3,130,147 United States Patent Office Patented Apr. 21, 1964 2 ponent as described above, be employed for reforming or 3,130,147 hydrocracking operations. Another reaction employing ZRCONUM-AJMNUMA - POSPHRUS CATA LYST AND WETHOY FOR PREPARNG THE a catalyst of the above dual-function type is a desulfuriza SAME, EMPLOYED FOR THE CRACEKENG OF tion reaction in which hydrocarbon fractions containing HYDRO CAR3CNS combined sulfur are subjected to mild hydrogenating con Francis G. Bwyer, Daiayware Township, Canadea County, ditions in the presence of an acidic catalyst to effect the and Sylvander C. Eastwood, Woodbary, N.J., assigliors hydrogenation and desulfurization of molecules to pro to Socoay Mobil Gi Conigaay, Inc., a coregration of duce hydrogen sulfide and the corresponding hydrocarbon. New York The dual-function type catalyst may be prepared by inti No Drawing. Fied Sept. 18, 1961, Ser. No. 138,563 mately combining the acidic composite described herein 7 Cairns. (C. 208-114) O with a dehydrogenation component comprising a heavy This invention relates to an acidic catalytic composite metal of groups V through VII of the periodic table or a and to a method for manufacture thereof. More particul compound thereof. Examples of suitable metals for such larly, the present invention is directed to an acidic catalyst purpose are platinum, palladium, nickel, cobalt, iron, consisting essentially of an oxygen-containing combina 5 manganese, chromium, molybdenum, tungsten, vanadium tion of aluminum, zirconium and phosphorus and to a and copper. Certain combinations of these metals pro method for preparing said catalyst. duce synergistic effects such as combinations of cobalt It has heretofore been known to prepare catalytic com and moiybdenum, nickel and tungsten, and chromium and posites of alumina and zirconia. Such composites have copper. been produced, for example, by reacting a solution of an 20 One of the principal objects of the present invention is aluminum salt and an alkali metal zirconium carbonate. the provision of an acidic catalyst consisting essentially It has also been known to prepare metal phosphate cata of any oxygen-containing combination of aluminum, zir lysts, particularly applicable for use in polymerization re conium, and phosphorus. Another object is to afford a actions, by treating suitable porous adsorbent materials method for producing hydrosols of such composition with phosphoric acid. 25 characterized by a short gelation time. A still further ob The present invention is directed to a new acidic cata ject is the provision of a process for manufacturing cogels lyst useful in hydrocarbon conversion processes utilizing consisting essentially of an oxygen-containing combination an acid-acting catalyst, such as isomerization, polym of alurhinum, zirconium, and phosphorus by forming a erization, alkylation and cracking. Also, the catalyst hydrogel of such composition which, after aging, may be described herein may effectively serve as the acidic com 30 washed free of water-soluble matter and dried to form ponent of a dual-function catalyst comprising an acid a porous adsorbent catalytic product. acting component and a dehydrogenation component. The above and other objects which will be apparent to Such latter type catalysts are useful in hydrocarbon con those skilled in the art are achieved in accordance with version operations such as hydrocracking and reforming. the present invention wherein composites consisting es In one embodiment, the present invention provides Sentially of an oxygen-containing combination of alu for a process for the manufacture of an acidic catalyst minum, zirconium and phosphorus are prepared by re by reacting, in aqueous solution, a water-soluble aluminum acting, in aqueous solution, a water-soluble salt of zir compound, a water-soluble zirconium compound and a conium, a water-soluble salt of aluminum, and a water water-soluble oxyacid of phosphorus or salt thereof to soluble oxyacid of phosphorus or salt of such acid to yield an acidic hydrosol in which the atomic ratio of 40 yield a sol which sets to an all-embracing hydrogel in aluminum to zirconium is between about 0.1 and about which the atomic ratio of aluminum to zirconium is be 10 in which the atomic ratio of the combined content of tween about 0.1 and about 10, and in which the atomic aluminum and zirconium to phosphorus is between about ratio of the combined content of aluminum and zirconium 0.1 and about 10, permitting the resulting hydrosol to set to phosphorus is between about 0.1 and about 10. The to a hydrogel, aging the hydrogel in an aqueous solution hydrogel so obtained, is thereafter aged in a solution of of an alkali metal or ammonium sait of an acid char a weak acid ammonium or alkali metal salt and subse acterized by a dissociation constant of less than about