled and charged to an au an alkanol in the presence of an acid-acting cat_ about 5% by weight of ferric chloride dissolved in water and the volume of this solution is ap proximately equal to that of the mixture of gly col and alcohol introduced thereto. The charged drocarbon which comprises reacting a glycol having at least 4 carbon atoms per molecule and alyst at a temperature of from about 150° to about 400° C. toclave containing a solution of ferric chloride in 5. A‘process for producing a cyclo-ole?nic hy water. The aqueous solution 50 utilized contains 10 an alkanol in the presence of an acid-acting cat alyst ‘at a temperature of from about 150° to autoclave is then heated at about 250° C. for a 15 about 400° C. and at a pressure of from about 1 time of 2-4 hours. After cooling, the reaction mixture contains a hydrocarbon layer compris ing essentially 1,3,5-trimethylcyclohexene which to about 100 atmospheres. 6. A process for producing a cyclo-ole?nic hy drocarbon which comprises reacting a glycol is produced in a yield of.about 30% of the theo retical. Trimethylcyclohexene so formed is con having at least 4 carbon atoms per molecule and vertible into mesitylene ‘by hydrogenation- and dehydrogenation treatments. tion of a hydrolyzable metal salt at'a'tempera ture of from about 150° to about 400° C. and at an alkanol in the presence of an aqueous solu a pressure of from about 1 to about 100 atmos The novelty and utility of the._ process of the pheres. present invention are evident from the preceding 7. A process for producing a benzene hydro speci?cation and example, although ‘neither sec 25 carbon which comprises condensing an alkanol tion is introduced to limit unduly the broad scope and a glycol containing at least 4 carbon atoms of our invention. per molecule to produce a cyclohexene hydrocar We claim as our invention: bon, hydrogenating said cyclohexene hydrocar 1. A process for producing a cyclo-ole?nic hy drocarbon which comprises reacting a glycol 30 bon to a cyclohexane hydrocarbon, dehydrogen ating said cyclohexane' hydrocarbon to a'ben having at least 4 carbon atoms per molecule and zene hydrocarbon and hydrogen and utilizing at a monohydric alcohol at a su?icient temperature least a portion of said hydrogen in the conden and pressure that condensation of said glycol sation of said cyclohexene hydrocarbon. and monohydric alcohol is the principal reaction 8. A process for producing a benzene hydro 35 of the process. carbon which comprises reacting an’alkanol and 2. A process for producing a cyclo-ole?nic hy a glycol containing at least 4 carbon atoms per drocarbon which comprises reacting a glycol molecule to produce a. cyclohexene hydrocarbon having at least 4 carbon atoms per molecule and and dehydrogenating said cyclohexene hydrocar an alkanol at a temperature of from about 150° 40 bon to a benzene hydrocarbon. to about 400° C‘. ' 3. A process for producing a cyclo-ole?nic hy drocarbon which comprises reacting a glycol HERMAN PINES. having at least 4 carbon atoms per molecule and VLADIMIR N. IPATIEFF.‘ ' '