Патент USA US2406869код для вставки
72,406,869 Patented Sept. 3, 1946 UNITED I STATES‘ PATENT OFFICE 2,406,869 ca'rursrrasmmi'non ‘John D. Upham, Bartlesville, Okla" aoaignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application August- 18, 1942, Serial No.'455,241 7 Claims. (01.25%211) 1 2 . This invention relates to the manufacture of catalysts, and more particularly catalysts com prising or consisting essentially of normally solid. or liquid,’ 1. e. non-gaseous halides of the Friedel substantially so, with respect to the, dissolved metal halide’ in order to reduce the expense of preparation of the catalyst. , With this solution may be ‘admixed a solid adsorbent particulate porous carrier material, Crafts type, namely, non-gaseous halides of poly valent metals and metalloids. Still more particu larly it relates to the manufacture of catalysts of the foregoing type which are supported on such as charcoal, activated carbon, fuller’s earth, activated clay, bauxite, Activated Alumina, silica gel, kieselguhr, pumice, etc. Alternatively the an inert adsorbent carrier material. carrier material may have been admixed with The principal object of this invention is to pro 10 the liquid hydrogen halide prior to dissolution of vide an improved process of making a catalyst of the metal or metalloid halide. the Friedel-Crafts type. Another object is to The proportions of the solution and the carrier provide an improved process of preparing a sup material relative to one another may vary within ported catalyst of the Friedel-Crafts type. An wide limits from the point where the. carrier is in other object is to provide an improved method 15 completely saturated, that is, is in excess, to the of making an aluminum chloride catalyst in point where the carrier amounts to say only 25% highly active powdered form. Still another ob by weight of the solution. The relative propor Ject is to make a supported aluminum chloride tions of solution and carrier are chosen to give catalyst in an ‘improved manner. Numerous a finished catalyst containing any desired propor other objects will more fully hereinafter appear. 20 tion of metal or metalloid halide on the carrier. Catalysts prepared‘in accordance with my in The carrier material may be either coarse or vention may be used for catalyzing any reaction ?nely divided, and preferably of not over 100 which has heretofore been catalyzed .with nor mesh size ranging therefrom down to 300 mesh. mally solid or liquid halides of the Friedel-Craits It is preferred in many reactions to use the cata type, such as isomerization, for example, conver 25 lyst in-the form of a suspension or slurry. In sion of normal para?lns'toisoparailins, such as other cases the catalyst is suspended or floated normal butane to isobutane, cracking, reforming, in a gaseous medium. For such reactions the car polymerization, alkylation, for example, alkyla rier particles should be extremely iine in size. tion of isopara?ins with ole?ns such as of isobu In some cases the catalyst is used in the form tane with butene to give isooctane, alkylation of 30 of lumps or large granules packed into a reac aromatics with ole?ns such as of benzene with tion tower, the liquid or gaseous reaction stream ethylene to give ethylbenzene which is an inter being passed thereto. My invention may also be mediate in the manufacture of styrene, condensa practiced using such large lumps of carrier. tion, arylation, reactions of the Friedel-Crafts The temperature at which the foregoing oper type, etc. , The halides which are employed ‘as the active ‘component of’ the catalysts of my invention are the normally non-gaseous halides of polyvalent metals and metalloids which are of the Friedel 35 ations are conducted may be atmospheric or may be substantially thereabove. However, the tem perature must not be above the critical temper ature of the pure hydrogen halide or of the solu - tion of metal halide therein. In practice it will Crafts type. Examples are the normally liquid 40 be desirable to stay below the critical temper or solid ?uorides, chlorides, bromides or iodides atures of the pure hydrogen halides which are as of aluminum, zinc, tin, arsenic, antimony, zir follows: conium, beryllium, titanium, iron, molybdenum, boron, etc. Usually the normally solidhalides of polyvalent metals, the hydroxides of which are 45 -, ~ ° C. Hydrogen ?uoride___; _________________ __ 230.2 amphoteric, and especially of aluminum, are pre Hydrogen chloride _____________________ __ 51.4 ferred. Hydrogen'bromide ______ -.’ _____________ __ 90.0 _ Hydrogen iodide? _______________ __‘ ____ __ 151.0 In accordance with my invention, in a typical embodiment, a solution of the anhydrous metal The pressure during these steps of the process or metalloid halide in a liquid anhydrous hydro 60 will be at least sufficient to maintain the hydro gen halide, such as lique?ed hydrogen ?uoride, gen halide in liquid phase. .This will depend upon chloride, bromide or iodide may ?rst be prepared the temperature and may range from atmospheric preferably by dissolution of the anhydrous metal where the‘temperature is below the boiling point or metalloid halide in the liquid hydrogen halide. of the pure hydrogen halide or of the solution Preferably the solution so formed is saturated or 56 obtained up to the critical pressure of the pure 9,406,869 - 4 3 hydrogen halide or of the solution or higher but seldom above 100 atmospheres. The critical pressures of the several hydrogen halides are: immediately or after lapse of a suf?cient period of time to allow soaking of the solution into the pores of the carrier, the hydrogen halide is vola tilized from the mixture to eifect precipitation Atmospheres Hydrogen ?uoride ______________________ __ 90 Hydrogen chloride ______________________ __ 81.8‘ . of the metal or metalloid halide in solid or liquid form, as the case may be, within the pores of the carrier. This vaporization of hydrogen halide and consequent deposition of the metal halide upon the carrier may be brought about by Ordinarily the carrier material and the solu 10 the release ,of pressure to a‘suitable ?gure or the tion of metal or metalloid halide in the liquid or elevation of the temperature to a suitable level, lique?ed hydrogen halide are thoroughly mixed or by both of these measures. The selection of with one another as by vigorous agitation so pressure and temperature to accomplish this re as to effect impregnation of the carrier with the sult will be well within the skill of the art in the solution. Other methods of effecting contact and 15 light of this disclosure. . impregnation may be employed, however. For If in the contacting step the carrier is at a example the carrier may be sprayed with the solu temperature above the boiling point under the tion in any desired manner, as by exposing a prevailing pressure, this causes vaporization of a layer of carrier agitated to continuously expose portion of the hydrogen halide and partial pre Hydrogen bromide ______________________ __ 84 Hydrogen iodide _.... 82 fresh surfaces as in a rotating drum or cylinder 20 cipitation of the metal or metalloid halide. Like while spraying the solution thereon, or by inti mately dispersing both carrier and droplets of wise if the pressure prevailing in this step is below that upon the solution and the level necessary to solution with one another in a suitable gaseous keep thehydrogen halide in liquid form, this ef medium. The method of impregnation may be fects vaporization of some hydrogen halide. Or, analogous to spray drying. Thus, a cloud or sus 25 both higher temperature and lower pressure may pension of the carrier in a suitable gaseous me bring about some precipitation. Usually, how dium may be sprayed with the solution in such ever, it will be desirable to e?ect additional vola manner that the solution coats and impregnates tilization and precipitation by subsequently ele the carrier particles. vating the temperature and/or releasing the If desired the carrier may have been previously 30 pressure in the manner described in the preced treated in such a manner as to promote more ing paragraph. 4 rapid and more thorough contact, wetting, and Generally, all or substantially all of the hydro impregnation with the hydrogen halide solution. gen halide solvent is volatilized so that all or sub For example it may have been evacuated to re stantially all of the dissolved solid or liquid halide move the air, and kept under vacuum until, the 35 is precipitated upon the carrier. However, a time of contact with the solution. Alternatively small amount of residual hydrogen halide may be the air may have been displaced with a gas which ' is soluble in or wetted by the solution, preferably left in the product to act as promoter in the re action catalyzed therewith; usually such residual a hydrogen halide, as by sweeping with such a hydrogen halide will not exceed 5% by weight gas, evacuating the carrier and then contacting 40 based on the weight of the metal or metalloid with the gas, or in any other way. For example, halide. Such hydrogen halide will be very inti in an especially suitable mode of operation, the mately distributed throughout the precipitated carrier may be heated to an elevated temperature metal or metalloid halide. and then cooled in an atmosphere of hydrogen Occasionally use of a carrier described above halide gas whereby the pores of the carrier are 45 may be dispensed with and the solution of nor substantially ?lled with said gas. The carrier mally solid metal halide in the hydrogen halide may be treated or impregnated with any other simply treated in such manner, for example, by material which facilitates the wetting of the car spray drying, as to volatilize the hydrogen halide rier by the solution. Certain solids or liquids solvent in substantial entirety and precipitate the may have this wetting power. 50 solid halide in ?nely divided form. Such pul Another mode of effecting rapid impregnation verulent solid metal halide has an unusually high is to heat the carrier to drive 03 the air and to activity, much greater than that of conventional contact while hot with the solution and allow the powdered metal halide. carrier to cool while thus in contact with the so The product of the foregoing process should be lution, thereby forcibly drawing the solution into 55 stored in an inert atmosphere until use,for ex ample, in moistureprcof receptacles in which a the pores. dry inert gaseous atmosphere such as nitrogen, Since the solution is maintained and the con tacting step is ordinarily carried out under ele vated pressure su?icient to hold the'hydrogen hydrogen halide, etc. is maintained over the cat alyst. The catalysts so prepared may be used by halide under pressure, this pressure aids in forc 60 transfer to the reaction zone for example a sta tionary catalyst case. ing the solution into the pores of the carrier. If desired this action may be accentuated by vary If desired, the catalysts of the present inven ing the pressure or effecting alternate increase tion may be prepared in situ in the reaction zone and decrease in the extraneous pressure applied through which the reactants are subsequently throughout the impregnation step as by intermit 65 passed. In some cases an initial portion of the tent application of additional pressure, or by al reactants may be employed to aid in the volatili ternate release and application of high pressure, zation and sweeping out of the hydrogen halide or by alternate evacuation and application of from the solution and consequently in the precip high pressure. For example, a, piston and cylin itation of the metal or metalloid halide. der may be arranged with the space above the The catalysts of my invention may be used as piston connected to the contacting zone and the suspensions in ?uid reactants, that is, in the so piston alternately retracted and advanced to ef called “?uid catalyst" processes now being intro~ fect the desired periodic ?uctuations in pressure. duced commercially. During or following impregnation of the car The product is a highly satisfactory catalyst rier with the solution, and in the latter case either 76 for reactions of the type enumerated in detail 2,406,869 above. It is particularly useful in those reactions substantially all of the hydrogen halide from the resulting solution by spray drying under condi tions to effect precipitation of solid metal halide tion, acylationy isomerization, etc., in that small in the form of ‘finely divided solid particles hav amounts of such hydrogen chloride or other 5 ing intimately associated therewith less than halide may be left in intimate contact with the about 5 weight per cent residual hydrogen halide metal halide in the manner described in the fore in substantial and effective catalyst-activating going. where hydrogen chloride or other halide is em ployed as an activator or promoter such as alkyla amount. An especially preferred combination employed - 2. The process of claim 1 wherein said metal in carrying out the present invention is alumi num chloride and hydrogen chloride. Following halide is aluminum chloride and said hydrogen halide is hydrogen chloride. is a typical example of such an embodiment of my 3. The process of claim 1 in which said solu tion is spray dried in contact with a ?nely divided solid adsorbent carrier material having a particle size within the range of about 100 to about 300 invention. Example , By way of example, the preparation of a cata mesh,"said carrier thereby being impregnated lyst comprising anhydrous aluminum chloride on bauxite will be described. with said metal halide forming a ?nely divided A solution of alu supported catalyst having residual hydrogen hal minum chloride in liquid anhydrous hydrogen chloride is prepared by dissolving anhydrous alu ide associated therewith in substantial and e?ec " tive catalyst-activating amount. minum chloride in a slight excess of anhydrous 4. The process of preparing a catalyst which comprises ?lling the pores of a solid adsorbent lique?ed hydrogen chloride whichis held under sui?cient pressure to maintain liquid phase. This may conveniently be done at ordinary at particulate carrier material with gaseous anhy drous hydrogen halide, contacting the resulting mospheric temperatures, although other temper carrier with a solution of a normally non-gase atures may be used if desired. The solution thus formed is then thoroughly mixed with bauxite of ous anhydrous halide of the Friedel-Crafts type in a liquid anhydrous hydrogen halide and there by impregnating said carrier with at least part of a desired particle size, so as to impregnate the bauxite with the solution. The pressure is then said solution, the presence of said gas in said released and/or the temperature increased to pores facilitating said impregnation, and volatiliz vaporize the hydrogen chloride, which results in 30 ing hydrogen halide from the mixture to e?'ect the deposition of aluminum chloride within the precipitation of-said non-gaseous halide in and pores of the bauxite. The relative proportions of solution and bauxite are chosen to give a cata lyst containing any preferred amount of alu minum chloride on the bauxite. ' It will be understood that both the hydrogen halide and the metal or metalloid halide should be anhydrous and harmful water should be ex cluded throughout the process. However, use of a solid adsorbent carrier‘ containing chemically combined water, that is only partially dehy 35 upon said carrier. 5. The process of preparing a catalyst which comprises filling the pores of a solid adsorbent particulate carrier material with a gaseous an hydrous hydrogen halide, contacting the result ing carrier with a solution of a normally non gaseous anhydrous halide of the Friedel-Crafts type in a liquid anhydrous hydrogen halide and thereby impregnating said carrier with at least part of said solution, the presence of said gas in said pores facilitating said impregnation, and volatilizing hydrogen halide from the mixture drated, is not precluded in the practice of my in vention. Reference is made to my copending applica 45 substantially completely by spray drying to ef tion Serial No. 454,310, ?led August 10, 1942, now fect precipitation of said non-gaseous halide in U. S. Patent 2,356,487 which discloses certain and upon said carrier. subject matter disclosed and claimed herein and ' 6. The process of claim 4 wherein said non of which this application is therefore a continu gaseous halide is aluminum chloride and said hy ation-in-part as to such common subject matter. drogen halide is hydrogen chloride. I claim: "1. The process of claim 5 wherein said non 1. The process of preparing a catalyst which gaseous halide is aluminum chloride and said hy comprises dissolving a normally solid anhydrous drogen halide is hydrogen chloride. metal halide of the Friedel-Crafts type in a lid uid anhydrous hydrogen halide, and volatilizing JOHN D. UPHAM.