quently contacted with such aqueous treating solutions 1.7Xi 02, washing the aged hydroge! free of water as are desired for density control, base-exchange, impreg soluble matter and drying the washed hydrogel. nation or the like; water-washed free of soluble matter In another embodiment, the invention provides for an 50 and dried. The resulting product is thereafter calcined acidic catalyst consisting essentially of an oxygen-con generally at a temperature between about 800 F. and taining combination of aluminum, zirconium and phos about 1400 F. phorus prepared by the foregoing method. Hydrogels prepared by the process described herein are In still another embodiment, the invention comprises generally characterized by a gelation time of not more an acidic catalyst consisting essentially of an oxygen 55 than 2 hours although it is to be realized that hydrogels containing combination of aluminum, zirconium and phos having a longer time of set when desired may also be phorus wherein the atomic ratio of aluminum to zirconium produced by the present method. The method of this is between about 0.1 and about 10 and in which the atomic invention is particularly adaptable for the production of ratio of the combined aluminum and zirconium content hydrogels characterized by a time of set of less than about 60 20 seconds which hydrogels are capable of being formed to phosphorus is between about 0.1 and about 10. into spheroidal particles upon introducing the hydrosol in In yet another embodiment, the invention provides for the form of globules into a water-immiscible medium and a dual function catalyst wherein the above acidic com maintaining the hydrosol globules in the medium until ponent is intimately combined with a dehydrogenation they set to globules of hydrogel. component, comprising a heavy metal constituent, for 65 The essential compounds required for forming inor example, metals or compounds of metals of groups V ganic Oxygen-containing cogels of aluminum, zirconium through VIII of the periodic table. and phosphorus in accordance with the present process The catalyst described herein is thus applicable for use include a water-soluble aluminum salt, a water-soluble in numerous hydrocarbon conversion reactions. The zirconium salt and a water soluble oxyacid of phosphorus catalyst may be employed by itself, for example, in effect 70 or a Salt thereof. These compounds may be intimately ing isomerization, polymerization, alkylation and crack mixed, in aqueous solution, in any desired manner to ing or may, in combination with a dehydrogenation com yield a resulting hydrosol. The solutions may be con 3,130,147 4. tacted by flowing streams thereof together under con pounds. The present composites have been found to ditions of rapid flow such as in a mixing nozzle. Addi be particularly useful as acidic catalysts in promoting tional components may, if so desired, be introduced at acid catalyzed reactions such as cracking, isomerization, this stage by dissolving a suitable. compound of the de polymerization, and alkylation when used alone. The sired component in one of the hydrosol forming solutions catalyst described herein may also be used as one com or by mixing a stream of a compound of such desired ponent of a dual-function catalyst wherein it is present as component with the streams of the reactants. The an acidic component and intimately combined either by water-soluble aluminum salt employed may include any suitable mechanical admixture or by impregnation with of the readily available water-soluble salts of this metal a dehydrogenation component as described hereinabove. and, particularly, the salts of mineral acids such as the O The following examples will serve to illustrate the sulfate, chloride and nitrate. Likewise, the water-soluble catalyst of the invention, its method of preparation and zirconium salt employed may include any of the readily its use in hydrocarbon conversion. available zirconium salts such as zirconium tetrachloride, zirconium tetraiodide, zirconium sulfate, zirconyl bromide, Example 1 zirconyl chloride, and zirconyl iodide. The water-solu 5 A hydrosol was prepared by mixing 6629 grams of ble oxyacid of phosphorus or salt thereof may include, an aqueous solution containing 128 grams of AlO3 as by way of example, orthophosphoric acid, pyrophos Al2(SO4)3 and 622 grams ZrO2 as Zr(SO4)2.4H2O with phoric acid, and metaphosphoric acid, phosphorus acid 3870 grams of a solution containing 1158 grams of so and hypophosphorus acid and salts of said acids, particu dium hexametaphosphate. The resulting sol set to a larly, the alkali metal and ammonium salts which may 20 firm, all-embracing hydrogel having a pH of less than be monobasic, dibasic or tribasic salts of the specified 1 in about 10 minutes. The hydrogel was broken up acids including, for example, sodium