3,140,251 United States Patent Office Patented July 7, 1964 1 2 The high activity catalysts contemplated herein are alu 3,140,251 minosilicate compositions which are strongly acidic in PROCESS FOR CRACKING HYDROCARBONS WITH A CRYSTALLINE ZEOLTE character as a result of treatment with a fluid medium Charles J. Plank, Woodbury, and Edward J. Rosinski, containing at least one metallic cation and a hydrogen ion Almonesson, N.J., assignors to Socony Mobi Oil Com or ion capable of conversion to a hydrogen ion. Inor pany, Eric a corporation of New York ganic and organic acids broadly represent the source of No Drawing. Filled Dec. 21, 1961, Ser. No. 161,241. hydrogen ions; metallic salts the source of metal cations; 19 Claims. (CI. 208-120) and ammonium compounds the source of cations capable of conversion to hydrogen ions. The product resulting This invention relates to the catalytic conversion of 0. from treatment with the fluid medium is an activated hydrocarbons and more particularly to the catalytic crack crystalline and/or amorphous aluminosilicate in which ing of high boiling hydrocarbon oils into hydrocarbons of the nuclear structure thereof has been modified solely to lower boiling range in the presence of a new and im the extent of having protons and metallic cations chem proved catalyst. isorbed or ionically bonded thereto. The activated alu A wide variety of materials have heretofore been pro 5 minosilicate contains at least 0.5 equivalent and prefer posed as catalysts for the cracking of high boiling hydro ably contains more than 0.9 equivalent of ions of positive carbons, such as gas oils, topped crudes, reduced crudes valence per gram atom of aluminum. Except for alkali or similar materials, into lower boiling hydrocarbons boil metal cations which may be present as impurities to the ing in the motor fuel range. The cracking catalysts most extent of less than 0.25 equivalent per gram atom of alu Widely used are solid materials which behave in an acidic 20 minum, no other cations of metals of Group A of the manner. Although catalysts of this type possess one or Periodic Table are associated with the aluminosilicate. more desired characteristics, a great many of the acidic When subsequently dried, washed and further used as an catalysts have undesirable characteristics, such as lack of intermediate, this product has been found to be extremely thermal stability, availability, or mechanical strength, etc., active as a catalyst for hydrocarbon conversion. whereby a wide range of suitable properties cannot be 25 In preparing the catalyst composition, the aluminosili maintained. Synthetic silica-alumina composites, the cate can be contacted with a non-aqueous or aqueous fluid most popular catalysts known to have been proposed here medium comprising a gas, polar solvent or water solution tofore, provide limited yields of gasoline for a given yield containing the desired hydrogen ion or ammonium ion of coke and further suffer the disadvantage of rapidly de capable of conversion to a hydrogen ion and at least one teriorating and becoming inactive in the presence of steam, 30 metallic salt soluble in the fluid medium. Alternatively, particularly at temperatures above 1000 F. Other cata the aluminosilicate can be first contacted with a fluid me lysts less widely used are materials of an argillaceous na dium containing a hydrogen ion or ammonium ion capa ture, e.g., bentonite and montmorillonite, which have been ble of conversion to a hydrogen ion and then with a fluid treated with acid to bring out their latent cracking charac medium containing at least one metallic salt. Similarly, teristics. Catalysts of this general type are relatively in 35 the aluminosilicate can be first contacted with a fluid me expensive, but are only moderately active and exhibit a dium containing at least one metallic salt and then with decline in activity over periods of many conversion and a fluid medium containing a hydrogen ion or an ion ca regeneration cycles. Some synthetic materials, such as pable of conversion to a hydrogen ion or a mixture of silica-magnesia complexes, are more active than conven both. Water is the preferred medium for reasons of tional silica-alumina catalysts and undergo normal aging, 40 economy and ease of preparation in large scale operations but have limited utility because of their poor product dis involving continuous or batchwise treatment. Similarly, tribution as evidenced, for example, by low octane num for this reason, organic solvents are less preferred but can ber of the gasoline. be employed providing the solvent permits ionization of Other disadvantages of heretofore proposed cracking the acid, ammonium compound and metallic salt. Typical catalysts include poor activity, chemical stability and 45 solvents include cyclic and acyclic ethers such as dioxane, product distribution in obtaining desired yields of useful tetrahydrofuran, ethyl ether, diethyl ether, diisopropyl products. ether, and the like; ketones such as acetone and methyl The present invention is based on the discovery that ethyl ketone; esters such as ethyl acetate, propyl acetate; highly active hydrocarbon cracking catalysts can be ob alcohols such as ethanol, propanol, butanol, etc.; and mis tained by admixing an inorganic oxide gel with an alu 50 cellaneous solvents such as dimethylformamide, and the minosilicate containing a total of 0.5 to 1.0 equivalent like. of ion of positive valence per gram atom of aluminum The hydrogen ion, metal cation, or ammonium ion may wherein from 0.01 to 0.99 equivalent of said ions are hy be present in the fluid medium in an amount varying with drogen ions and from 0.99 to 0.01 equivalent of said ions in wide limits dependent upon the pH value of the fluid are cations of metals selected from Group IB through 55 medium. Where the aluminosilicate material has a molar Group VIII of the Periodic Table. The catalyst of this ratio of silica to alumina greater than about 5.0, the fluid invention possesses a wide spectrum in magnitude of cata medium may contain a hydrogen ion, metal cation, am lytic activity; can be used in relatively small concentra monium ion, or a mixture thereof, equivalent to a pH tions; and permit certain hydrocarbon conversion process value ranging from less than 1.0 up to a pH value of es to be carried out under practicable and controllable 60 about 12.0. Within these limits, pH values for fluid media rates at lower temperatures than those previously em containing a metallic cation and/or an ammonium ion ployed. In the catalytic cracking of hydrocarbon oils into range from 4.0 to 10.0, and are preferably between a pH hydrocarbon products of lower molecular weight, the re value of 4.5 to 8.5. For fluid media containing a hydro action rates per unit volume of catalyst that are obtain gen ion alone or with a metallic cation, the pH values able by the catalyst of the invention vary up to many 65 range from less than 1.0 up to about 7.0, and are prefer thousand times the rates achieved with the best siliceous ably within the range of less than 1.0 up to 4.5. Where catalysts heretofore proposed. The present invention fur the molar ratio of the aluminosilicate is greater than thermore provides a means whereby aluminosilicate mate about 2.2 and less than about 5.0, the pH value for the rials having no internally available surfaces and only ex fluid media containing a hydrogen ion or a metal cation ternal particle surface areas can be readily converted to 70 ranges from 3.8 to 8.5. Where ammonium ions are em useful catalysts which thus broadens considerably their ployed, either alone or in combination with metallic realm of practical utility. cations, the pH value ranges from 4.5 to 9.5 and is 3,140,251 es preferably within the limit of 4.5 to 8.5. When the 2-bromopropionic acid, 3-bromopropionic acid, lactic aluminosilicate material has a molar ratio of silica to acid, n-butyric acid, isobutyric acid, crotonic acid, n alumina less than about 3.0, the preferred medium is a valeric acid, isovaleric acid, n-caproic acid, oenanthic fluid medium containing an ammonium ion instead of a acid, pelargonic acid, capric acid, undecyclic acid, lauric hydrogen ion. acid, myristic acid, palmitic acid, Stearic acid, oxalic acid, In carrying out the treatment with the fluid medium, malonic acid, succinic acid, glutaric acid, adipic acid, the procedure employed comprises contacting the alumino pimelic acid, suberic acid, azelaic acid, sebacic acid, silicate with the desired fluid medium or media until such alkylsuccinic acid, alkenylsuccinic acid, maleic aid, fu time as metallic cations originally present in the alumino maric acid, itaconic acid, citraconic acid, mesaconic acid, silicate are virtually exhausted. Cations of metals of 0. glutonic acid, muconic acid, ethylidene malonic acid, Group IA of the Periodic Table, if present in the modified isoprypylidene malonic acid, ally malonic acid. aluminosilicate, tend to suppress or limit catalytic proper Representative aromatic and cycloaliphatic monocar ties, the activity of which, as a general rule, decreases with boxylic, dicarboxylic and polycarboxylic acids include increasing content of these metallic cations. Effective 1,2-cyclohexane-dicarboxylic acid, 1,4-cyclohexanedicar treatment with the fluid medium to obtain a modified 15 boxylic acid, 2-carboxy-2-methylcyclohexaneacetic acid, aluminosilicate having high catalytic activity will vary, of phthalic acid, isophthalic acid, terephthalic acid, 1,8- course, with the duration of the treatment and tempera naphthalenedicarboxylic acid, 12-naphthalenedicarboxyl ture at which it is carried out. Elevated temperatures ic acid, tetrahydrophthalic acid, 3-carboxy-cinnamic acid, tend to hasten the speed of treatment whereas the dura hydrocinnamic acid, pyrogallic acid, benzoic acid, ortho, tion thereof varies inversely with the concentration of the 20 meta and para-methyl, hydroxyl, chloro, bromo and ions in the fluid medium. In general, the temperatures nitro-substituted benzoic acids, phenylacetic acid, man employed range from below ambient room temperature of delic acid, benzylic acid, hippuric acid, benzenesulfonic 24 C. up to temperatures below the decomposition tem acid, toluenesulfonic acid, methanesulfonic acid and the perature of the aluminosilicate. Following the fluid treat like. ment, the treated aluminosilicate is washed with water, 25 Other sources of hydrogen ions include carboxy poly preferably distilled water, until the effluent wash water has esters prepared by the reaction of an excess polycarboxylic a pH value of wash water, i.e., between about 5 and 8. acid or an anhydride thereof and a polyhydric alcohol The aluminosilicate material is thereafter analyzed for to provide pendant carboxyl groups. metallic ion content by methods well known in the art. Still other materials capable of providing hydrogen ions Analysis also involves analyzing the effluent wash for 30 are ion exchange resins having exchangeable hydrogen anions obtained in the wash as a result of the treatment, ions attached to base resins comprising cross-linked res as well as determination of and correction for anions that inous polymers of monovinyl aromatic monomers and pass into the effluent wash from soluble substances or de polyvinyl compounds. These resins are well known ma composition products of insoluble substances which are terials which are generally prepared by copolymerizing otherwise present in the aluminosilicate as impurities. 35 in the presence of a polymerization catalyst one or more The actual procedure employed for carrying out the monovinyl aromatic compounds, such as styrene, vinyl fluid treatment of the aluminosilicate may be accom toluene, vinyl Xylene, with one or more divinyl aromatic plished in a batchwise or continuous method under atmos compounds such as divinyl benzene, divinyl toluene, di pheric, subatmospheric or superatmospheric pressure. A vinyl Xylene, divinyl naphthalene and divinyl acetylene. solution of the ions of positive valence in the form of a 40 Following copolymerization, the resins are further treated molten material, vapor, aqueous or nonaqueous solution, with suitable acids to provide the hydrogen form of the may be passed slowly through a fixed bed of the alumino reS, silicate. If desired, hydrothermal treatment or a corre Still another class of compounds which can be em spondingly non-aqueous treatment with polar solvents may ployed are ammonium compounds which decompose to be effected by introducing the aluminosilicate and fluid 45 provide hydrogen ions when an aluminosilicate treated medium into a closed vessel maintained under autogenous with a solution of said ammonium compound is sub pressure. Similarly, treatments involving fusion or vapor jected to temperatures below the decomposition tempera phase contact may be employed providing the melting ture of the aluminosilicate. point or vaporization temperature of the acid or ammo Representative ammonium compounds which can be nium compound is below the decomposition temperature 50 employed include ammonium chloride, ammonium bro of the aluminosilicate. mide, ammonium iodide, ammonium carbonate, am A wide variety of acidic compounds can be employed monium bicarbonate, ammonium sulfate, ammonium hy with facility as a source of hydrogen ions and include droxide, ammonium sulfide, ammonium thiocyanate, am both inorganic and organic acids. monium dithiocarbamate, ammonium peroxysulfate, ann Representative inorganic acids which can be employed 55 monium acetate, ammonium tungstate, ammonium molyb include acids such as hydrochloric acid, hypochlorous date, ammonium benzoate, ammonium borate, ammonium acid, chloroplatinic acid, sulfuric acid, sulfurous acid, hy carbamate, ammonium sesquicarbonate, ammonium chlo drosulfuric acid, peroxydisulfonic acid (H2S2O3), peroxy roplumbate, ammonium citrate, ammonium dithionate, monosulfuric acid (HSO5), dithionic acid (H2SOs), ammonium fluoride, ammonium gallate, ammonium ni sulfamic acid (HNHSH), amidodisulfonic acid 60 