Патент USA US2404498код для вставки
Patented July 23, 1946 ' 2,404,498 , UNITED STATE s rATENTJ omceff 2,404,498 PRODUCTION OF TOLUENE I ' VladimirN. Ipatieff and George S. Monroe, River-7 side, 111., assignors to Universal Oil Products ‘ Company, Chicago, 111., a corporation ofvDela I ' ware No Drawing. Application Mai-011' 27, 1944, . Serial No. 528,345 , 7 Claims. (01. 2604-671) 1 2.. ' refractory carriers such as natural-‘occurring’s'ili This invention relates to the production of tolu ene from benzene and methane in therpresence of a catalyst and is more speci?cally concerned with ceous or aluminiferous materials or synthetically ' prepared'supportsn ‘_ ' ’ " v ' 5' clude kieselguhr, acid-treated‘ clays, bauxite and stantial yields of toluene in the presence of a par similar substances. Synthetic carriers may-com‘ prise silica, alumina, thoria and similar refractory .4 ticular catalyst and under speci?c conditions'of temperature and pressure. ' Natural-occurring supporting materials will in the conversion of benzene and methane into- sub- - ‘ materials. ‘The various catalysts ‘produced by compositing the above refractory carriers and the conversion processes such as cracking, reforming; 10 active metals or metal 'oxides'are not necessarily equivalent in their ability to accelerate the de-v etc. 'Heretofore, because in ordinary operation sired reaction. The activity of each catalyst will it is chemically inert, the primary uses of meth be dependent to a certain extent ‘upon the vpar ane in industry has been for fuel, for the manu / Methane’ is obtained in abundancefrom natural gases or as a by-product of various hydrocarbon facture of carbon black or as an inert diluent in ticular metal or metal oxide and carrier chosen. reactants. guhr, 'A-detailed method‘of preparing this cata: various hydrocarbon conversion ‘processes to ef 15 A particularly active catalyst comprises a com posite of metallic nickel, nickel oxide and kiesel fect a ‘lowering of the partial pressure of the ' ' lyst is given hereinafter in this speci?cationl. 5 , The'carrier materials maybe‘ obtained by a number of methods, some‘ of ‘which are herein It_ is recognized that methane has been con verted to methyl chloride and the methyl'chlo ride employed as an alkylating agent to alkylate benzene in the presence of aluminum chloride to produce toluene and more highly alkylated ben zenes.‘ However, the preparation of the methyl chloride is expensive and, for this reason, the process has not assumed any commercial impor tance. ' after set forth: In' one broad embodiment, the‘present inven tion comprises a process for producing toluene by subjecting a mixture‘ of benzene and methane to contact with a catalyst'comprising at least one substance selected from the group consisting of the metals having an ‘atomic number of 26 to 29 . inclusive and the oxides thereof. vention comprises a process for producing toluene by subjecting a mixture of benzene and methane to contact with a catalyst comprising at least one‘ ~ ' " ‘ i > ' ' occurinnature, to Wit, hydrargillite or gibbsite, and dihydrated minerals are suitable for the man-. ufacture of the present types of catalysts‘and these materials have furnished types of activated alumina which are entirely satisfactory; Precipi tated trihydrates can also be‘ dehydrated at mod erately- elevated temperatures-to form satisfac tory types of alumina; crystallographically and X-ray -spectroscopically,,"this; most satisfactory type of alumina is referred to as gamma-alumina, crystallizing in the cubic system; the length of edge of the unit cube being about 7.9 "Angstrom units. In a more speci?c" embodiment, the present in ' 25 bauxite, and diaspore. Of these three minerals the corresponding oxides from the trihydrated It is an object of the present invention to pro vide a method for producing toluene from ben zene and methane directly thereby obviating the necessity of ‘forming expensive intermediate al 30 kylating agents such as'methyl chloride. ‘ ‘ In regard to the production of alumina, it may be stated that three hydrated oxides of aluminum ,, , . t, . It is best practice in the ?nal steps of prepara tion of aluminum oxides for use in the'catalyst composites