tripolyphosphate into cubes and aged in a 10 percent weight aqueous solu and sodium hexametaphosphate. tion of ammonium acetate for 16 hours at 160 F. After The quantity and concentration of the reactant solu aging, the gel was water-washed for 24 hours to remove tions employed is, in accordance with the invention, 25 soluble salts and thereafter dried in superheated steam controlled to afford a resulting gel product in which the at 250 F. and finally calcined in air at 900 F. for 3 atomic ratio of aluminum to zirconium is within the hours. range of 0.1 to 10, and in which the atomic ratio of com The gel catalyst, so prepared had a surface area of bined aluminum and zirconium, i.e. total metals content, 230 m./g. and contained aluminum and zirconium in an to phosphorus is within the approximate range of 0.1 30 atomic ratio of 1:2 and an atomic ratio of total metals to 10. (combined aluminum and zirconium) content to phos The hydrosols prepared in accordance with the present phorus of 1:1.5. process may be allowed to set to an all-embracing hy The above catalyst was evaluated for isomerization drogel in the form of a mass which is thereafter broken activity by passing a mixture of cyclohexene and hydrogen up or cut up into particles for wet processing. An al 35 (10 parts of hydrogen to 1 part of cyclohexene) over ternate method of preparing the hydrogel particles is to the catalyst at 600 F. and atmospheric pressure, em drop the hydrosol in the form of globules into a body ploying a liquid hourly space velocity of 1.4. A con of water-immiscible liquid so that spheroidal bead-like version of cyclohexene to methyl cyclopentene isomers particles of hydrogel are formed upon gelation of the in the amount of 68% by weight was achieved. hydrosol globules while maintained in the liquid. 40 The catalyst was also evaluated for cracking activity The hydrogel particles so obtained are thereafter aged employing as charge a Mid-Continent gas oil having a for a period of between about 1 and about 48 hours boiling range of 450 to 950 F., a temperature of 875 F., at a temperature within the approximate range of 120 a liquid hourly space velocity of 1.5 and a catalyst to oil to 212 F. in an aqueous solution of an alkali metal or ratio of 4.0. The catalyst afforded a conversion of ammonium salt of an acid having a dissociation constant 45 59.4% volume. The catalytic advantage of this catalyst of less than about 1.7x10. Typical of such salts are is evident from a comparison of results obtained under the ammonium and alkali metal salts of acetic, formic, identical cracking conditions with alumina-zirconia, and Sulfurous and other weak organic and inorganic acids. zirconium phosphate catalysts. A comparison of such The aging treatment serves to raise the pH of the hy results is set forth below: drogel and set the structure to the cogel. After aging, 50 the hydrogel particles are water-washed free of soluble Percent matter. A particularly preferred method for washing Catalyst Wolume the hydrogel is by percolation either with upward or Conversion downward flow of water. After washing, the hydrogel 11.25% wt. Al2O3-54.5% wt. ZrO2-34.25% wt. P.-- 59.4 particles are dried at a temperature generally from about 55 85% Al2O3-15% ZrO2--- 17.7 150 to about 350 F. for 2 to 24 hours or more or dried 15% Al2O3-85% ZrO2.-- 27.9 at Such temperature and then calcined at a temperature Zirconium phosphate--- 25.2 of from about 350 to about 1400° F. for about 2 to 12 hours or more. Usually, it is preferred to dry the hy It is evident from the above data that the catalyst de drogel particles in air or an atmosphere of superheated 60 steam at a slow rate since such manner of operation scribed herein afforded a marked advantage in catalytic has been found to result in less breakage of the gel par cracking over previously known alumina-zirconia, and ticles. Calcining is ordinarily carried out in air and zirconium phosphate catalysts. generally at a temperature between about 800 F. and Example 2 about 1400 F. although other inert atmospheres may, 65 A hydrosol was prepared by mixing 1700.8 grams of likewise, be used. If desired, the hydrogel particles may an aqueous solution containing 34.4 grams of Al-O as be treated with catalytic components prior to the drying Al2(SO4)3 and 165.6 grams of ZrO2 as Zr(SO4)2.4H2O or drying and calcination operations and the composite with 685.5 grams of a solution containing 205.5 grams so obtained may then be subjected to the above-described of sodium hexametaphosphate. The resulting sol set to drying and calcination. a firm hydrogel having a pH of about 1 in about 10 The oxygen-containing cogels of aluminum, zirconium minutes. The hydrogel was then split into four equal and phosphorus produced in accordance with the process parts and aged separately in solutions of ammonium of this