trate, ammonium nitrite, ammonium formate, ammonium (NH(SOH)) propionate, ammonium butyrate, ammonium valerate, ammonium lactate, ammonium malonate, ammonium chlorosulfuric acid, thiocyanic acid, hyposulfurous acid oxalate, ammonium palmitate, ammonium tartarate and (H2SO4), pyrosulfuric acid (H2S2O), thiosulfuric acid the like. Still other ammonium compounds which can (HS2O3), nitrosulfonic acid (HSONO), hydroxyl 65 be employed include tetraalkyl and tetraaryl ammonium amine disulfonic acid ((HSO)NOH), nitric acid, ni salts such as tetramethylammonium hydroxide, trimethyl trous acid, hyponitrous acid, carbonic acid and the like. ammonium hydroxide. Other compounds which can be Typical organic acids which find utility in the practice employed are nitrogen bases such as the salts of guani of the invention include the monocarboxylic, dicarboxylic dine, pyridine, quinoline, etc. and polycarboxylic acids which can be aliphatic, aromatic 70 A wide variety of metallic compounds can be employed or cycloaliphatic in nature. with facility as a source of metallic cations and include Representative aliphatic monocarboxylic, dicarboxylic both inorganic and organic salts of the metals of Group and polycarboxylic acids include the saturated and un IB through Group VIII of the Periodic Table. saturated, substituted and unsubstituted acids such as Representative of the salts which can be employed in formic acid, acetic acid, bromoacetic acid, propionic acid, 75 clude chlorides, bromides, iodides, carbonates, bicarbon 3,140,251 5 6 ates, sulfates, sulfides, thiocyanates, dithiocarbamates, per sulfate, neodymium chloride, neodymium oxide, neody oxysulfates, acetates, benzoates, citrates, fluorides, ni mium sulfide, neodymium sulfate, praseodymium chlo trates, nitrites, formates, propionates, butyrates, valerates, ride, praseodymium bromide, praseodymium sulfate, lactates, malonates, oxalates, palmitates, hydroxides, tar praseodymium sulfide, etc. tarates and the like. The only limitations on the par The aluminosilicates treated in accordance with the ticular metal salt or salts employed are that it be soluble invention include a wide variety of aluminosilicates, both in the fluid medium in which it is used and compatible natural and synthetic, which have an amorphous or crys with the hydrogen ion source, especially if both the metal talline structure. These aluminosilicates can be described lic salt and the hydrogen ion source are in the same fluid as a three dimensional framework of SiO4 and AlO4 tetra medium. The preferred salts are the chlorides, nitrates, O hedra in which the tetrahedra are cross-linked by the acetates and sulfates. sharing of oxygen atoms whereby the ratio of the total Of the wide variety of metallic salts which can be em aluminum and silicon atoms to oxygen atoms is 1:2. In ployed, the most preferred are salts of trivalent metals, their hydrated form the aluminosilicates may be repre then of divalent metals and lastly, of monovalent metals. sented by the formula: Of the divalent metals, the preferred ones are of Group 5 IIA of the Periodic Table. The particularly preferred salts are those of the rare earth metals including cerium, lanthanum, praseodymium, neodymium, illinium, Sama rium, europium, gadolinium, terbium, dysprosium, hol wherein M is a cation which balances the electrovalence mium, erbium, thulium, ytterbium and lutecium. 20 of the tetrahedra, in represents the valence of the cation, The rare earth salts employed can either be the salt w the moles of SiO, and y the moles of H2O. The cation of a single metal or preferably of mixtures of metals such may be any or more of a number of metal ions depending as a rare earth chloride or didymium chlorides. As here on whether the aluminosilicate is synthesized or occurs inafter referred to, a rare earth chloride solution is a naturally. Typical cations include sodium, linthium, po mixture of rare earth chlorides consisting essentially of 25 tassium, silver, magnesium, calcium, zinc, barium, iron the chlorides of lanthanum, cerium, neodymium and and manganese. Although the proportions of inorganic praseodymium with minor amounts of samarium, gado oxides in the silicates and their spatial arrangement may linium and yttrium. The rare earth chloride solution is vary, effecting distinct properties in the aluminosilicates, commercially available and it contains the chlorides of the two main characteristics of these materials is the a rare earth mixture having the relative composition cer 30 presence in their molecular structure of at least 0.5 equiv ium (as CeO2) 48% by weight, lanthanum (as LaC3) alent of an ion of positive valence per gram atom of 24% by weight, praseodymium (as PrsO11) 5% by weight, aluminum, and an ability to undergo dehydration without neodymium (as Nd2O3) 17% by weight, Samarium (as substantially affecting the SiO4 and AlO4 framework. In SmO) 3% by weight, gadolinium (as Gd2O3) 2% by this respect, these characteristics are essential for obtain weight, yttrium (as YO) 0.2% by weight and other rare 35 ing catalyst compositions of high activity in accordance earth oxides 0.8% by weight. Didymium chloride is also with the invention. a mixture of rare earth chlorides, but having a low cerium Representative materials include synthesized crystal content. It consists of the following rare earths deter line aluminosilicates, designated Zeolite X, which can be mined as oxides: anthanum, 45-46% by weight; cerium represented in terms of mole ratios of oxides as follows: 1-2% by weight; praseodymium, 9-10% by weight, 40 neodymium, 32-33% by weight; samarium, 5-6% by 1.0.0.2M 2 O:AO3:2.5-0.5SiO2: HO (II) weight, gadolinium 3-4% by weight, yttrium, 0.4% by weight, other rare earth earths 1-2% by weight. It is to be understood that other mixtures of rare earths are wherein M is a cation having a valence of not more than equally applicable in the instant invention. three, in represents the valence of M, and y is a value Representative metal salts which can be employed, 45 up to eight depending on the identity of M and degree aside from the mixtures mentioned above, include silver of hydration of the crystal. The sodium form may be chloride, silver sulfate, silver nitrate, silver acetate, silver represented in terms of mole ratios of oxides as follows: arsinate, silver bromide, silver citrate, silver carbonate, sil 0.9 NaO:Al2O3:2.5 SiO2:6.1 HO (III) ver oxide, silver tartrate, calcium acetate, calcium arsen ate, calcium benzoate, calcium bromide, calcium carbon 50 Another synthesized crystalline aluminosilicate, desig ate, calcium chloride, calcium citrate, beryllium bromide, nated Zeolite A, can be represented in mole ratios of beryllium carbonate, beryllium hydroxide, beryllium sul oxide as: fate, barium acetate, barium bromide, barium carbonate, 1.0.0.2MO:Al2O3:185-0.5SiO2: H2O barium citrate, barium malonate, barium nitrite, barium 2. (IV) oxide, barium sulfide, magnesium chloride, magnesium 55 bromide, magnesium sulfate, magnesium sulfide, magnes wherein M represents a metal, n is the valence of M, ium acetate, magnesium formate, magnesium stearate, and y is any value up to about 6. As prepared, Zeolite magnesium tartrate, zinc sulfate, zinc nitrate, zinc ace A contains primarily sodium cations and is designated so tate, zinc chloride, zinc bromide, aluminum chloride, 60 dium Zeolite A. aluminum bromide, aluminum acetate, aluminum citrate, Other suitable synthesized crystalline aluminosilicates aluminum nitrate, aluminum oxide, aluminum phosphate, are those designated Zeolite Y, L and D. aluminum sulfate, titanium bromide, titanium chloride, The formula for Zeolite Y expressed in oxide mole titanium nitrate, titanium sulfate, zirconium chloride, zir ratios is: conium nitrate, zirconium sulfate, chromic acetate, chro 0.9–0.2NaO: AlO:wSiO:yHO (V) mic chloride, chromic nitrate, chromic sulfate, ferric 65 wherein w is a value ranging from 3 to 6 and y may be chloride, ferric bromide, ferric acetate, ferrous chloride, any value up to about 9. ferrous arsenate, ferrous lactate, ferrous sulfate, nickel The composition of Zeolite L in oxide mole ratios may chloride, nickel bromide, cerous acetate, cerous bromide, be represented as: cerous carbonate, cerous chloride, cerous iodide, cerous 70 sulfate, cerous sulfide, lanthanum chloride, lanthanum 1.00.M 2 O: Al2O3:6.4-0.5SiO3:yEO (VI) bromide, lanthanum nitrate, lanthanum sulfate, lanth anum sulfide, yttrium bromate, yttrium bromide, yttrium chloride, yttrium nitrate, yttrium sulfate, Samarium ace wherein M designates a metal, in represents the valence of tate, samarium chloride, Samarium bromide, Samarium 5 M, and y is any value from 0 to 7. 3,140,251 7 8 The formula for Zeolite D, in terms of oxide mole about 3.5 to about 5.5. As synthesized, Zeolite ZK-4 ratios, may be represented as: contains primarily sodium cations and can be represented by unit cell formula: wherein x is a value of 0 to 1, w is from 4.5 to about 4.9, and y, in the fully hydrated form, is about 7. Other synthetic crystalline aluminosilicates which can The major lines of the X-ray diffraction pattern of be used include those designated as Zeolite R, S, T, Z, ZK-4 are set forth in the table below: E, F, Q and B. TABLE

The formula for Zeolite R in terms of oxide mole 0 ratios may be written as follows: d Walue of Reflection 100 IIIo 0.9-0.2NaO:Al2O3:wSiO:yHO (VIII) in A. wherein w is from 2.45 to 3.65, and y, in the hydrated form, is about 7. 2.00 100 The formula for Zeolite S in terms of oxide mole ratios 5 9, 2 29 8.578 73 may be written as: 7.035 52 6.358 5 0.9-0.2Na2O: AlO3:wSiO2:yHO (IX) 5.426 23 4.262 1. 4.062 49 wherein w is from 4.6 to 5.9 and y, in the hydrated form, 3.662 65 is about 6 to 7. 20 3.391 30 The formula for Zeolite T in terms of oxide mole ratios 3.254 41 2.950 54 may be written as: 2.725 0 2. 663 7 1.1 --0.4xNaO ( 1. -x) KO: AlO3 : 2.593 15 2.48 2 6.9-0.5SiO2:yH2O (X) 25 2.435 2.34 2 wherein x is any value from about 0.1 to about 0.8 and 2.225 2 2.59 4 y is any value from about 0 to about 8. 2.2. 5 The formula for Zeolite Z in terms of oxide mole ratios 2.085 2 2.061 2 may be written as: 2.033 5 30 1.90 2 (XI) 1,880 2 828 1. wherein y is any value not exceeding 3. 1.83 1. The formula for Zeolite E in terms of oxide mole i.759 1. .735 1. ratios may be written as: 1.720 5 35 1703 (XII) 1,669 2 1.60 1.58 2 1.559 wherein M is a cation, n is the valence of the cation, and y is a value of 0 to 4. The formula for Zeolite F in terms of oxide mole 40 ZK-4 can be prepared by preparing an aqueous solu ratios may be written as follows: tion of oxides containing as Na2O, Al2O3, SiO2, H2O and tetramethylammonium ion having a composition, in (XIII) terms of oxide mole ratios, which falls within the foll lowing ranges: 45 wherein M is a cation, n is the valence of the cation, and SiO2/Al2O3------2.5 to 11 y is any value from 0 to about 3. Na2O The formula for Zeolite Z, expressed in terms of oxide Nao--(CH)No ------0.05 to 0.25 mole ratios, may be written as: HO ad 50 Nao--(CH)No ------25 to 50 0.95-0.05M 2 O:Al2O3:2.2-0.05SiO2: H2O (XIV) n Na2OHCHS)N).0...... SiO2 1 to 2 wherein M is a cation, n is the valence of the cation, maintaining the mixture at a temperature of about 100 and y is any value from 0 to 5. 55 C. to 120° C. until the crystals are formed, and sepa The formula for Zeolite B may be written in terms rating the crystals from the mother liquor. The crystal of oxide mole ratios as: material is thereafter washed until the wash effluent has a pH essentially that of wash water and Subsequently 1.0+0.2M O:Al2O3:3.5-1.5SiO2:yHO (XV) dried. 60 ZK-5 is representative of another crystalline alumino wherein M represents a cation, n is the valence of the silicate which is prepared in the same manner as Zeolite cation and y has an average value of 5.1 but may range ZK-4 except that N,N'-dimethyltriethylenediammonium from 0 to 6. hydroxide is used in place of tetramethylammonium hy Other synthesized crystalline aluminosilicates include droxide. ZK-5 may be prepared from an aqueous sodium those designated as ZK-4 and ZK-5. - 65 aluminosilicate mixture having the following composi ZK-4 can be represented in terms of mole ratios of tion expressed in terms of oxide mole ratios as: oxides as: SiO2/Al2O3------2.5 to 11 0.1 to 0.3R:9.7 to 1.0M 2 O:Al2O3:2.5 to 4.0SiO2:yH2O (XVI) Na2O - 70 NaOHCII)N(CHOII------0.05 to 0.25 - A - 25 to 50 wherein R is a member selected from the group consist Nago--((CH3)N(CH3)OH------) O ing of methylammonium oxide, hydrogen oxide and mix tures thereof with one another, M is a metal cation, in Na2O+(CH2)N(CH3)2OH. 1 to 2 is the valence of the cation, and y is any value from 5 SiO2 3,140,251 O The N,N'-dimethyltriethylenediammonium hydroxide varying degrees of crystallinity are crystallized out of used in preparing ZK-5 can be prepared by methylating solution. The solid material is separated from the alka 1,4-diazobicyclo-(2.2.2)-octane with methyl iodide or line material and thereafter washed and dried. The treat dimethyl sulfate, followed by conversion to the hydroxide ment can be effected by reacting mixtures falling within by treatment with silver oxide or barium hydroxide. The 5 the following weight ratios: reaction may be illustrated as: Na2O/clay (dry basis) ------1.0-6.6 to 1 N SiO2/clay (dry basis) ------0.01-3.7 to 1. cí1. GoH, H2O/Na2O (mole ratio) ------35-180 to 1. 