to ignite them for- some time at tem peratures within the approximate range of 500° to 600°, C; jThisdoes not correspond-‘to ‘complete. substance selected from the group consisting of dehydration of ‘the hydrated oxides but gives the metals having an atomic number of 26' to 29 inclusive and the oxides thereof at a temperature 45 catalytic materials of goodstrength and porosity, so that they are able to resistior along time the within the range of about 275° C. to about 450° C. deterioration effects of the service and there and under‘ superatmospheric pressure within the range _ of about 10 atmospheres to about 450 atmospheres. . t "' As previously set forth,’the catalysts useful in the process of the present invention comprise‘ metals having an atomic number of 26 to 29 and include nickel, cobalt, iron, copper and the oxides thereof. JThesecataly'sts can‘beused alone or in activation periods to which they aresubjected. Aluminasv having ;the physical characteristics of “activated alumina” of commerce arewelladapt editor use as a supportjfor these ‘catalysts. - ' » Silica suitable-for compositing with activating oxides to produce catalysts maybev obtained con-1 veniently by‘ precipitating silica gel “from a-solu admixture-with one another oncomposited with 5.5. tion of a water-soluble‘ silicate bythe addition‘ of " 2,404,498 an aqueous solution of a mineral acid followed by washing to remove water soluble salts and dry:v of this invention, consists in passing a mixture ' of benzene and methane over a fixed bed of cata- . lyst maintained at a ' temperature from about " ing to produce a granular material comprising essentially silica. v I 275 to 450° C. under a pressure of from about ‘ Thoria utilized in the production of- dehydro 10 to about 450 atmospheres. The reaction mix-' genating catalysts may be obtained by. known_ _ tureundergoing treatment preferably contains methods from a number ‘of minerals including, between about 21 and about 20 molecular pro thorite, orangite, and thorianite. The catalyst may be prepared employing varié. portions of methane per one molecular propor "tion of benzene in order to favor production of ' ous procedures; for example, the prepared re 10. toluene and to diminish the reactions which re fractory material such as calcined silica,- alumina ' ‘ sultin'the formation of diphenyl and alkylated or thoria or natural-occurring siliceous material diphenyl which are valuable products although such as kieselguhr may be suspended in aqueous, , not preferred products of the present process. solutions of soluble salts of the various metals > The reaction may also be conducted in a ?uid- Y and the entire solution evaporated .to dryness. 15 ized or moving-bed, type of operation wherein the reactants are introduced into a bed of ?nely The residue may then be dried and calcinedto divided catalyst at suf?cient velocity such that decompose the salt deposited thereon to form the ‘ the catalyst particles are motionalized to form oxide of the metal. This composite may be’fur; a catalyst bed resembling a liquid in appearance. 'ther treated with a reducing gas such as hydrogen or carbon monoxide to convert the oxide into the 20 The reaction products are withdrawn from the catalyst zone, entrained catalyst separatedwthere metal," said reduction forming a very active cataT v from’ recycled tothelreaction zone. The’ reac- v lyst. ' The extent. of reduction can be variedso that the i?nal catalyst is a composite" of ref-rac tory carrier, metal and metal oxide. ‘ tion products are then passed through suitable fractionating systems wherein the desiredprod Another procedure which may be employed for manufacturingnthe catalyst consists of ‘suspend ing the 'hydrogel of the refractory carrier such rial and the latter recycled to. the ‘reaction-zone.‘ In the compact moving-bed type ofoperation,‘ as silica orralumina hydrogel in an aqueous solu a compact bed of ?nely divided'catalysts may be ucts are separated from’ the unconverted .mate passed through the reactiorrzonev eitheri courier tion of thevmetal salt followed by drying and cal- V cining and the reduction as set forth above. 