invention may be used as treating, refining, puri acetate, ammonium sulfite, sodium acetate and ammoni fying agents or as a catalyst, catalyst support or com um formate for 16 hours at 200 F. After aging, the ponent of a catalyst for the conversion or organic com 75 gel samples were washed free of soluble salts, dried in 3,130,147 5 6 air at 250 F. and finally calcined in air at 900 F. for washing the hydrogel free of water-soluble matter, dry three hours. ing and calcining the dried gel. The gels so prepared contained aluminum and zir 3. A process for the manufacture of an acidic catalyst conium in an atomic ratio of 1:2 and an atomic ratio of which comprises reacting, in aqueous solution, a water total metals content to phosphorus of 1:1.5. soluble aluminum salt of a mineral acid, a water-soluble The above catalysts were evaluated for cracking ac 5 Zirconium salt of a mineral acid and an alkali metal tivity by passing n-decane over the catalyst at 900 F. phosphate to yield a hydrosol in which the atomic ratio and atmospheric pressure, employing a liquid hourly of aluminum to zirconium is between about 0.1 and space velocity of 1.0. The catalysts were also evaluated about 10 and the atomic ratio of combined aluminum for cracking activity by passing methyl cyclohexane over and zirconium to phosphorus is between about 0.1 and the catalyst at 900 F. and atmospheric pressure, em O about 10, permitting said hydrosol to set to a hydrogel, ploying a liquid hourly space velocity of 1.0. The results aging the resulting hydrogel for a period of between of these evaluations determined by the extent of con about 1 and about 48 hours at a temperature within the version to cracked products from a sample of products approximate range of 120 to 212 F. in an aqueous solu taken 3 minutes after introduction of the charge into 5 tion of a salt of an acid having a dissociation constant the reactor are shown below: of less than about 1.7x102, which salt is selected from the group consisting of those of ammonium and alkali metal salts, washing the hydrogel free of water-soluble 3M 3M 3 M 3M matter and drying the washed hydrogel. Aging Solution Ammo- Ammo- Sodium Ammo nium. nium Acetate nium 4. A process for the manufacture of an acidic catalyst Acetate Sulfite Formate which comprises reacting, in aqueous solution, aluminum sulfate, zirconium sulfate and sodium hexametaphosphate in - Decane Cracking-Con to yield a hydrosol in which the atomic ratio of aluminum version, percent Wit------28.7 37.5 3.6 38.9 Methylcyclohexane Crack to zirconium is between about 0.1 and about 10 and the ing-Conversion, Percent atonic ratio of combined aluminum and zirconium to Wit------8.7 19.7 21.7 28. 25 phosphorus is between about 0.1 and about 10, permit ting said hydrosol to set to a hydrogel, aging the result A composite prepared in the same manner as the above ing hydrogel for a period of between about 1 and about catalysts but with omission of the aging step afforded 48 hours at a temperature within the approximate range a material of low surface area and negligible catalytic 30 of 120 to 212 F. in an aqueous solution of a salt of an activity, establishing the essential and beneficial effect acid having a dissociation constant of less than about of the aging step in the process described herein. 1.7X 10, which salt is selected from the group consist It will be understood that the above description is ing of those of ammonium and alkali metal salts, wash merely illustrative of preferred embodiments of this in ing the hydrogel free of water-soluble matter, drying and vention of which many variations may be made within calcining the dried gel. the scope of the following claims by those skilled in the 5. An acidic catalyst consisting essentially of an oxy art without departing from the spirit thereof. gen-containing combination of aluminum, zirconium and We claim: phosphorus wherein the atomic ratio of aluminum to zir 1. A process for the manufacture of an acidic catalyst conium is between about 0.1 and about 10 and in which which comprises reacting, in aqueous solution, a water 40 the atomic ratio of the combined aluminum and zirconi Soluble salt of aluminum, a water-soluble salt of zir um content to phosphorus is between about 0.1 and conium and a water-soluble compound selected from about 10, prepared by reacting, in aqueous solution, a the group consisting of oxyacids of phosphorus and salts Water-soluble salt of aluminum, a water-soluble salt of of said acids in concentrations and quantities to yield Zirconium and a water-soluble compound selected from an acidic hydrosol in which the atomic ratio of aluminum the group consisting of oxyacids of phosphorus and salts to zirconium is between about 0.1 and about 10 and the of said acids yielding an acidic hydrosol, permitting said atomic ratio of combined aluminum