2CHI. - (XVIII) ch, H, B, * '' O As previously noted, the active aluminosilicates used for purposes of the invention are characterized as having at least 0.5 equivalent of an ion of positive valence per gram atom of aluminum, as determined by base exchang ing with other cations by recognized techniques. Alu is 5 minosilicate starting materials not possessing this charac ff d RoH, - 2AgOH - (XIX) teristic, however, may be employed providing they are either pretreated or acquire this characteristic as a result of treatment with a fluid medium. As an example of pretreatment, argillaceous materials contacted with caustic 20 or caustic-silica mixtures, as above described, results in the formation of amorphous and/or crystalline alumino silicates having at least 0.5 equivalent, usually about 1.0 equivalent, or cation per gram atom of aluminum. Simi (XX) larly, treatment of an amorphous silica-alumina com 25 posite with a fluid medium containing an ammonium ion capable of conversion to a hydrogen ion, for example, tetramethylammonium hydroxide, also results in an in crease in the cation concentration per gram atom of alu In using the N,N-dimethyltriethylene-diammonium hy minum to values above 0.5 equivalent. droxide compound in the preparation of ZK-5, the hy 30 The preparation of aluminosilicate compositions in ac droxide may be employed per se, or further treated with cordance with the invention provides a means for obtain a source of silica, such as silica gel, and thereafter re ing exceptionally good catalysts. While the alumino acted with aqueous sodium aluminate in a reaction mix silicate component may contain varying amounts of silicon ture whose chemical composition corresponds to the and aluminum, it has been found that extremely good re above-noted oxide mole ratios. Upon heating at tem 35 sults can be obtained through use of crystalline alumino peratures of about 200 to 600° C., the methyl ammonium silicates having atomic ratios of silicon to aluminum ion is converted to hydrogen ion. greater than 1.1, preferably greater than 1.67, and more Among the naturally occurring crystalline alumino preferably above 2.7. Preferred aluminosilicates thus silicates which can be employed for purposes of the in include natural materials such as gmelinite, chabazite and vention are included levynite, erionite, faujasite, analcite, 40 mordenite, and synthetic crystalline aluminosilicates such paulingite, noselite, ferriorite, heulandite, scolecite, stil as Zeolites X, Y, T, ZK-4, and ZK-5. bite, clinoptilolite, harmotome, phillipsite, brewsterite, The active aluminosilicate component prepared in the flakite, datolite, and aluminosilicates represented as fol foregoing manner is combined, dispersed or otherwise in lows: timately admixed with an inorganic oxide gel which serves 45 as a base, binder, matrix or promoter, in such propor Chabazite, NaO. AlO4SiO2.6H2O tions that the resulting product contains from about 2 to Gmelinite, NaO. AlO3.4SiO2.6H2O 95% by weight and preferably about 5 to 50% by weight Cancrinite, 3 (Na2O.AlO3.2SiO2).Na2CO3 of the aluminosilicate in the final composite. The re Leucite, KO.Al2O3.4SiO2 sulting aluminosilicate-inorganic oxide gel composition is Lazurite, (Na,Ca)sAlsSi6O24.2(S,Cl,So4) 50 then preferably precalcined in an inert atmosphere near Scapolite, Na4AlSigO24Cl the temperature contemplated for conversion but may be Ptilolite, NaO. Al2O3. 10SiO2.4H2O calcined initially during use in the conversion process. Mesolite, NaO. AlO3.3SiO2.2-3H2O Generally, the catalyst composition is dried between 150 Mordenite, NaO.A.O.10SiO2.6.6H2O F. and 600 F., and thereafter calcined in air or an inert Nepheline, NaO.Al2O3.2SiO2 55 atmosphere of nitrogen, hydrogen, helium, flue gas or Natrolite, NaO. AlO3.3SiO2.2H2O other inert gas at temperatures ranging from about 500 Sodalite, 3 (NaO. Al2O3.2SiO2).2NaCl F. to 1500 F. for periods of time ranging from 1 to 48 Other aluminosilicates which can be used are caustic hours or more. It is to be understood that the active treated clays. aluminosilicate component can be calcined prior to in Of the clay materials, montmorillonite and kaolin 60 corporation with the inorganic oxide gel. families are representative types which include the sub The aluminosilicate-inorganic oxide gel compositions bentonites, such as bentonite, and the kaolins commonly can be prepared by several methods wherein the alumino identified as Dixie, McNamee, Georgia and Florida clays silicate having a particle size less than 40 microns, prefer in which the main mineral constituent is halloysite, kaoli ably within the range of 2 to 7 microns, is intimately ad nite, dickite, nacrite, or anauxite. Such clays may be 65 mixed with the inorganic oxide gel while the latter is in used in the raw state as originally mined or initially sub a hydrous state such as in the form of a hydrosol, hydro jected to calcination, acid treatment or chemical modifi gel, wet gelatinous precipitate, or a mixture thereof. cation. In order to render the clays suitable for use, Thus, finely divided active aluminosilicate can be mixed however, the clay material is treated with sodium hydrox directly with a siliceous gel formed by hydrolyzing a ide or potassium hydroxide, preferably in admixture with 70 basic solution of alkali metal silicate with an acid such as a source of silica, such as sand, silica gel or sodium sili hydrochloric, sulfuric, etc. The mixing of the two com cate, and calcined at temperatures ranging from 230 to ponents can be accomplished in any desired manner, such 1600 F. Following calcination, the fused material is as in a ball mill or other types of kneading mills. The crushed, dispersed in water and digested in the resulting aluminosilicate also may be dispersed in a hydrosol ob alkaline solution. During the digestion, materials with 75 tained by reacting an alkali metal silicate with an acid or 3,140,251 2 an alkaline coagulent. The hydrosol is then permitted resentative hydrocarbon charge. In the examples herein to set in mass to a hydrogel which is thereafter dried and after set forth, the reference catalyst employed consisted broken into pieces of desired shape, or dispersed through of a conventional silica-alumina "bead' type cracking a nozzle into a bath of oil or other water-immiscible sus catalyst. The silica-alumina catalyst contained about 10 pending medium to obtain spheroidally shaped "bead' weight percent Al2O3 and the remainder SiO2. In some particles of catalyst such as described in U.S. Patent No. instances it also contained a trace amount of Cr2O3, i.e., 2,384,946. The aluminosilicate-siliceous gel thus ob about 0.15 weight percent. tained is washed free of soluble salts and thereafter dried The cracking activity of the catalyst is further illus and/or calcined as desired. The total alkali metal con trated by its ability to catalyze the conversion of a Mid tent of the resulting composite, including alkali metals O Continent gas oil having a boiling range of 450-950 F. which may be present in the aluminosilicate as an im to gasoline having an end point of 410 F. Vapors of purity, is less than about 4% and preferably less than the gas oil are passed through the catalyst at tempera about 3% by weight based on the total composition. tures of 875 F. or 900 F. Substantially at atmospheric In a like manner, the active aluminosilicate may be pressure at a feed rate of 1.5 to 16.0 volumes of liquid incorporated with an aluminiferous oxide. Such gels are 5 oil per volume of catalyst per hour for ten minutes. well known in the art and may be prepared, for example, The method of measuring the instant catalyst was to by adding ammonium hydroxide, ammonium carbonate, compare the various product yields obtained with such etc., to a salt of nitrate, etc., in an amount sufficient to catalyst with yields of the same products given by con form aluminum hydroxide which upon drying is con ventional silica-alumina catalyst at the same conversion verted to alumina. The aluminosilicate may be incor 20 level. The differences (A values) shown hereinafter rep porated with the aluminiferous oxide while the latter is in resent the yields given by the present catalyst minus yields the form of hydrosol, hydrogel or wet gelatinous precipi given by the conventional catalyst. In these tests the tate. catalyst composition of the invention was precalcined at The inorganic oxide gel may also consist of a plural about 1000 F. prior to their evaluation as a cracking gel comprising a predominant amount of silica with one 25 catalyst. or more metals or oxides thereof selected from Groups Cracking operations carried out with the catalysts pre IB, II, III, IV, V, VI, VII and VIII of the Periodic Table. pared in accordance with the invention may be effected at Particular preference is given to plural gels of silica with temperatures ranging from about 700° F. to 1200° F. metal oxides of Groups A, IIIB and IVA of the Periodic under reduced atmospheric or superatmospheric pres Table wherein the metal oxide is magnesia, alumina, 30 Sure. The catalyst can be utilized in the form of sphe zirconia, beryllia or thoria. The preparation of plural roidal particles or beads disposed in a stationary bed, or gels is well known and generally involves either separate in the fluid procedures wherein the catalyst is disposed precipitation or coprecipitation techniques in which a suit in a reaction Zone to which catalyst is continuously added able salt of the metal oxide is added to an alkali metal and from which catalyst is continuously removed. A silicate and an acid or base, as required, is added to pre 35 particularly effective cracking process can be achieved cipitate the corresponding oxide. The silica content of When the catalyst is used to obtain the inherent advan the siliceous gel matrix contemplated herein is generally tages realized in the moving bed technique referred to within the range of 55 to 100 weight percent with the as the Thermofor catalytic cracking process. metal oxide content ranging from 0 to 45 percent. Minor amounts of promoters or other materials which may be 40 Example 1 present in the composition include cerium, chromium, A Synthetic crystalline aluminosilicate identified as cobalt, tungsten, uranium, platinum, lead, zinc, calcium, Zeolite 13X was subjected to 12 two-hour treatments at magnesium, lithium, nickel and their compounds as well 180° F. with an aqueous solution containing 5% by as silica, alumina, or other siliceous oxide combination as Weight mixture of rare earth chlorides and 2% by weight fines. of ammonium chloride. The aluminosilicate was then As a further embodiment of the invention, alumino Washed with water until there were no chloride ions in silicate catalysts having exceptionally high orders of ac the effluent, dried, and then treated for 20 hours at 1225 tivity can be prepared by incorporating a metal alumino F. with 100% atmospheric steam to yield a catalyst hav silicate in an inorganic oxide gel matrix, and thereafter ing a sodium content of 0.31 weight percent. contacting the aluminosilicate with the above-mentioned 50 The following table shows the cracking data obtained fluid medium containing a hydrogen ion or ammonium when the catalyst was evaluated for cracking gas oil at ion capable of conversion to a hydrogen ion. The treat 900 F. ment is carried out for a sufficient period of time under TABLE 1. conditions previously described for obtaining active Cracking data: aluminosilicates. It has been found that catalysts pre 55 Conversion, Vol. percent ------60.9 pared in this manner are extremely active for hydro LHSV ------16 carbon conversion, and particularly in the cracking of 10 R.V.P. gaso., Vol. percent ------54.6 hydrocarbon oils wherein exceptionally high ratios of Excess C4's, Vol. percent ------9.5 gasoline to low grade products, such as coke and gas, are C5 gasoline, Vol. percent ------51.7 obtained. 60 Total C4's, Vol. percent ------12.5 It has been further found in accordance with the in Dry gas, wt. percent ------5.6 vention that catalysts of improved activity and having Coke, wt. percent ------2.3 other beneficial properties in the conversion of hydro H2 Wt. percent ------0.02 carbons are obtained by subjecting the treated alumino A advantage: silicate to a mild steam treatment carried out at elevated 65 10 R.V.P., vol. percent ------9.3 temperatures of 800 F. to 1500 F., preferably at tem Excess Ca's, Vol. percent ------4.5 peratures of about 1000 F. to 1300 F. The treatment Cs-- gasoline, vol. percent ------7.4 may be accomplished in an atmosphere of 100% steam or Total C4's, vol. percent ------3.7 in an atmosphere consisting of steam and a gas which is Dry gas, wt. percent ------2.2 Substantially inert to the aluminosilcate. The steam 70 Coke, wt. percent ------2.4 treatment apparently provides beneficial properties in the aluminosilicate. Example 2 The high catalytic activities obtainied by alumnosilicate The procedure of Example 1 was repeated with the compositions prepared in accordance with the invention exception that the crystalline aluminosilicate was sub are illustrated in connection with the cracking of a rep 75 jected to a continuous treatment for 24 hours instead of 3,140,251 13 14 12 two-hour treatments. The following table shows the The following table shows the cracking data obtained cracking data obtained with the catalyst was evaluated when the catalyst was evaluated for cracking gas oil at for cracking gas oil at 900°F.: 900 F.: TABLE 2. TABLE 4 Cracking data: 5 Cracking data: Conversion, vol. percent ------60.7 Conversion, vol. percent------63.1 LHSV ------16 LHSV------16 10 R.V.P. gaso., vol. percent ------51.7 10 R.V.P. gaso., vol. percent------526 Excess C4's, Vol. percent ------11.2 Excess C4's, Vol. percent------12.3 Cs-- gasoline, vol. percent ------49.2 O Cs+ gasoline, Vol. percent------50.4 Total C's, Vol. percent ------13.7 Total C4's, Vol. percent.------14.5 Dry gas, wt. percent ------6.4 Dry gas, wt. percent------6.8 Coke, wt. percent ------3.0 Coke, wt. percent------3.6 Has Wt. percent ------0.03 H2, wt. percent------0.04 A advantage: 5 A advantage: 10 R.V.P. gaso., vol. percent ------6.5 10 R.V.P., vol. percent------6.2 Excess C4's, vol. percent ------2.8 Excess C4's, Vol. percent------2.7 C5+ gasoline, vol. percent ------6.2 C5-- gasoline, vol. percent------6.2 Total C4's, Vol. percent ------2.5 Total C4's, vol. percent------2.5 Dry gas, wt. percent ------1.3 20 Dry gas, wt. percent------1.4 Coke, wt. percent ------1.7 Coke, wt. percent------1.5 Example 3 Example 6 A crystalline aluminosilicate identified as Zeolite 13X was subjected to three 2-hour treatments with a 5% by The procedure of Example 5 was repeated with the Weight aqueous solution of ammonium chloride and then 25 exception that the aluminosilicate was steamed for 24 treated for 48 hours with an aqueous solution consisting hours at 1200° F. with steam at 15 p.s. i.g. The cracking of 5% by weight mixture of rare earth chlorides and 2% data obtained when using this catalyst for cracking gas by Weight of ammonium chloride. The aluminosilicate oil at 900 F. is shown in the following table. was then washed with water until there were no chloride 30 TABLE 5 ions in the effluent, dried and then treated for 24 hours Cracking data: at 1200 F. with steam at 15 p.s.i.g. to yield a catalyst Conversion, vol. percent.------65.9 having a sodium content of 0.2 weight percent. LHSV------16 Example 4 10 R.V.P. gaso., vol. percent------56.5 A synthetic crystalline aluminosilicate identified as 35 Excess C4's, Vol. percent------12.1 Zeolite 13X was treated for 72 continuous hours with an C5+ gasoline, Vol. percent------53.9 aqueous solution containing 10% by weight of ammoni Total Ca's, vol. percent------14.7 um chloride, 10% by weight of ammonium acetate, and Dry gas, wt. percent------6.6 1% by weight of rare earth chlorides. The alumino Coke, wt. percent------3.0 silicate was then washed with water until there were no 40 H2, wt. percent------0.03 chloride or acetate ions in the effluent, dried and then A advantage: treated for 24 hours at 1200 F. with steam at a pressure 10 R.V.P., vol. percent------8.8 of 15 p.s.i.g. Excess C4's, vol. percent.------3.9 The following table shows the cracking data obtained Cs-- gasoline, vol. percent.------8.4 when the catalyst was evaluated for cracking gas oil at 45 Total C4's, vol. percent------3.3 900 F.: Dry gas, wt. percent------2.1 TABLE 3 Coke, wt. percent------2.7 Cracking data: Conversion, vol. percent ------56.6 Example 7 LHSV ------16 50 The procedure of Example 6 was repeated with the 10 R.V.P. gaso., vol. percent ------50.9 exception that 36 two-hour contacts of the lanthanum Excess C4's, Vol. percent ------9.2 chloride and ammonium chloride solution were employed Cs gasoline, Vol. percent ------48.3 instead of 24 two-hour contacts. The resulting catalyst Total C4's, Vol. percent ------11.8 had a sodium content of 0.46 weight percent. Table 6 Dry gas, wt. percent ------5.4 55 shows the cracking data obtained when the catalyst was Coke, wt. percent ------1.4 evaluated for cracking gas oil at 900 F. He wt. percent ------0.01 TABLE 6 A advantage: Cracking data: 10 R.V.P. gaso., vol. percent ------7.9 Conversion, vol. percent------63.7 Excess C4's, vol. percent ------3.4 60 LHSV------16 Cs+ gasoline, Vol. percent ------7.4 10 R.V.P. gaso., vol. percent------55.3 Total C4's, vol. percent ------3.0 Excess C4's, Vol. percent------8.1 Dry gas, wt. percent ------1.6 C5+ gasoline, vol. percent------51.8 Coke, wt. percent ------2.5 Total C4's, vol. percent------11.6 Example 5 65 Dry gas, wt. percent------7.6 A Synthetic crystalline aluminosilicate identified as Coke, wt. percent------3.1 Zeolite 13X was subjected to 24 two-hour treatments with H2, wt. percent------0.03 an aqueous solution consisting of 5% by weight of lantha A advantage: num chloride and 2% by weight of ammonium chloride 70 10 R.V.P., vol. percent------8.7 at 180° F. The aluminosilicate was then washed with Excess C4's, Vol. percent.------7.0 water until there were no chloride ions in the effluent, Cs+ gasoline, vol. percent------7.3 dried and then treated for 20 hours at 1225 F. with 100% Total Ca's, vol. percent.------5.7 atmospheric steam to yield a catalyst having a sodium Dry gas, wt. percent------0.7 -content of 0.36 weight percent. 75 Coke, wt. percent------2.2 3,140,251. 15 a 1. Example 8 TABLE 9 A synthetic crystalline aluminosilicate identified as Cracking data: Zeolite 13X was treated with an aqueous solution contain Conversion, vol. percent ------61.8 ing 2% by weight mixture of rare earth chlorides for 18 LHSV ------10 continuous hours and then treated with an aqueous solu 5 10 R.V.P. gaso., vol. percent ------57.0 tion of ammonium sulfate containing 5% by weight of Excess Ca's, Vol. percent ------9.5 ammonium sulfate for 3 contacts of 16 hours each and Cs-- gasoline, vol. percent ------54.0 then with 9 contacts of 2 hours each of the same solution. Total C4's, Vol. percent ------12.5 The treated aluminosilicate was washed with water until Dry gas, wi. percent ------4.8 the effluent contained no chloride or sulfate ions, dried O Coke, wt. percent ------1.5 and then treated for 30 hours at 1200° F. with steam at H2, wt. percent ------0.01 15 p.s.i.g. The resulting catalyst contained 0.12 weight A advantage: percent sodium. The catalytic evaluation of the alumino silicate for cracking gas oil at 900 F. is shown in the 10 R.V.P., Vol. percent ------11.2 5 Excess C4's, Vol. percent ------4.9 following table. Cs-- gasoline, vol. percent ------10.4 TABLE 7 Total C4's, vol. percent ------4.1 Cracking data: Dry gas, wt. percent ------3.2 Conversion, vol. percent------37.5 Coke, wt. percent ------3.3 LHSV------4. 20 Example 11 10 R.V.P. gaso., vol. percent.------32.5 Excess C4's, Vol. percent------6.5 The procedure of Example 9 was repeated with the C5 gasoline, vol. percent------30.9 exception that the treatment solution consisted of 5% by Total C4's, Vol. percent------8.1 Weight of lanthanum chloride and 2% by weight of am Dry gas, wt. percent------4.1 25 monium chloride. The catalytic evaluation for cracking Coke, wt. percent------1.4 gas oil at 900 F. is shown in the following table: He wt. percent------0.02 TABLE 10 Cracking data: A advantage: Conversion, vol. percent ------66.1 10 R.V.P., vol. percent------0.1 30 LHSV ------16 Excess C4's, Vol. percent------0.5 10 R.V.P. gaso., vol. percent ------59.0 C5-- gasoline, vol. percent------0.9 Excess C4's, vol. percent ------9.3 Total C4's, vol. percent------1.4 Cs-- gasoline, vol. percent ------55.7 Dry gas, wt. percent------0.1 Total C4's, Vol. percent ------12.6 Coke, wt. percent------0.2 Dry gas, wt. percent ------7.0 Example 9 Coke, wt. percent ------2.3 H2, wt. percent ------0.02 A synthetic crystalline aluminosilicate identified as A advantage: Zeolite Y was treated with an aqueous solution consist 40 10 R.V.P., Vol. percent ------11.2 ing of 5% by weight mixture of rare earth chlorides and Excess C4's, vol. percent ------6.9 2% by weight of ammonium chloride and then washed Cs-F gasoline, vol. percent ------10.1 with water until the effluent contained no chloride ions, dried and then treated for 24 hours at 1200° F. with 15 Total C4's, vol. percent ------5.7 p.s.i.g. steam. The resulting aluminosilicate contained Dry gas, wt. percent ------1.7 0.52 weight percent sodium and gave the following results Coke, wt. percent ------3.4 when tested for cracking gas oil at 900 F. Example 12 A synthetic crystalline aluminosilicate was prepared by TABLE 8 mixing the following solutions: Cracking data: Conversion, vol. percent ------61.6 50 (A) Sodium silicate solution: LHSV ------16 N-Brand sodium silicate ------77.5 lbs. 10 R.V.P. gaso., vol. percent ------54.9 NaOH pellets ------11.0 lbs. Excess C4's, vol. percent ------9.8 Water ------143.0 lbs. Cs-- gasoline, vol. percent ------52. Specific gravity ------1.172 at 68 F. 55 8.8 weight percent Na20, 28.5 weight percent SiO2, 62.7 Total C4's, Vol. percent ------12.5 weight percent water. Dry gas, wt. percent ------6.1 (B) Sodium aluminate solution: Coke, wt. percent ------1.9 Sodium aluminate ------. 25.6 lbs. H2, wt. percent ------0.02 Sodium hydroxide pellets ------11.0 lbs, 60 A advantage: Water ------. 195.0 lbs. 10 R.V.P., vol. percent ------9.0 Specific gravity ------1140 at 68 F. Excess C4's, Vol. percent ------4.6 Solution (B) was added to solution (A) while agitating Cs-- gasoline, vol. percent ------8.6 vigorously to break up the hydrogel as it formed into Total C4's, Vol. percent ------4.1 65 a creamy slurry. The slurry was heated for 12 hours Dry gas, wt. percent ------1.8 at 205 F., filtered, washed to 11 pH and then dried Coke, wt. percent ------2.9 in air at 280 F. to yield a crystalline aluminosilicate. 3.3 pounds of the aluminosilicate was treated with 4 Example 10 batches of a 27.5% by weight aqueous solution of cal 70 cium chloride, each bath having 1 lb. of calcium chlo The procedure of Example 9 was repeated with the ex ride per pound of aluminosilicate. Three treatments ception that the solution consisted of 5% by weight of Were for 24 hours each at 180° F. and the fourth one calcium chloride and 2% by weight of ammonium chlo was for 72 hours at room temperature. After the four ride. The catalytic evaluation for cracking gas oil at treatments with the calcium chloride solution, the alu 900 F, is shown in the following table. 75 minosilicate was further treated four times with an aque 3,140,251 17 3 ous solution containing 2% by weight of calcium chlo mesh and calcined in air for 2 hours at 650 F. 5 grams ride and 1% by weight of aluminum chloride for 4 con of the calcined crushed gmelinite was treated 10 times tacts, 3 of which were for 2 hours and 1 was overnight, with 10 cc. of a solution containing 4% by weight mix all 4 contacts being at room temperature. The alu ture of rare earth chlorides and 1% by weight ammonium minosilicate was then washed with water until the effluent chloride. Each of the treatments was for 1 hour at a contained no chloride ions, dried, pelleted to /2' size, temperature of 173-186 F. The aluminosilicate was ground to 4Ao mesh and calcined for 10 hours in air at then washed with water until the effluent contained no 1000 F. The aluminosilicate catalyst was then treated chloride ions, dried overnight at 190 F., pelleted, re with 100% steam at 1225 F. for 20 hours at atmospheric crushed to a particle size of less than 12 mesh and cal pressure. The resulting catalyst was evaluated for crack 10 cined for three hours at 900 F. in air. The resulting ing gas oil at 875 F. and gave the following results. product was employed as a catalyst for the cracking of decane at a catalyst concentration of 3.3 cc., at a feed TABLE 11 rate of 3.0 LHSV, and temperature of 900 F. A conver Cracking data: sion of 91.6% by weight was obtained. Conversion, Vol. percent ------64.3 15 LHSV ------7.5 Example 18 Cs+ gaso, vol. percent ------53.5 Total C4's, vol. percent ------12.7 The procedure of Example 17 was repeated with the Total dry gas, wt. percent ------5.0 exception that ptilolite was employed instead of gmelinite. Coke, Wt. percent ------4.6 20 When the the resulting catalyst was used to crack decane, A advantage: it gave a conversion of 58.7% by weight. Cs+ gaso., vol. percent ------1.8 Total C4's, Vol. percent ------8.4 Example 19 Total dry gas, Wt, percent ------3.6 25 The procedure of Example 17 was repeated with the Coke, Wt. percent ------1.0 exception that the aluminosilicate employed was identified Example 13 as chabazite. The resulting catalyst gave a conversion of A synthetic crystalline aluminosilicate identified as Zeo 95% by weight when employed to crack decane. lite 4A was treated three times for 24 hours and one time for 72 hours with a 26 weight percent aqueous solution of 30 Example 20 calcium chloride at 180° F. After the treatment with A synthetic crystalline aluminosilicate, identified as calcium chloride, the aluminosilicate was then treated for Zeolite 13X, was subjected to 12 two-hour treatments at three two-hour contacts and one overnight contact at 180 - F. with an aqueous solution containing 5% by room temperature with an aqueous solution consisting of 35 weight mixture of rare earth chlorides and 2% by weight 2% by weight of calcium chloride and 1% by weight am of ammonium chloride. The aluminosilicate was then monium chloride. The aluminosilicate was then washed treated with a 10% by weight aqueous solution of am with water until the effluent contained no chloride ions, monium carbonate for 4 hours at 180° F. The resulting dried, calcined for 10 hours at 1000 F. in air, and then modified aluminosilicate was then washed with water treated with steam for 20 hours at 1225 F. to yield a 40 until there were no chloride or carbonate ions in the catalyst having a sodium content of 0.6 percent by weight. effluent, dried and then treated for 24 hours at 1200 F. Example 14 with steam at 15 p.s.i.g. to yield a catalyst having a so dium content of 0.65 weight percent. A synthetic crystalline aluminosilicate identified as The following table shows the cracking data obtained Zeolite 5A was treated with a chloroplatinic acid solution 45 when the catalyst was evaluated for cracking gas oil at containing 2.0 grams platinum and an ammonium hy 900 F.: droxide solution containing 28% by weight ammonia. The aluminosilicate was washed with water until the TABLE 12 effluent contained no chloride ions, dried and then treated Cracking data: for 20 hours at 1225 F. with atmospheric steam to yield 50 Conversion, vol. percent ------43.4 an aluminosilicate having excellent catalytic properties. LHSV------8 10 R.V.P. gaso, vol. percent ------40.9 Example 15 Excess C4's, vol. percent ------5.8 1800 grams of a crystalline aluminosilicate identified C5+ gasoline, vol. percent ------38.6 as Zeolite 13X was treated with a solution consisting of 55 Total C4's, vol. percent ------8.2 cerium chloride and ammonium hydroxide. The treat Dry gas, wt. percent ------3.6 ment was carried out at a temperature of 160-180° F. Coke, wt. percent ------0.9 for 4 hour after which time the slurry was filtered and H2 wt. percent ------0.02 then the operation repeated for another 4 hour. The resulting aluminosilicate contained 0.81 weight percent 60 A advantage: sodium and 24.7 weight percent cerium. 10 R.V.P., vol. percent ------5.1 Excess C4's, vol. percent ------2.9 Example 16 C5- gasoline, Vol. percent ------5.1 66.5 grams of a synthetic crystalline aluminosilicate Total C4's, vol. percent ------2.8 identified as Zeolite 5A was pelleted and treated with 26.6 65 Dry gas, wt. percent ------1.3 grams of ammonium nitrate dissolved in 1 gallon of dis Coke, Wt, percent ------1.12 tilled water. The product was rinsed with distilled water until the effluent contained no nitrate ions and then cal Example 21 cined at 650-700' F. for several hours in a stream of nitrogen. The resulting aluminosilicate analyzed at 9.08 70 The procedure of Example 20 was repeated with the Weight percent calcium. exception that a 10% by weight aqueous solution of am monium phosphate was employed instead of the ammo Example 17 nium carbonate. The resulting catalyst had a sodium A natural crystalline aluminosilicate identified as content of 0.5 weight percent and the cracking data shown gmelinite was crushed to a particle size of less than 32 75 in the following table when used at 900 F.: 3,140,251 19 20 TABLE 13 Example 24 Cracking data: 25 parts by weight of a crystalline aluminisolicate iden Conversion, vol. percent ------42.2 tified as Zeolite 13X was dispersed in 75 parts by weight LHSV------16 of silicon dioxide and the resulting composition treated 10 R.V.P. gaso., vol. percent ------35.1 for 24 continuous hours with an aqueous solution consist Excess C4's, vol. percent------7.7 ing of 1% by weight mixture of rare earth chlorides and Cs-- gasoline, vol. percent ------33.5 1% by weight of ammonium chloride. The aluminosili Total C4's, Vol. percent ------9.3 cate was then washed with water, until there were no Dry gas, wt. percent ------4.7 chloride ions in the effluent, dried and then treated for Coke, Wt. percent ------2.1 0 24 hours at a temperature of 1200 F. with steam at 15 H2, wt. percent ------0.02 p.si.g. to yield a catalyst having the cracking data shown Example 22 in the following table when evaluated for cracking gas oil at 900 F.: TABLE 16 5 parts by weight of the synthetic crystalline alumino 5 silicate identified as Zeolite 13X was incorporated into Cracking data: 95 parts by weight of a silica-alumina matrix consisting Conversion, Vol. percent ------61.5 of 94 weight percent of SiO2 and 4 weight percent of LHSV------4 AlO3. The resulting composition was then treated with 10 R.V.P. gaso., vol. percent ------53.8 an aqueous solution containing 1% by weight mixture 20 Excess C4's, Vol. percent ------9.8 of rare earth chlorides and 1% by weight of ammonium Cs-- gasoline, vol. percent ------50.9 chloride for 12 contacts of 2 hours each. The treated Total C4's, Vol. percent ------12.6 aluminosilicate was then washed with water until there Dry gas, wt. percent ------5.9 were no chloride ions in the effluent, dried and treated Coke, wt. percent ------3.0 for 24 hours at 1200 F. with steam at 15 p.s.i.g. to yield 25 H2 Wt. percent ------0.02 a catalyst having a sodium content of 0.07 weight percent. A advantage: The following table shows the cracking data obtained 10 R.V.P., Vol. percent ------8.2 when the catalyst was evaluated for cracking gas oil at Excess C4's, Vol. percent ------4.6 900 F.: Cs-- gasoline, Vol. percent ------+7.5 TABLE 14 30 Total C4's, Vol. percent ------3.9 Cracking data: Dry gas, wt. percent ------1.9 Conversion, Vol. percent ------50.5 Coke, Wt. percent ------1.7 LHSV------4. 10 R.V.P. gaso, vol. percent ------45.0 Example 25 Excess Ca's, vol. percent ------8.7 35 The procedure of Example 24 was repeated with the Cs-- gasoline, Vol. percent ------42.7 exception that the composition was first treated with a Total C4's, vol. percent ------11.0 2% by weight aqueous solution of a mixture of rare earth Dry gas, wt. percent ------4.7 chlorides for 16 continuous hours, washed and then treat Coke, wt. percent ------1.6 ed with a 1% by weight aqueous solution of ammonium H2, wt. percent ------0.04 40 chloride for 24 continuous hours. The resulting catalyst contained 4.35 weight percent rare earths, determined as A advantage: rare earth oxide, and had the cracking data shown in the 10 R.V.P., Vol. percent ------5.1 following table: Excess C4's, vol. percent ------2.0 TABLE 17 Cs-- gasoline, Vol. percent ------5.2 45 Cracking data: Total C4's, Vol. percent ------2.0 Conversion, vol. percent ------48.4 Dry gas, wt. percent ------1.4 LHSV------4 Coke, wt. percent ------1.4 10 R.V.P. gaso., Vol. percent ------44.6 Example 23 Excess C4's, Vol. percent ------6.5 50 C5+ gasoline, vol. percent ------42.1 The procedure of Example 22 was repeated with the Total C4's, Vol. percent ------9.0 exception that one contact of 24 continuous hours was Dry gas, wt. percent ------4.6 employed instead of 12 two-hour contacts. The sodium Coke, wt. percent ------1.3 content of the resulting aluminosilicate was 0.1 weight per H2 Wt. Percent ------0.02 cent and it had the cracking data shown in the following 55 table when employed at a temperature of 900 F.: A advantage: 10 R.V.P., Vol. percent ------5.8 TABLE 1.5 Excess C4's, Vol. percent ------3.5 Cracking data: C5+ gasoline, Vol. percent ------5.6 Conversion, Vol. percent ------515 Total C4's, Vol. percent ------3.5 LHSV------4. 60 Dry gas, wt. percent ------1.1 10 R.V.P. gaso., vol. percent ------45.8 Coke, wt. percent ------1.4 Excess C4's, vol. percent ------9.4 C5-- gasoline, Vol. percent ------43.5 Example 26 Total C4's, vol. percent ------11.7 10 parts by weight of a synthetic crystalline alumino Dry gas, wt. percent ------4.7 65 silicate identified as Zeolite 13X was dispersed into 90 Coke, wt. percent ------1.5 parts by Weight of a silica alumina matrix consisting of H2 Wt. percent ------0.03 93% by weight SiO, and 7% by weight of Al-O. The composition was then treated for one two-hour contact A advantage: with a 1% by weight aqueous solution of rare earth chlo 10 R.V.P., vol. percent ------5.3 70 rides, washed and then subjected to one 24 hour continu Excess C4's, Vol. percent ------1.6 ous contact with an aqueous solution consisting of 2% by Cs+ gasoline, Vol. percent ------5.3 Weight of calcium chloride and 1% by weight of ammo Total C4's, Vol. percent ------1.6 nium chloride. The aluminosilicate was then washed with Dry gas, wt. percent ------1.6 Water until there were no chloride ions in the effluent, dried Coke, Wt. percent ------1.7 75 and then treated for 20 hours at 1225 F. with 1% atmos 3,140,251 21. . pheric steam to yield a catalyst having a sodium content . TABLE 2.0 of 0.1% by weight, a calcium content of 2.2% by weight, Cracking data: and a rare earth content, determined as rare earth oxides, Conversion, Vol. percent ------54.8 of 5.1% by-weight.------...- LHSV------4 - The following table-shows cracking data obtained when 5 10 R.V.P. gaso., Vol. percent ------...------48.3 the catalyst was evaluated for cracking gas oil at 900 F.: Excess. C4's, Vol. percent ------9.1 Cs---gasoline, Vol. percent.------45.8 ------TABLE 8 Total C's, Vol. percent ------...------11. Dry gas, wt. percent ------4.8 Cracking data:------O Conversion, vol. percent ------51.1 Coke, Wii. percent ------2.5 LHSV------4 H2, wt. percent ------0.03 - 10.R.V.P. gaso., Vol. percent------44. A advantage: m ' ' ...... "Excess-CA's, Vol. percent ------8.8 10 R.V.P., Vol., percent ------6.1 Cs+ gasoline, vol. percent ------42.4 5 Excess C4's, Vol. percent ------2.9 Total C4's, Vol. percent ------10.9 C5+ gasoline, Vol. percent ------+6.0 Dry gas, Wt. percent------4.8 Total C4's, Vol. percent ------2.7 Coke, wt. percent------22 Dry gas, wt. percent ------1.9 A advantage: ...... Coke, wt. percent ------1.1 10 R.V.P., Yol. percent.------4.3 20 Excess C4's, Vol. percent ------2.1 . Example 29. Cs--gasoline, Vol. percent------. --4.4 10 parts by weight of a synthetic crystalline alumino Total Ca's, vol. percent ------2.3 silicate identified as Zeolite 13X was dispersed into 90 Dry gas, wt. percent ------1:4 25 parts of a silica alumina matrix and the composition was Coke, wt. percent ------, -0.4 treated with an aqueous solution containing 2% by weight of a mixture of rare earth chlorides for 24 continuous Example 27. hours. The aluminosilicate was then washed and treated The procedure of Example 26 was repeated with the with a 1% by weight aqueous solution of ammonium sul 30 fate for three 16 hour contacts and then for 9 two-hour exception that 2 two-hour contacts of a rare earth chloride contacts with the same solution. The aluminosilicate was mixture were employed instead of 1 two-hour contact. then washed with water until there were no chloride or The resulting aluminosilicate had a sodium content of sulfate ions in the effluent, dried and then treated for 30 0.1% by weight, a calcium content of 1.8% by Weight, hours at 1200 F. with steam at a pressure of 15 p.s.i.g. and a rare earth content, determined as rare earth oxides, to yield a catalyst having a sodium content of 0.17% by of 7.7% by weight. u- - - -- ... -- Yu---- weight and a rare earths content, determined as rare The following table shows the cracking data of the earth oxides, of 4.5% by weight. catalyst when evaluated for cracking gas oil at 900. F.: The following table shows the cracking data of the

-- ...... TABLE 19. - - - - 40 catalyst when evaluated for cracking gas oil at 900 F.: Cracking-data: ------...... TABLE 21 Conversion, vol. percent ------53. LHSV------Cracking data: . . . - ...... O.R.V.P. gaso., vol. percent. ------Conversion, Vol. percent.------57.4 Excess Ca's, vol. percent ------45 LHSV------4. Cs---gasoline, Vol. percent.------4 10 R.V.P. gaso., vol. percent ------48.3 Total C's, Vol. percent -- 1. Excess C4's, vol. percent ------11.1 Dry gas, wt. percent --. C5+ gasoline, Vol. percent ------46.2 Total C4's, Vol. percent ...------13.3 - - - - Coke, Wt percent ------Dry gas, wt. percent ------6.0 A advantage: ...... Coke, wt. percent ------2.5 10 R.V.P., vol. percent. H2, wt. percent ------0.02 Excess. C's, Vol. percent Cs+ gasoline, Vol. percent.---- A advantage: ------...Total C's, Vol. percent 10 R.V.P., Vol. percent ------4.8 ... Drygas, Wt, percent -- ExceSSC's, Vol. percent------1.7 Coke, Wt. percent ------C5-gasoline, Vol. percent ------4.8 Total C's, vol. percent ... -1.8 Example 28 . 60 Dry gas, Wt. percent ------1.3 10 parts by weight of a synthetic crystalline alumino Coke, wt. percent ------1.6 silicate identified as Zeolite 13X was dispersed in 90 parts by weight of a silica alumina matrix consisting of 93% - - - - Example 30 . SiO, and 7% AlOs. The composition was then treated ... 10 parts by weight of a crystalline synthetic alumino for 24 continuous hours with a 1% by weight solution of 65 a mixture of rare earth chloride and a 1% by Weight solu silicate identified as: Zeolite. 13X was dispersed into 90 tion of ammonium-chloride....The aluminosilicate Was parts of a silica alumina matrix-and the composition was then washed with water until there was no chloride ions treated with an aqueous solution consisting of 1% by in the effluent, dried...and then treated for 30 hours at weight of didymium-chloride and 1% by weight of am 1200°F. with steam at a pressure of 15 p.si.g. to yield a 70 monium chloride for 24 continuous hours. The alumino catalyst having a sodium content of 0.09% by weight and silicate was then washed with water until there were no a rare earth content determined as rare earth oxides, of chloride ions in the effluent, dried and then treated for 24 hours at 1200.F., with steam at a pressure of 15 p.si.g. 0.92%.The byfollowing weight..... table shows the cracking datav of the . to yield a catalyst having 8.77%. by weight of rare earths, catalyst when evaluated for cracking gas oil at 900 F.: 75 determined as rare earth oxides. 3,140,251 23 24 The following table shows the cracking data of the TABLE 24 catalyst when evaluated for cracking gas oil at 900 F.: Cracking data: Conversion, vol. percent ------57.3 TABLE 22 LHSV ------4 10 R.V.P. gaso., vol. percent ------46.1 Cracking data: Excess C4's, Vol. percent ------11.3 Conversion, Vol. percent ------63.1 Cs-- gasoline, vol. percent ------43.3 LHSV ------4 Total C4's, vol. percent ------14.1 10 R.V.P gaso., vol. percent ------52.7 Dry gas, wt. percent ------6.1 Excess C4's, vol. percent ------11.8 10 Coke, wt. percent ------4.0 Cs+ gasoline, vol. percent ------50.1. H2, wt. percent ------0.03 Total C4's, vol. percent ------14.4 A advantage: Dry gas, Wt. percent ------7.1 10 R.V.P., vol. percent.------2.7 Coke, wt. percent ------3.3 Excess C4's, Vol. percent------1.6 H2, wt. percent ------0.18 5 Cs+ gasoline, vol. percent.------2.0 A advantage: Total C4's, vol. percent------1.0 10 R.V.P., Vol. percent------6.2 Dry gas, wt. percent------0.6 Excess Ca's, vol. percent------3.2 Coke, wt. percent------0.1 Cs+ gasoline, vol. percent------5.9 Total C4's, Vol. percent------2.6 20 Example 33 Dry gas, wt. percent------1.1 25 parts by weight of a synthetic crystalline alumino Coke, Wt. percent------1.8 silicate identified as Zeolite 13X was dispersed in 75 parts by weight of a silica alumina matrix and the resulting Example 31 composition treated with an aqueous solution consisting 25 of 2% by weight mixture of rare earth chlorides and The procedure of Example 30 was repeated with the 0.5% by weight of acetic acid for 12 contacts each being exception that a 2% by weight solution of didynium chlo two hours in duration. The aluminosilicate was then ride was employed for 16 continuous hours and then a washed with water until there were no chloride or acetate 1% by weight solution of ammonium chloride was em ions in the effluent, dried and then treated for 20 hours ployed for 24 continuous hours. The cracking data of 30 at 1225 F. with a 100% atmospheric steam to yield a the resulting catalyst is shown in the following table: catalyst having a rare earths content, determined as rare earth oxides, of 3.17. TABLE 23 The following table shows the cracking data of the catalyst when evaluated for cracking gas oil at 900 F.: Cracking data: 35 Conversion, vol. percent ------58.6 TABLE 2.5 LHSV ------4. Cracking data: 10 R.V.P. gaso., vol. percent ------50.8 Conversion, vol. percent ------43.0 Excess C4's, Vol. percent ------11.1 40 LHSV ------4. Cs+ gasoline, vol. percent ------48.6 10 R.V.P. gaso., vol. percent ------34.3 Total C4's, vol. percent ------13.3 Excess C4's, Vol. percent ------9.6 Dry gas, Wt. percent ------5.6 Cs-- gasoline, vol. percent ------32.6 Coke, wt. percent ------2.1. Total C4's, vol. percent ------11.1 H2, wt. percent ------0.04 45 Dry gas, wt. percent------5.1 A advantage: Coke, wt. percent ------2.4 10 R.V.P., vol. percent------6.7 H2, wt. percent ------0.02 Excess C4's, vol. percent.------2.1 Example 34 C5+ gasoline, vol. percent.------6.7 50 25 parts by weight of a synthetic crystalline alumino Total C4's, Vol. percent------2.2 silicate identified as Zeolite 13X was dispersed into 75 Dry gas, Wt. percent------1.8 parts of a silica alumina matrix and the resulting compo Coke, wt. percent------2.1 sition treated with an aqueous solution consisting of 2% by weight of calcium chloride and 1% by weight of am Example 32 55 monium chloride for 2 treatments of 2 hours each. The aluminosilicate was then washed with water until there 25 parts by weight of a synthetic crystalline alumino were no chloride ions in the effluent, dried and then silicate identified as Zeolite 13X was dispersed in 75 parts treated for 20 hours at 1225 F. with 100 atmospheric of a silica alumina matrix and the resulting composition steam to yield a catalyst having a sodium content of 0.69 treated with a 2% by weight solution of calcium chloride 60 and a calcium content of 3.44. for 8 continuous hours, followed by treatment with an The following table shows the cracking data of the aqueous solution consisting of 2% by weight of calcium catalyst when evaluated for cracking gas oil at 900 F.: chloride and 0.5% by weight of ammonium chloride for TABLE 26 16 continuous hours and then treated with a 2% by 65 weight aqueous solution of rare earth chlorides for 2 con Cracking data: tacts each of 2 hours. The aluminosilicate was then Conversion, vol. percent ------48.3 washed with water until there was no chloride ions in the LHSV ------4. effluent, dried and then treated for 20 hours at 1225 F. 10 R.V.P. gaso., vol. percent ------46.6 with 1% atmospheric steam to yield a catalyst having 70 Excess C4's, vol. percent ------4.0 calcium content of 2.15% by weight and a rare earths Cs-- gasoline, vol. percent ------43.2 content, determined as rare earth oxides, of 7.2% by Total C4's, vol. percent ------7.4 weight. Dry gas, wt. percent ------4.1 The following table shows the cracking data of the Coke, Wt, percent ------1.5 catalyst when evaluated for cracking gas oil at 900 F.: 75 H2 Wt, percent ------0.02 3,140,251 25 26 TABLE 26-Continued by weight of ammonium chloride for 24 continuous hours. A advantage: - - ...... " The aluminosilicate was then washed with water until 10 R.V.P., vol. percent------+7.9 there were no chloride ions in the effluent, dried and then Excess Ca's, vol. percent------6.0 treated for 20 hours at 1225 F. with 100% atmospheric Cs-- gasoline, vol. percent------6.8 5 steam to yield a catalyst having a sodium content of 0.12 Total CA's, vol. percent------4.0 weight percent, calcium content of 2.5 weight percent, Dry gas, wt. percent. -1.6 and a rare earths content, determined as rare earth oxides, Coke, Wt. percent------1.2 of 24 weight-percent. ------Example 35 The following table shows the cracking data of the The procedure of Example 34 was repeated with the 10 catalyst when evaluated for cracking gas oil at 900 F.: exception that 12 two-hour contacts of treating solution TABLE 29 were employed instead of 2 two-hour contacts. The so Cracking data: ...... dium content of the resulting aluminosilicate was 0.17% by weight and the calcium content was 3.24% by weight. Conversion, vol. percent ------, 46.2 The cracking data of the catalyst are shown in the follow 15 LHSV------10 R.V.P. gaso, vol. percent------37.14 ing table: . . . . . Excess Ca's, vol. percent.------9.3 TABLE 27 Cs+ gasoline, vol. percent ------35.4 Cracking data: Total C4's, Vol. percent ------11.0 ... Conversion, vol. percent ------, 66.1 20 Dry gas, wt. percent ------5.4 LHSV------... 4 ... Coke, Wt, percent ------3:0 10 R.V.P. gaso., vol. percent ------, 55.7 H2.wt. percent. ------0:0 Excess C4's, vol. percent ------13.0 C5+ gasoline, vol. percent ------53.3 r Example 38 . . . . . Total C4's, Vol. percent ------15.7 25 . The procedu Example 37 was repeated with the Dry gas, wt. percent ------7.0 exception that the treating solution was a 1% by weight Coke, wt. percent ------28 solution of ammonium chloride instead of a solution of H2, wt. percent ------0:03 calcium and ammonium chlorides. The resulting catalyst A advantage: "...... - contained 0.11% by weight sodium and 2.05% by weight 10 R.V.P., vol. percent ------|-7.9 30 rare earths and had the cracking data listed in the follow Excess C's, vol. percent ------3.0 ing table: ------Cs+ gasoline, vol. percent ------|-7.0 Total C4's, vol. percent ------2.8 Cracking data: r - ... - - - Dry gas, wt. percent ------1.7 "Conversion, vol. percent ------. 59.9 Coke, wt. percent ------2.9 35 LHSV------4 Example 36, "10 R.V.P. gaso, vol. percent ------49.2 10 parts by weight of a synthetic crystalline alumino Excess C4's, vol. percent ------13.1 silicate identified as Zeolite 13X was dispersed into 90 ... Cs+ gasoline, vol. percent ----. -- 47.5 parts by weight of a silica alumina matrix and the result 40 : Total C4's, vol. percent ---- ing composition was treated with a 2% aqueous solution . . . . . Drygas, wt. percent --- of lanthanum chloride for one continuous 16 hour con ... Coke, wt. percent - tact and then treated with a 1% solution of ammonium ...: H2, wt. percent - chloride for 24 continuous hours. The aluminosilicate A advantage: ...... was then washed with water until there was no chloride 45 ... 10: R.V.P., vol. percent -- ions in the effluent, dried and then treated for 24 hours Excess Ca's, vol. percent - at 1200°F. with steam at 15 p.si.g. to yield a catalyst C5-gasoline, vol. percent - having a lanthanum oxide content of 5.92...... Total C4's, Vol. percent ------1.1 The following table shows the cracking data of the Dry gas, wt. percent ------1.4 catalyst when evaluated for cracking gas oil at 900 F.: so Coke, wt. percent -- ...... Example 39 - Cracking- - - - - da TABLE 28 - - - - 10 parts by weight of a cerium aluminosilicate prepared Conversion, vol. percent ------' 59.9 by reacting an aluminosilicate identified as Zeolite. 13X LHSV -- renees: re-re------C- -- 4 10 R.V.P. gaso., Vol. percent ------, 51.0 withsilica aalumina solution matrix of cerium and thechloride resulting was compositiondispersed into was a Excess C4's, Vol. percent ------7.9 treated with a 1% by weight solution of ammonium Cs+ gasoline, vol. percent ------47.8 chloride for 24 continuous hours. The aluminosilicate Total C's, vol. percent -. ------, 11.1 was then washed with water until there were no chloride Dry gas, wt. percent.-- 7.3 60 ions in the effluent, dried and then treated for 24 hours Coke, wt. percent ------3.4 at 1200.F. with steam at 15 p.si.g. to yield a catalyst H2, wt. percent ------0:03 having a cerium content of 2.2% by weight. A advantage: ...... The...following table shows the cracking data for the 10 R.V.P., vol. percent ------6.2 catalyst when evaluated for cracking gas oil at 900 F.: Excess Ca's, vol. percent ------, -5.9 Cs-- gasoline, Vol. percent ------5.2 65 ... r. TABLE 31 . . - Total C's, vol. percent.------4.8 Cracking data: ...... - Dry gas, wt. percent------0.3 ... Conversion, Vol. percent ------51.1 Coke, wt. percent ------1:1 . LHSV------4 - 10 R.V.P. gaso., vol. percent ----- 44.1 Example 37 70 - Excess C4's, Vol. percent ------9.1 10 parts by weight of a rare earth synthetic alumino ... --C5-gasoline, Vol. percent silicate prepared by reacting Zeolite 13X with a rare earth - Total C's vol. percent -- 11.2 chloride solution was dispersed in a silica alumina matrix . . . Drygas, Wt. percent ------4.9 and the resulting composition was treated with a solution . ... --Coke, Wt. percent.------2.4 consisting of 2% by weight of calcium chloride and 1% 75 - H2, wt. percent.------0:02 3,140,251 27 23 TABLE 31-Continued Example 43 A advantage: 10 R.S.V., Vol. percent ------4.0 The procedure of Example 38 was repeated with the Excess C4's, vol. percent ------1.8 exception that the matrix was SiO2 instead of a silica C5+ gasoline, vol. percent ------4.0 alumina matrix. The resulting catalyst had a rare earth Total C4's, Vol. percent ------1.9 content of 3.7% by weight. Dry gas, wt. percent ------1.3 Example 44 Coke, wt. percent ------0.6 The procedure of Example 39 was repeated with the Example 40 exception that the matrix was SiO, instead of silica The procedure of Example 39 was repeated with the 0. alumina. The resulting catalyst had a rare earth content exception that the cerium aluminosilicate dispersed in of 5.3% by weight. the matrix was first treated with a 2% by weight solution Example 45 of cerium chloride for 16 hours and then with a 1% by The procedure of Example 41 was repeated with the weight solution of ammonium chloride for 24 continuous exception that the matrix was SiO2 instead of silica hours. The resulting catalyst contained 6.6% by weight alumina. The resulting aluminosilicate had a rare earth of cerium and its cracking data is shown in the following content of 3.7% by weight. table when evaluated for cracking gas oil at 900 F.: Example 46 TABLE 32 The procedure of Example 42 was repeated with the Cracking data: 20 exception that the matrix was SiO, instead of silica Conversion, vol. percent ------54.3 alumina. The resulting catalyst had a rare earth content LHSV ------4 of 9.1% by weight. 10 R.S.V. gas, Vol. percent ------45.4 Example 47 Excess C4's, Vol. percent ------10.7 Cs-- gasoline, Vol. percent ------43.5 25 25 parts by weight of a synthetic crystalline calcium Total C4's, vol. percent ------12.6 aluminosilicate was dispersed into 75 parts by weight of Dry gas, Wt. percent ------5.4 a silica alumina matrix and the resulting composition. Coke, wt. percent ------3.0 treated with a 2% aqueous solution of rare earth chlo H2, wt. percent ------0.02 rides for 16 continuous hours and then with a 1% by A advantage: 30 weight solution of ammonium chloride for 24 continuous 10 R.S.V., Vol. percent ------3.4 hours. The aluminosilicate was washed with Water until Excess C4's, vol. percent ------1.2 the effluent contained no chloride ions and then treated Cs-- gasoline, Vol. percent ------3.7 for 24 hours at 1200 F. with steam at 15 p.si.g. to yield Total C4's, vol. percent ------1.6 a catalyst having a rare earth content, determined as rare Dry gas, wt. percent ------1.3 35 earth oxides, of 4.97% by weight. Coke, wt. percent ------0.6 The following table shows the cracking data for the Example 41 catalyst when evaluated for cracking gas oil at 900 F.: 10 parts by weight of a lanthanum aluminosilicate pre TABLE 34 pared by reacting Zeolite 13X with a 5% by weight 40 Cracking data: lanthanum chloride at 180° F. for one two-hour contact Conversion, vol. percent ------51.5 was dispersed in a silica alumina matrix and the result LHSV ------4 ing composition treated with a 1% by weight solution 10 R.V.P. gaso., Vol. percent ------49.3 of ammonium chloride for 24 continuous hours. The Excess C4's, Vol. percent ------8.0 aluminosilicate was then washed with water, dried and 45 Cs+ gasoline, vol. percent ------47.0 then treated for 24 hours at 1200 F. with steam at 15 Total C4's, Vol. percent ------10.3 p.s.i.g. to yield a catalyst having a rare earth content of Dry gas, wt. percent ------6.1 0.52% by weight, determined as rare earth oxides. Coke, wt. percent ------2.1 Example 42 He wt. percent ------0.01 The procedure of Example 41 was repeated with the 50 A advantage: exception that the aluminosilicate in the matrix was first 10 R.V.P., vol. percent ------8.9 treated with a 2% by weight solution of lanthanum chlo Excess Ca's, Vol. percent ------3.0 ride for 16 hours prior to the treatment with the 1% by Cs- gasoline, vol. percent ------9.0 weight solution of ammonium chloride for 24 hours. Total C4's, Vol. percent ------3.0 The resulting catalyst had a lanthanum content of 6.1% 55 Dry gas, wt. percent ------0.2 by weight and its cracking data is shown in the follow Coke, wt. percent ------1.0 ing table when evaluated for cracking gas oil at 900 F.: Example 48 TABLE 33 10 parts by weight of a crystalline aluminosilicate Cracking data: identified as Zeolite 13X was dispersed into 90 parts by Conversion, vol. percent ------60.5 60 Weight of a silica lanthanum matrix containing 98.5% by LHSV ------4. weight of SiO2 and 1.5% by weight of lanthanum oxides. 10 R.V.P. gaso., vol. percent ------515 The resulting composition was treated with a 2% aque Excess C4's, Vol. percent ------12.2 ous solution of lanthanum chloride for 16 continuous Cs-- gasoline, Vol. percent ------49.1 hours and then with a 1% solution of ammonium chlo Total C's, vol. percent ------14.5 ride for 24 continuous hours. The aluminosilicate was Dry gas, wt. percent ------6.0 then washed with water until there were no chloride ions Coke, wt. percent ------2.0 in the effluent, dried and then treated for 24 hours at H2 Wt. Percent ------0.02 1200 F. with steam at a pressure of 15 p.si.g. to yield A advantage: a catalyst having a rare earth content of 9.32% by weight. 10 R.V.P., vol. percent ------6.5 70 Excess C4's, Vol. percent ------1.8 Example 49 Cs-- gasoline, Vol. percent ------6.1 10 parts by weight of a synthetic crystalline alumino Total C4's, vol. percent ------1.5 silicate identified as Zeolite 13X was dispered into 90 Dry gas, wt. percent ------1.7 parts by weight of a silica rare earth oxide matrix con Coke, wt. percent ------2.6 75 sisting of 97% by weight of SiO, and 3% by weight of 3,140,251 29 30 rare earth oxides. The resulting composition was treated Example 52 with an aqueous solution consisting of 2% by weight of a mixture of rare earth chlorides for 16 hours and then 10 parts by weight of a synthetic crystalline alumino with a 1% by weight solution of ammonium chloride for silicate identified as Zeolite 13X was dispersed in 90 parts 24 continuous hours. The resulting aluminosilicate was by weight of a silica alumina lanthanum matrix consist Washed with Water until the effluent contained no chloride ing of 91% by weight SiO2, 3% by weight AlO3, and ions, dried and then treated for 24 hours at 1200° F. at 6% by weight of lanthanum oxides. The resulting com 15 p.s.i.g. with steam to yield a catalyst having a rare position was treated with a 1% by weight aqueous solu earth content of 7.8% by weight, determined as rare earth tion of lanthanum chloride and then with a 1% by weight oxides. solution of ammonium chloride, each treatment being O for 24 continuous hours. The aluminosilicate was then Example 50 washed with water until the effluent contained no chloride 10 parts by weight of a synthetic crystalline alumino ions, dried and then treated for 24 hours at 1200 F. silicate identified as Zeolite 13X was dispersed into 90 with steam at 15 p.s.i.g. to yield a catalyst having a parts by Weight of a silica didymium matrix consisting of sodium content of 0.15% by weight, and a rare earth con 97% by weight SiO2 and 3% by weight didymium oxides. 15 tent of 11.5% by weight, determined as rare earth oxides. The resulting composition was then treated for 16 con The cracking data of the resulting catalyst are shown tinuous hours with an aqueous solution consisting of 2% in the following table, when the catalyst was evaluated by weight of lanthanum chloride and then for 24 con for cracking gas oil at 900 F.: tinuous hours with 1% by weight aqueous solution of 20 ammonium chloride. The aluminosilicate was then M - - - TABLE 37 washed with water until the effluent contained no chlo Cracking data: -- . . . . ------, ride ions, dried and then treated for 24 hours at 1200 Conversion, Vol. percent ------54.0 F. with steam at 15 p.s.i.g. to yield a catalyst having a LHSV ------4 rare earth content of 7.79% by weight, determined as 25 10 R.V.P. gaso., Vol. percent ------49.8 rare earth oxides. Excess Ca's, Vol. percent ------7.5 The resulting catalyst had the cracking data shown in Cs-- gasoline, Vol. percent ------, 46.9 the following table when evaluated for cracking gas oil Total Ca's, Vol. percent ------10.4 at 900 F.: Dry gas, Wt. percent ------4.8 TABLE 35 30 Coke, wt. percent ------8 Cracking data: H2, wt. percent ------as a low aw we end row over O.O. Conversion, Vol. percent ------53.3 A advantage: LHSV ------4 10 R.V.P., Vol. percent ------8.0 10. R.V.P. gaso., Vol. percent ------47.8 Excess C4's, vol. percent ------, -5.9 Excess C4's, Vol. percent ------7.8 35 C5+ gasoline, Vol. percent ------7.4 Cs+ gasoline, Vol. percent ------45.3 Total C's, Vol. percent ------5.2 Total C4's, Vol. percent ------0.3 Dry gas, Wt. percent ------e - - - a sea one a -2.7 Dry gas, Wt. percent ------5.1 Coke, wt. percent ------2.6 Coke, wt. percent ------2.0 H2 Wt. percent ------0.05 40 ... Example 53 A advantage: 10, parts by weight of a crystalline aluminosilicate 10 R.V.P., Vol. percent ------6.4 identified as Zeolite Y was dispersed into 90 parts by Excess C4's, Vol. percent ------5.4 weight of a silica alumina matrix and the resulting com C5- gasoline, Vol. percent ------6.2 position was treated for 16 continuous hours with an Total C4's, Vol. percent ------5.1 45 aqueous solution comprising a 2% by weight mixture of rare earth chlorides and then for 24 continuous hours Dry gas, Wt. percent ------1.4 with a 1% by weight aqueous ammonium chloride solu Coke, Wt. percent ------1.4 tion. The aluminosilicate was then washed with water Example .51 until the effluent contained no chloride ions, dried and The procedure of Example. 50 was repeated with the 50 then treated for 24 hours at 1200° F. with steam at 15 exception that a 2% by weight aqueous solution of p.s.i.g. to yield a catalyst having a rare earth content of didymium chloride was employed instead of the lanthanum 3.35 weight percent. - - chloride. The resulting catalyst had a sodium content of The cracking data of the resulting catalyst is shown 0.5% by weight and a rare earth content of 11.2% by 55 in the following table when evaluated for cracking gas weight, and the cracking data shown in the following oil at 900 F.: " " ' - ...... table: " ------TABLE 38 TABLE 36 Cracking data: CrackingConversion, data: vol. percent.------v. . . . w 58.2 Conversion, Vol. percent ------48.1 60 LHSV ------4. LHSV ------4. 10 R.V.P. gaso., vol. percent ------43.4 10 R.V.P., gaso., vol. percent ------50.8 Excess Ca's, Vol. percent ------6.6 Excess C4's, Vol. percent ------, 10.6 Cs-- gasoline, Vol. percent ------440 Cs+-gasoline, Vol. percent------48.3 Total Ca's, vol. percent ------9.1 65 Total Ca's, vol. percent ------. 13.1 Dry gas, Wt. percent ------4.7 Dry gas, wt. percent ------5.4 Coke, Wt. percent ------1.6 Coke, wt. percent ------2.0 H2, wt. percent ------is 0.08 Ha, wt. percent ------0.01 A advantage: . A advantage:Tl 10 R.V.P., vol. percent ------4.9 70 10 R.V.P., vol. percent ------6.8 Excess C4's, Vol. percent ------2.5

Excess C4's, vol. percent ------3.4 Cs-- gasoline, Vol. percent ------4.8 Cs+ gasoline, Vol. percent ------, -6.5 Total C's, Vol. percent ------3.2 Total C's, Vol. percent ------2.3 Dry gas, Wt. percent ------1.0 Drygas, wt. percent ------a -1.9 Coke, Wt. percent ------10 75 Coke, Wt. percent ------2.2 3,140,251 31 32 Example 54 Example 57 The procedure of Example 53 was repeated with the 10 parts by weight of a caustic treated McNamee clay exception that a 2% by weight aqueous solution of was dispersed into a silica lanthanum matrix consisting lanthanum chloride was employed instead of the rare of 97 parts by weight of SiO, and 3 parts by weight of earth chloride solution. The resulting catalyst had a 5 lanthanum oxide. The resulting composition was sub lanthanum content of 3.9 weight percent determined as jected to a 24 hour continuous treatment with an aqueous lanthanum oxide. solution consisting of 1% by weight lanthanum chlo The cracking data of the resulting catalyst is shown ride and 1% by weight ammonium chloride. The alu in the following table: 0 minosilicate was then washed with water until the effluent TABLE 39 contained no chloride ions, dried and then treated for Cracking data: 24 hours at 1200 F. with steam at 15 p.s.i.g. to yield Conversion, vol. percent ------61.8 a catalyst having a lanthanum content of 10.2% by LHSV------4 Weight, determined as lanthanum oxide. 10 R.V.P. gaso., vol. percent ------54.0 5 Example 58 Excess C4's, vol. percent ------11.1 Cs-- gasoline, Vol. percent ------51.5 25 parts by weight of caustic treated McNamee clay Total C4's, Vol. percent ------13.7 was dispersed in 75 parts by weight of a silica lanthanum Dry gas, Wt. percent ------5.8 matrix consisting of 97% by weight of silica and 3% Coke, wt. percent ------2.0 20 by weight of lanthanum oxide. The resulting compo H2, wt. percent ------0.02 sition was then treated with a 2% solution of didynium chloride for 16 continuous hours and then with a 1% A advantage: solution of ammonium chloride for 24 hours. The result 10 R.V.P., vol. percent ------8.2 ing aluminosilicate was then washed with water until the Excess C4's, vol. percent ------3.3 effluent contained no chloride ions, dried and then treated C5+ gasoline, vol. percent ------8.0 25 for 24 hours at 1200 F. with steam at 15 p.s.i.g. to Total C4's, vol. percent ------2.8 yield a catalyst having a rare earth content of 9.45% Dry gas, Wt. percent ------2.2 by weight, determined as rare earth oxides. Coke, wt. percent ------2.8 The following table shows the cracking data of the Examples 55-67 illustrate the use of clays which have 30 catalyst when evaluated for cracking gas oil at 900 F.: been treated with caustic admixture with a source of silica, such as sand, silica gel or sodium silicate, calcined TABLE 41 at temperatures ranging from 350 F. to 1600 F., Cracking data: crushed, dispersed in water and digested. Conversion, vol. percent ------61.6 LHSV------4 Example 55 35 10 R.V.P. gaso., Vol. percent ------53.3 10% by weight of a McNamee clay which had been Excess C4's, Vol. percent ------10.8 caustic treated was dispersed in 90 parts by weight of Csh gasoline, vol. percent ------50.7 a silica alumina matrix. The resulting composition was Total C4's, Vol. percent ------13.4 treated with a 2% aqueous solution of lanthanum chlo 40 Dry gas, wt. percent ------5.9 ride for 16 continuous hours and then with a 1% by Coke, wt. percent ------2.5 weight solution of ammonium chloride for 24 continuous He wt. percent ------0.11 hours. The resulting aluminosilicate was washed with A advantage: water until the effluent contained no chloride ions, dried 10 R.V.P., Vol. percent ------7.6 and then treated for 24 hours at 1200 F. with steam Excess C4's, Vol. percent ------3.6 at 15 p.s.i.g. to yield a catalyst having a lanthanum con C5 gasoline, Vol. percent ------7.2 tent of 5.15, determined as lanthanum oxide. Total C4's, Vol. percent ------3.1 The following table shows the cracking data of the Dry gas, wt. percent ------2.0 catalyst when evaluated for cracking gas oil at 900 F.: Coke, wt. percent ------2.3 50 TABLE 40 Example 59 Cracking data: Conversion, vol. percent ------54.2 10 parts by weight of a caustic treated bentonite clay LHSV------4 was dispersed in 90 parts of a silica alumina matrix and 10 R.V.P. gaso., vol. percent ------48.8 the resulting composition was subjected to a 16 hour con Excess C4's, vol. percent ------9.8 tinuous treatment with an aqueous solution consisting of Cs-- gasoline, vol. percent ------46.6 2% by weight of lanthanum chloride and then with a 1% Total C4's, vol. percent ------11.9 aqueous solution of ammonium chloride for 24 continu Dry gas, wt. percent ------4.8 ous hours. The resulting aluminosilicate was then washed Coke, wt. percent ------1.4 with water until the effluent contained no chloride ions, 60 dried and then treated for 24 hours at 1200° F. to obtain H2, wt. percent ------0.04 a catalyst having a lanthanum content of 5.66% by weight. A advantage: The following table shows the cracking data of the 10 R.V.P., vol. percent ------6.9 catalyst when evaluated for cracking gas oil at 900 F.: Excess C4's, vol. percent ------2.0 Cs- gasoline, Vol. percent ------7.0 65 TABLE 42 Total C4's, Vol. percent ------2.1 Cracking data: Dry gas, wt. percent ------1.9 Conversion, vol. percent------51.1 Coke, wt. percent ------2.1 LHSV ------4 10 R.V.P. gaso., vol. percent.------44.6 Example 56 70 Excess C4's, Vol. percent------8.7 The process of Example 55 was repeated with the ex Cs-- gasoline, Vol. percent------42.3 ception that the matrix was a silica gel instead of the Total C4's, vol. percent------10.9 silica alumina employed. The resulting aluminosilicate Dry gas, Wt. percent------5.4 catalyst had a lanthanum oxide content of 6.06% by Coke, wt. percent------1.5 weight. 75 H2, Wt. percent------0.11 3,140,251 m 33 34 TABLE 42-Continued for 20 hours at 1225 F. with 100% atmospheric steam A advantage: to yield a catalyst having a sodium content of 0.56% by 10 R.V.P., Vol. percent------4.5 weight and a rare earth content of 8.2% by weight, de Excess C4's, Vol. percent------2.3 termined as rare earth oxides. C5+ gasoline------4.3 The following table shows the cracking data of the Total Ca's, vol. percent------2.3 catalyst when evaluated for cracking gas oil at 900 F.: Dry gas, wt. percent------0.8 Coke Wt. percent------1.6 TABLE 45 Example 60 Cracking data: O Conversion, vol. percent------46.2 10 parts by weight of halloysite clay which had been LHSV ------4 caustic treated was dispersed in 90 parts by weight of a 10 R.V.P. gaso., Vol. percent------40.0 silica alumina matrix and the resulting composition Excess C4's, Vol. percent------7.3 treated with a 2% by weight aqueous solution of a mix Cs-- gasoline, Vol. percent------37.7 ture of rare earth chlorides for 16 hours and then with a Total C4's, Vol. percent------9.6 1% by weight aqueous solution of ammonium chloride for 5 Dry gas, wt. percent------4.7 24 continuous hours. The aluminosilicate was then Coke, Wt. percent------2.6 washed with water until the effluent contained no chloride H2 Wt. percent------0.22 ions, dried and then treated for 24 hours at 1200 F. with A advantage: - steam at a pressure of 15 p.s.i.g. to yield a catalyst having 20 10 R.V.P., Vol. percent.------2.5 a rare earth content of 6.08. Excess C4's, vol. percent------2.2 The following table shows the cracking data of the Cs- gasoline, Vol. percent------2.6 catalyst when evaluated for cracking gas oil at 900 F.: Total C4's, Vol. percent------2.2 TABLE 43 Dry gas, Wt. percent------0.7 Cracking data: 25 Coke, wt. percent------0.2 Conversion, Vol. percent------57.6 LHSV ------4. Example 63 10 R.V.P. gaso., vol. percent------50.6 Excess C4's, Vol. percent------10.9 25 parts by weight of a caustic treated Dixie clay was Cs-- gasoline, vol. percent------48.3 30 dispersed into a silica alumina matrix and the resulting Total C's, Vol. percent------3.4 composition was subjected to 4 two-hour treatments with Dry gas, wt. percent------5.3 a 2% aqueous solution of calcium chloride and then to 8 Coke, Wt. percent.------7 two-hour treatments with a solution consisting of 2% H2, wt. percent------0.03 by weight of calcium chloride and 1% by weight of am A advantage: 35 monium chloride. The resulting aluminosilicate Was then 10 R.V.P., Vol. percent------7.0 washed with water until the effluent contained no Excess C4's, Vol. percent------2.1 chloride ions, dried and then treated for 20 hours at 1225 Cs+ gasoline, Vol. percent------6.8 F. with 100% atmospheric steam to yield a catalyst hav Total C's, Vol. percent------1.7 ing a calcium content of 3.88% by Weight. Dry gas, Wt. percent------2.0 40 Coke, Wt. percent ------2.5 Example 64 Example 61 McNamee clay, an aluminosilicate which had been caustic treated, was subjected to treatment with an aqueous The procedure of Example 60 was repeated with the solution consisting of 5% by weight of a mixture of rare exception that a 2% by weight aqueous solution of lan 45 thanum chloride was employed instead of the rare earth earth chlorides and 2% by weight ammonium chloride. chloride solution. The resulting catalyst had a lanthanum The aluminosilicate was then washed with water until the content of 6.82% by weight and the cracking data shown effluent contained no chloride ions and treated for 20 in the following table: hours at 1225 F. with steam at atmospheric pressure. TABLE 44 50 The resulting aluminosilicate was evaluated for cracking Cracking data: gas oil at 900 F. and gave the following results: Conversion, vol. percent.------58.4 TABLE 46 LHSV ------4 10 R.V.P. gaso., vol. percent------49.3 Cracking data: Excess C4's, Vol. percent------1.3 55 Conversion, vol. percent ------57.2 Cs-- gasoline, Vol. percent------47.0 LHSV------16 Total C4's, Vol. percent------13.6 10 R.V.P. gaso, Vol. percent ------49.9 Dry gas, Wt. percent------6.3 Excess C4's, Vol. percent ------9.5 Coke, wt. percent------2.0 Cs-- gasoline, vol. percent ------47.4 H2, wt. percent------0.03 60 Total C4's, Vol. percent ------12.0 A advantage: 10 R.V.P., Vol. percent------5.3 Dry gas, wt. percent ------5.6 Excess CA's, Vol. percent------1.9 Coke, Wt. percent ------2.8 Cs-- gasoline, Vol. percent.------5.2 H2 Wt. percent ------0.05 Total C's, Vol. percent------1.8 65 A advantage: Dry gas, Wt, percent------1.1 10 R.V.P., vol. percent ------6.5 Coke, wt. percent.------2.3 Excess Ca's, vol. percent ------3.2 Example 62 Cs-- gasoline, vol. percent ------6.2 25 parts by weight of a caustic treated Dixie clay was Total C4's, vol. percent ------3.0 dispersed into a silica alumina matrix and the composi 70 Dry gas, Wt, percent ------1.6 tion was treated with an aqueous solution consisting of Coke, wt. percent ------1.2 1% by weight of a mixture of rare earth chlorides and 1% by weight ammonium chloride for 24 continuous hours. 1. AOs. 39.85 wt. percent, SiO2-44.9 wt. percent, Fe2O8 The aluminosilicate was then washed with water until the 0.35 wt. percent, TiO-0.73 wt. percent, CaO-trace, MgO effluent contained no chloride ions, dried and then treated 75 trace, NaO-0.12 wt. percent, K.O-0.10 wt. percent. 3,140,251 35 36 Example 65 The cracking properties of the resulting catalyst are Dixie clay, an aluminosilicate, which had been caustic shown in the following table when it was evaluated for treated, was treated with an aqueous solution consisting cracking gas oil at 900 F.: of 5% by weight mixture of rare earth chlorides and 2% by weight of ammonium chloride for 2 treatments of 24 TABLE 47 hours each. The aluminosilicate was then washed with Cracking data: water until the effluent contained no chloride ions, dried Conversion, vol. percent ------62.2 and treated with steam for 20 hours at 1225 F. at atmos LHSV------4 pheric pressure. 10 R.V.P. gaso., vol. percent ------51.6 The catalytic evaluation of the resulting aluminosilicate 0. Excess C4's, vol. percent ------12.1 is shown in the following table for cracking gas oil at C5+ gasoline, vol. percent ------49.2 900 F.: Total Ca's, Vol. percent ------14.5 Dry gas, Wt. percent ------6.9 TABLE 47 Coke, wt. percent ------3.2 15 H2, wt. percent ------0.03 Cracking data: A advantage: Conversion, vol. percent ------36.9 10 R.V.P., vol. percent ------5.6 LHSV------10 Excess C4's, Vol. percent ------2.4 10 R.V.P. gaso, vol. percent ------36.2 Cs-- gasoline, vol. percent ------5.4 Excess Ca's, vol. percent ------2.0 20 Total Ca's, Vol. percent ------2.2 Cs-- gasoline, Vol. percent ------33.7 Dry gas, wt. percent ------1.1 Total Ca's, Vol. percent ------4.5 Coke, wt. percent ------1.8 Dry gas, wt. percent ------3.5 Coke, wt. percent ------1.8 What is claimed is: H2, wt. percent ------0.15 25 1. In the catalytic cracking of a hydrocarbon oil to produce hydrocarbons of lower boiling range, the im A advantage: provement of contacting said oil under cracking condi 10 R.V.P., vol. percent ------4.2 tions with discrete particles of a catalyst composition Excess C4's, vol. percent ------5.0 consisting of an inorganic oxide matrix with a crystalline Cs+ gasoline, Vol. percent ------4.0 30 aluminosilicate containing from 0.5 to 1.0 equivalents Total CA's, Vol. percent ------4.8 per gram atom of aluminum of ions of positive valence Dry gas, wt. percent ------0.5 consisting of both hydrogen ions and cations of metals Coke, wt. percent ------0.3 selected from Groups IB through VIII of the Periodic Table characterized by containing from 0.01 to 0.99 Example 66 35 equivalent of hydrogen ion per gram atom of aluminum and from 0.99 to 0.01 equivalent per gram atom of Bentonite, an aluminosilicate, which had been caustic aluminum, of cations of metals selected from Group IB treated, was treated with an aqueous solution consisting of through Group VIII of the Periodic Table. 5% by weight of a mixture of rare earth chlorides and 2. In the catalytic cracking of a hydrocarbon oil to 2% by weight of ammonium chloride. The treated alu 40 produce hydrocarbons of lower boiling range, the im minosilicate was then washed with water until there was provement of contacting said oil under cracking condi no chloride ions in the effluent, dried and then treated with tions with discrete particles of a catalyst composition steam for 24 hours at 1200 F. at a pressure of 15 p.s.i.g. consisting of an inorganic oxide matrix with a crystalline The resulting aluminosilicate contained 0.2% by Weight aluminosilicate containing from 0.8 to 1.0 equivalent calcium and possessed excellent catalytic properties. 45 per gram atom of aluminum of ions of positive valence consisting of both hydrogen ions and cations of metals Example 67 selected from Groups IB through VIII of the Periodic Table characterized by containing from 0.01 to 0.99 A silicate solution was prepared by adding 2.28 lbs. of equivalent of hydrogen ion per gram atom of aluminum an aluminosilicate identified as Zeolite 13X which had 50 and from 0.99 to 0.01 equivalent, per gram atom of been treated with rare earth chlorides and 6.25 lbs. of aluminum, of cations of metals selected from Group IB water. To this was added 13.9 lbs. of sodium silicate and through Group VIII of the Periodic Table. 7.02 lbs. of water, with constant stirring. An acid solu 3. In the catalytic cracking of hydrocarbon oil to tion was then prepared by mixing 28.55 lbs. of water, produce hydrocarbons of lower boiling range, the im 2.12 lbs. of Al(SO4). 18H2O, and 0.97 lb. of 96.7 weight 55 provement of contacting said oil under cracking condi percent sulfuric acid. The silicate and the acid solution tions with discrete particles of a catalyst composition were mixed continuously through a nozzle adding 492 cc. consisting of an inorganic oxide matrix with a crystalline per minute of the silicate solution at 67° F. to 390 cc. aluminosilicate containing 1.0 equivalent per gram atom per minute of the acid solution at 42 F. to form a hydro of aluminum of positive ions consisting of both hydro sol having a pH of 8.5 which gelled to a firm hydrogel in 60 gen ions and cations of metals selected from Group IB 1.9 seconds at 63 F. The hydrogel was then formed through Group VIII of the Periodic Table character into a bead in a conventional manner and was treated ized by containing from 0.01 to 0.99 equivalent of hy with 1% solution of ammonium chloride using 3 over drogen ion per gram atom of aluminum and from 0.99 night and 9 two-hour contacts at room temperature. The to 0.01 equivalent, per gram atom of aluminum, of ca 65 tions of metals selected from Group IB through Group aluminosilicate was washed with water until the effluent VII of the Periodic Table. contained no chloride ions, dried for 20 hours at 275 F., 4. In the catalytic cracking of a hydrocarbon oil to calcined for 10 hours at 1000 F. and then treated for 30 produce hydrocarbons of lower boiling range, the im hours at 1200 F. with steam at 15 p.s.i.g. The resulting provement of contacting said oil under cracking condi catalyst had a sodium content of 0.05% by weight and 70 tions with discrete particles of a catalyst composition a rare earth content of 7.16% by weight determined as consisting of an inorganic oxide matrix with a crystalline rare earth oxides. aluminosilicate containing from 0.5 to 1.0 equivalent of ions of positive valence per gram atom of aluminum 44.51 wt. percent Ale08, 38.51 wt. percent SiO2, 1.27 wt. percent Fe2Oa, 147 wt. percent TiO2, 0.08 wt. percent CaO, consisting of both hydrogen ions and calcium ions 0.12 wt. percent MgO, 0.08 wt. percent NA2O. 75 characterized by containing from 0.01 to 0.99 equivalent 3,140,251 37 38 of hydrogen ion per gram atom of aluminum and from 15. A process for converting a hydrocarbon charge 0.99 to 0.01 equivalent per gram atom of aluminum of which comprises contacting the same under conversion calcium ions. conditions with a catalyst comprising a crystalline alu 5. In the catalytic cracking of a hydrocarbon oil to minosilicate containing from 0.5 to 1.0 equivalent per produce hydrocarbons of lower boiling range, the im gram atom of aluminum of ions of positive valence con provement of contacting said oil under cracking condi sisting of both hydrogen ions and cations of metals select tions with discrete particles of a catalyst composition ed from Group IB through Group VIII of the Periodic consisting of an inorganic oxide matrix with a crystalline Table characterized by containing from 0.01 to 0.99 aluminosilicate containing from 0.8 to 1.0 equivalent equivalent per gram atom of aluminum, of hydrogen of ions of positive valence per gram atom of aluminum ion, and from 0.99 to 0.01 equivalent, per gram atom consisting of both hydrogen ions and calcium ions where of aluminum, of cations of metals selected from Group in the calcium ions comprise from 40 to 85% of the IB through Group VIII of the Periodic Table, which total equivalents of ions of positive valence. aluminosilicate is contained in and distributed through 6. In the catalytic cracking of a hydrocarbon oil to out a matrix therefor. produce hydrocarbons of lower boiling range, the im 5 16. The process of claim 2 wherein the metal cations provement of contacting said oil under cracking condi are cations of trivalent metals. tions with discrete particles of a catalyst composition 17. The process of claim 2 wherein the metal cations consisting of an inorganic oxide matrix with a crystalline are cations of divalent metals. aluminosilicate containing from 0.5 to 1.0 equivalent 18. In the catalytic cracking of hydrocarbon oil to of ions of positive valence per gram atom of aluminum 20 produce hydrocarbons of lower boiling range, the im consisting of both hydrogen ions and magnesium ions provement of contacting said oil under cracking condi wherein the magnesium ions comprise from 40 to 85% tions with discrete particles of a catalyst composition of the total equivalents of ions of positive valence. consisting of an inorganic oxide matrix with a crystalline 7. In the catalytic cracking of a hydrocarbon oil to aluminosilicate having no more than 0.25 equivalent produce hydrocarbons of lower boiling range, the im 25 per gram atom of aluminum of alkali metal cations and provement of contacting said oil under cracking condi containing from 0.8 to 1.0 equivalent per gram atom tions with discrete particles of a catalyst composition of aluminum of ions of positive valence consisting of consisting of an inorganic oxide matrix with a crystalline both hydrogen ions and cations of metals selected from aluminosilicate containing from 0.8 to 1.0 equivalent Group IB through Group VIII of the Periodic Table. of ions of positive valence per gram atom of aluminum 30 19. In a process for the cracking of a hydrocarbon consisting of both hydrogen ions and magnesium ions charge with a solid porous catalyst wherein the products wherein the magnesium ions comprise 40 to 85% of the obtained comprise both economically valuable liquid hy total equivalents of ions of positive valence. drocarbons boiling in the motor fuel range and unde 8. In the catalytic cracking of a hydrocarbon oil to sirable by-products of lesser economic significance, the produce hydrocarbons of lower boiling range, the im 35 provement of contacting said oil under cracking condi improvement in selectively evidenced by the production tions with discrete particles of a catalyst composition of a substantially greater amount of said valuable liquid consisting of an inorganic oxide matrix with a crystalline hydrocarbons together with concomitant reduction in aluminosilicate containing 1.0 equivalent per gram atom the yield of undesired by-products from a given hydro of aluminum of ions of positive valence consisting of 40 carbon charge, which comprises contacting said charge both hydrogen ions and magnesium ions wherein the under cracking conditions with a catalyst composition magnesium ions comprise 40 to 85% of the total equiv comprising an inorganic oxide matrix having dispersed alents of ions of positive valence. therein an aluminosilicate having an ordered crystalline 9. The process of claim 2 wherein the aluminosilicate structure and containing from 0.5 to 1.0 equivalent per has an atomic ratio of silicon to aluminum greater than 45 gram atom of aluminum of ions of positive valence where 1.6. in the enhanced selectivity of said catalyst composition 10. The process of claim 2 wherein the aluminosilicate arises from the fact that the aluminosilicate has associated has an atomic ratio of silicon to aluminum greater than therewith both hydrogen ions and cations of metals select 2.7. ed from Group B through Group VIII of the Periodic 11. The process of claim 5 wherein the aluminosilicate 50 Table. has an atomic ratio of silicon to aluminum greater than 1.6. 12. The process of claim 5 wherein the aluminosilicate References Cited in the file of this patent has an atomic ratio of silicon to aluminum greater than UNITED STATES PATENTS 2.7. 55 13. The process of claim 7 wherein the aluminosilicate 2,369,074 Pitzer ------Feb. 6, 1945 has an atomic ratio of silicon to aluminum greater than 2.962,435 Fleck et al. ------Nov. 29, 1960 1.6. 2.971,903 Kimberlin et al. ------Feb. 14, 1961 14. The process of claim 7 wherein the aluminosilicate 2,971,904 GladroW et al. ------Feb. 14, 1961 has an atomic ratio of silicon to aluminum greater than 60 3,033,778 Frilette ------May 8, 1962 2.7.