30; current or concurrent with the hydrocarbon re-‘_ Still another. method may comprise impregnats actants, the reaction productswithdrawn from. the reaction zone into a'suitable'separation sys ing the prepared refractory carriers by immersing tem and the spent catalyst passedinto' a're‘geni eration’ zone in which it is reactivated andlreé the carrier for a short time in a solution of a ‘ soluble salt again followed by the calcination and reduction operations. Although all the catalysts, . I cycled to the reaction zone. ' ' ’ ' " The catalyst after continued use accumulates: a deposit of carbonaceous materials which’ impair the catalyst activity. The regeneration‘ofl the‘ catalyst may be accomplished by comb'ustion‘in mentioned herein ‘possess activityvfor the dis closed reaction, it, is not intended to infer that they are‘ the equivalent in their. ability to ac celerate the interaction of benzene and methane. ' . the presence "of regulated quantities‘ofoxy'gen, The general method of preparationof a nickel " or oxyge‘n-c'zontainir'igr gases; kieselguhr catalyst involves the following steps: Kieselguhr is suspended. ina relatively dilute ' Y ' ‘v ‘ * " I Another method of regeneration consistslof subjecting ‘the carbonaceous deposit to‘ contact‘ aqueous solution of nickel sulfate and a saturated hot solution of sodium carbonate is added grad. with high pressure hydrogen which hydrogenates, ually with constant agitation. ‘The proportions. the deposit to form hydrocarbons which are the'r'e- '‘ of kieselguhr, nickel sulfate and sodium carbonate.‘ beingchosen so that after washing, drying the precipitate and reduction with hydrogen, the de sired composition is obtained. The primary pre-v the‘ catalyst, this hydrogenation treatment‘will. after easily removed from the catalyst surface. i In case there is considerable sulfur present on convert the sulfur tohydrogen sul?de which is cipitate consists of kieselguhr, nickel carbonate,v 50 subsequently separated‘ along with thel'eii‘luent“ from the regeneration zone. In general, the prod and nickelous hydroxide. This precipitate is then ucts formed during treatment of mixturesofben- ‘ dried and mixed with about 4% of its Weight zene and methane witha dehydrogenating cata-. of powdered graphite and pelleted into small lyst are separated from theunreac'ted' benzene‘. cylindrical forms in any standard type operating. machine. The formed pellets that still contain 55 and methane‘ by suitable means as by distillation. I and the unreacted portions‘- of the‘_ benzene. and’. a mixture of carbonate and hydroxide are then heated in a stream ofair or nitrogen to eliminate carbon dioxide. After the requisite amount of carbonaterdecomposion has been effected, reduc tion of the nickel oxide is conducted at increase 60 ing temperatures in, a stream of hydrogen until a temperature of approximately 425° C. is reached. The weight per cent of nickel which maybe in; vcorporated in the composite catalyst will vary from about 20 to about 95% and preferably with; 65' in the range of about 60 to about 90 Weight per cent. ' ' - As previously stated, methane is ordinarily considered'chemically inert. - However, we havevdis covered that'in the presence of the-catalyst pre 70 viously described and under selected conditions of operation, toluene can be produced from a mixture of benzene and methane. ' The procedure preferably utilized for’ effecting"; methylation of benzene, according to the process’ methane recycled andlcommingled with .addi-. tional quantities of‘ these ‘hydrocarbons being’ charged to the‘catalyst zone- ‘Hydrogen or hy drogen-containing gasesproduced in the'process may alsobe recycled. ‘with the. recovered benzene ~ and methane. The reaction product boiling higher thanlbenzene‘ is'"separated in'to' desired" fractions or individual compounds including'tol-f. uene and diphenyl by distillation at;v ordinary; or reducedpressure or by other “suitable means.’ ‘The.’ following examples. are given to‘ illustrate! the} character of results obtained’by’the useof-the? present process although the data presentedjar'le' not introduced with theintention .of‘unduly lim-v itmg the generally broad scope of (they invention-.7 ~J EXAMPLE liif About" 72.8 grams ,of benzene ‘(grams _ of- methane were charged jalQng" With'j72" gramsf 75‘ of" reduced nickelkieselguhr catalystv into‘ a roe"e 2,404,49Q 2. A process for producing toluene which com tating autoclave of about 330 cc. capacity. The. prises subjecting a mixture of benzene and meth ane to contact with a catalyst comprising a re fractory carrier and at least one substance se lected from the group consisting of the metals having an atomic number of 26 to 29 inclusive and the oxides thereof at a temperature within products removed therefrom. The hydrocarbons the range of about 275° C. to about 450° C. and were separated from the catalyst and subjected under superatmospheric pressure within the to fractional distillation. The hydrocarbon prod ucts had the following analysis: 10 range of about 10 atmospheres to about 450 atmospheres. Per cent 3. A process for producing toluene which com Unreacted benzene ____________________ .. 74.5 prises subjecting a mixture of benzene and a Alkylate (chie?y toluene) ______________ __ 20.9 autoclave was heated to 400° C. and held at this temperature for 4 hours. The maximum pres sure reached in the autoclave was 7500 pounds per square inch. The autoclave was allowed to cool to approximately room temperature and the Naphthenes __________________________ __ 0.6 . molar excess of methane to the action of a cata 4.0 15 lyst comprising at least one substance selected ~ from the group consisting of the metals having an atomic number of 26 to 29 inclusive and the Total ___________________________ __ 100.0 oxides thereof at a temperature within the range The following table presents the results ob of about 275° C. to about 450° C. and under a Residue, no tar-naphthalene derivative--- tained in Examples 2 to 6 inclusive. These results pressure within the range of about 10 atmos were obtained in a continuous operation in which 20 pheres to about 450 atmospheres. a pelleted nickel-kieselguhr catalyst was disposed 4. A process for producing toluene which com in ?xed bed relationship to the incoming react prises subjecting a. mixture of benzene and meth ants. ane to the action of a catalyst comprising nickel Table and kieselguhr at a temperature within the 25 range of about 275° C. to about 450° C..and under Example No. a pressure within the range of about 10 atmos pheres to about 450 atmospheres. 2 3 ‘ 4 5 6 Operating conditions: emp., ° 5. A process for producing toluene which com- 1 30 372 348 370 351 366 Pres. #lsq. ” _____________ __ 8, 000 _____________ _. 6, 000 6, 000 4, 000 1, 000 0.6 0.5 0.5 0.6 41. 0 30. 7 36. 2 31. 7 28. 1 8. 6 1. 5 5. 3 1. 4 5. 6 1. 6 5. 7 1. 5 4. 5 l. 4 Benzene (recov.) ________ _. 48. 0 62.0 55.8 60.0 63. 7 Carbon ................. __ 0.9 0.6 0.8 1. 0 2. 3 100. 0 100. 0 100. 0 100. 0 100. 0 Mols 05H; per mol of CH4_ Products wt. per cent of total 0. 4 . _____ _. __ charge: Methane__ Toluene..Higher HC__‘_____ We claim as our invention; 1. A process for producing toluene which com 35 prises subjecting a mixture of benzene and meth ane to the action of a catalyst comprising nickel at a temperature within the range of about 275° C. to about 450° C. and under a pressure within the range of about 10 atmospheres to about 450 at mospheres. 6. A process for producing toluene which com prises subjecting a mixture of benzene and meth; ane to the action of a catalyst comprising iron. at a temperature within the range of about 275° C. 40 to about 450° C. and under a pressure within the. range of about 10 atmospheres to about 450 at mospheres. prises subjecting a mixture of benzene and methe 7. A process for producing toluene which com ane to contact with a catalyst comprising at least prises subjecting a mixture of benzene and meth one substance selected from the group consisting 45 ane to the action of a catalyst comprising cobalt of the metals having an atomic number of 26 to at a temperature within the range of about 275° C. 29 inclusive and the oxides thereof at a tempera ture within the range of about 275° C. to about to about 450° C. and under a pressure within the , 450° C. and under superatmospheric pressure mospheres. Within the range of about 10 atmospheres to about 450 atmospheres. range of about 10 atmospheres to about 450 at ' - VLADIMIR N. IPATIEFF. . GEORGE S. MONROE.