and zirconium con hydrosol to set to a hydrogel, aging the hydrogel for tent to phosphorus is between about 0.1 and about 10, a period of between about 1 and about 48 hours at a permitting said hydrosol to set to a hydrogel, aging the temperature within the approximate range of 120–212 hydrogel for a period of between about 1 and about 48 50 F. in an aqueous solution of a salt of an acid having a hours at a temperature within the approximate range dissociation constant of less than about 1.7x102, which of 120 to 212 F. in an aqueous solution of a salt of an Salt is selected from the group consisting of those of am acid having a dissociation constant of less than about moniuin and alkali metal salts, washing the hydrogel 1.7x10, which salt is selected from the group con free of water-soluble matter and drying the washed hy sisting of those of ammonium and alkali metal salts, drogel. washing the hydrogel free of water-soluble matter and 6. An acidic catalyst consisting essentially of an oxy drying the washed hydrogel. gen-containing combination of aluminum, zirconium and 2. A process for the manufacture of an acidic catalyst phosphorus wherein the atomic ratio of aluminum to zir which comprises reacting, in aqueous solution, a water conium is about 1 to about 2 and in which the atomic ratio soluble aluminum salt, a water-soluble zirconium salt 60 of the combined aluminum and zirconium content to phos and a water-soluble compound selected from the group phorus is between about 1 to about 1.5, prepared by react consisting of oxyacids of phosphorus and salts of said ing, in aqueous solution, a water-soluble salt of aluminum, acids in concentrations and quantities to yield a hydrosol a Water-soluble salt of zirconium and a water-soluble com capable of setting to a hydrogel in not more than two pound Selected from the group consisting of oxyacids of hours and in which the atomic ratio of aluminum to zir 65 phosphorus and salts of said acids yielding an acidic hy conium is between about 0.1 and about 10 and the atomic drosol, permitting said hydrosol to set to a hydrogel, aging ratio of combined aluminum and zirconium content to the hydrogel for a period of between about 1 and about phosphorus is between about 0.1 and about 10, per 48 hours at a temperature within the approximate range mitting said hydrosol to set to a hydrogel, aging the of 120-212 F. in an aqueous solution of a salt of an hydrogel for a period of between about 1 and about 48 70 acid having a dissociation constant of less than about hours at a temperature within the approximate range of 1.7X 10°, which salt is selected from the group con 120 to 212 F. in an aqueous solution of a salt of an sisting of those of ammonium and alkali metal salts, wash acid having a dissociation constant of less than about ing the hydrogel free of water-soluble matter and drying 1.7x102, which salt is selected from the group con the washed hydrogel. sisting of those of ammonium and alkali metal salts, 75 7. A method for cracking a hydrocarbon charge which 3,130,147 7 8 comprises contacting the same under catalytic cracking about 48 hours at a temperature within the approximate conditions with a catalyst consisting essentially of an range of 120-212 F. in an aqueous solution of a salt of oxygen-containing combination of aluminum, zirconium an acid having a dissociation constant of less than about and phosphorus wherein the atomic ratio of aluminum to 1.7x102, which salt is selected from the group consist zirconium is between about 0.1 and about 10 and in 5 ing of those of ammonium and alkali metal salts, washing which the atomic ratio of the combined aluminum and the hydrogel free of water-soluble matter and drying the zirconium content to phosphorus is between about 0.1 washed hydrogel. and about 10, said catalyst resulting from reaction, in aqueous solution, of a water-soluble salt of aluminum, a References Cited in the file of this patent water-soluble salt of zirconium and a water-soluble com O UNITED STATES PATENTS pound selected from the group consisting of oxyacids of 2,349,243 Bates ------May 23, 1944 phosphorus and salts of said acids yielding an acidic hy 2,349,827 Mattox ------May 30, 1944 drosol, permitting said hydrosol to set to a hydrogel, 2,611,738 Webb et al. ------Sept. 23, 1952 aging the hydrogel for a period of between about 1 and UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 130, 147 April 21, 1964 Francis G. Dwyer et al. It is hereby certified that error appears in the above numbered pat ent requiring correction and that the said Letters Patent should read as corrected below. Column 2 line 12, for "V through VII" read -- W through VIII --; column 2 line 22, for "any" read -- an --. Signed and sealed this 8th day of December 1964.

CSEAL) Attest: ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents