Patented Oct. 29, 1946 2,410,044. UNITED STATES PATENT OFFICE‘ 2,410,044 HYDROCARBON OATALYZING PROCESS Robert E. Burk and Everett 0. Hughes, Cleve land Heights, Ohio, assignors to The Standard Oil Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application May 29, 1941, 1 Serial No. 395,827 5 Claims. (Cl. 260——668) This invention relates to catalysis, and more particularly catalysis involving operation on hy drocarbons; and it is among the objects of the invention to provide improved operating e?‘i 2 onally adjacent atomic numbers 4 and 13 in the periodic table and chromium may be combined. Thus, antimony chloride and aluminum nitrate and chromium nitrate at the rate of 34.2, 2512 ciency, and without undue complication. Other 5 and 713 g. respectively per 18.8 liters of distilled objects and advantages will appear as the de water, being brought into solution, the solution is scription proceeds. warmed and with vigorous agitation ammonium To the accomplishment of the foregoing and hydroxide is introduced at the rate of 2310 g. of related ends, the invention, then, comprises the concentrated ammonium hydroxide with 1500 g. features hereinafter fully described, and particu 10 of ammonium acetate per 11.2 liters of distilled larly pointed out in the claims, the following de water. Again similarly, SnCh and Be(NO3) z and scription setting forth in detail certain illustra C‘r(NOa)s may be dissolved at the rate of 78.2, tive embodiments of the invention, these being 1550 and 713 g. respectively per 18.8 liters of dis indicative, however, of but a few of the various , tilled water, and the solution being warmed and Ways in which the principle of the invention may 15 agitated ammonium hydroxide is introduced at be employed. the rate of 1820 g. of concentrated (28%) ammo The raw material for reaction may be non nium hydroxide and ammonium acetate 1,500 g, benzenoid hydrocarbons, or fractions containing in 11.2 liters of distilled water. them, etc., as more particularly detailed herein Where a part of the tin or aluminum is replaced after, and it is subjected to the action of a com 20 by antimony or beryllium respectively, the cata pound catalyst of peculiar character, and heat. lyst involves tin and antimony and aluminum and This catalyst may be prepared preferably from chromium, or beryllium and aluminum and tin soluble salts of tin, aluminum and chromium for and chromium, or beryllium and aluminum and example by dissolving the salts in water at the tin and antimony and chromium, etc., on the lines rate of one mol percent of tin, seventy-nine mol 25 as indicated and within the proportions stated for per cent of aluminum and twenty mol per cent of the permissible ranges of the tin and aluminum chromium, and the solution is treated with am components, the generic properties of the catalyst monia to neutralization. Thus, tin chloride and being maintained. aluminum nitrate and chromium nitrate at the The compound catalyst is suitably granulated rate of 39.1, 2512, and ‘71.3 g, respectively, based 30 to provide interstitial spaces for passage of the on anhydrous salts, per 18.8 liters of distilled material to be treated, in adequate contact, and water, being brought into solution, the solution is is arranged in a reaction zone with adeguate warmed to about 55° 0., and being introduced into heating means, such that the temperature of the a container provided with an agitator, concen mass may be maintained at 800-l200° F., the trated ammonium hydroxide 2310 g. and 1500 g. . raw material being passed into contact with the ammonium acetate per 112 liters of distilled wa catalyst. The raw material generally involves ter is supplied. A blue-green precipitate is non-benzenoid hydrocarbons, as aliphatic hydro formed which is allowed to settle for about two carbons or paraf?ns and ole?ns and naphthenic hours, and the cake‘ resulting is washed three hydrocarbons or their mixtures, naphthas, dis times by dispersion into four liters of water, and is tillates, as naphthas or distillates from stocks ?ltered. The precipitate is dried at about 140° which are predominantly non-benzenoid, as for 15"., and then under vacuum‘ at about 400° F. A instance derived from Pennsylvania, Michigan, vitreous gel results. The proportions of tin and Kentucky, Ohio, Mid-Continent and the like pe aluminum and chromium are most desirably troleum, and therewith a gas providing hydrogen. those as above-indicated, but in general the tin " Hydrogen as occurrent in the off-gas may be em need not advisably be less than one or more than ployed, or relatively pure hydrogen. The hydro thirty mol per cent and the aluminum not less gen in the catalyst zone may be from 40-400 than ?fty nor more than ninety mol per cent, the pounds per square inch, Desirably also, butanes remainder being chromium. In some instances or four carbon atom gaseous hydrocarbons may antimony may replace all or part of the tin. 50 also be supplied, Such may be provided by the Again in some instances beryllium may replace oil-gas, or from special sources, as convenient. all or part of the aluminum. That is, an element When butanes are also included in the material from the group of laterally adjacent atomic num fed to the catalyst zone in excess of the mols of bers 50 and 51 in the periodic table and an amphoteric oxide forming element from the diag normally liquid hydrocarbon charged, the pres 55 sure may be as high as 800 pounds per square 2,410,044 3 inch. Conveniently, the gases formed may be re cycled, by adding such gas or any portion thereof to the naphtha vapors for passage over the cata lyst. Or, these gases may be added in successive portions to different, but not necessarily consecu tive, bodies in‘apparatus where arrangement of 4 We therefore particularly point out and dis tinctly claim as our invention: 1. In a process of aromatizing, subjecting hy drogen and a hydrocarbon of four carbon atoms and a naphtha containing non-benzenoid hydro carbons," at elevated pressure and la'ltemperature of 800-1200" "F., to the ‘action of an oxide con the catalyst is in a series of bodies. With this tact-mass formed from co-precipitation from dis combination of normally gaseous and normally solved salts of tin and aluminum and chromium, liquid hydrocarbons, an advantageous feature is that the catalyst does not tend to accumulate .10 the tin in the contact-mass being 1-30 mol per coke quickly, and at the same time a component cent. _2. In a process of aromatizing, subjecting of heat is generated in situ in the catalyst bed by hydrogen and a hydrocarbon of four carbon atoms the combining of hydrogen in ‘a reaction. ‘Flow and a naphtha containing non-benzenoid hydro rates of naphtha may be 0.1-10 liquid volumes carbons, at elevated pressure and a temperature per volume of catalyst per hour. ‘At the higher of»800-l200°'TF., to the action of an oxide con temperatures correspondingly shorter contact ' time may be used. Hydrogen is fed at the rate of 0.1-10 mols of H2 per mol of naphtha. And where hydrocarbons such as butane or isobutane are Provided, their feed rate may be l-lO mols thereof per mol of naphtha. tact-mass formed from col-precipitation from dissolved salts of antimony, aluminum and chromium, the antimony in the contact-mass be ing 1-30 mol per cent. 3. In a process of "aromatizing, subjecting ‘hy drogen and a hydrocarbon of four carbon atoms "After contacting with ‘the catalyst, aromatic and a naphtha containing non-benzenoid hydro and unsaturated hydrocarbons may be extracted carbons, at elevated pressure and a temperature orpartially extracted from the products, for ex ample by mixing with a solvent having‘ the se 25 of 800—1200° F., to the action of an oxide contact mass formed from co-precipitation from dissolved lective character of ‘sulphur dioxide, or a high salts of tin and beryllium and chromium, the tin boiling amine, or hydroxy compound, or other in the contact-mass being 1-30 mol per cent. solvents 'or combinations of such solvents ‘and 4. In a process of ‘aromatizing, subjecting hy the undissolved or non-benzenoid portion may be drogen' and a hydrocarbon of four carbon atoms re-passed into contact with the catalyst. The and a naphtha containing non-benzenoid hydro gases formed may be recycled in whole or in part. carbons, at elevated pressure and a temperature v'I‘he catalyst may be regenerated in situ by sup of 809-l200° R, to the action of an oxide contact plying to it, the temperature being 800-1200° II, oxygen-containing gas suchas air, or air diluted » mass formed from co-precipitation from "dis solved salts of chromiumand an amphoteric oxide ‘with forv instance ?ue gas. forming element from the group consisting of Operating with a naphtha for instance, at 980° beryllium and aluminum, and another oxide ‘F. and '100 pounds pressure, in a run for ?ve forming element from thegroup consisting of tin hours, and the flow rate of'naphtha 1.4 v. v. h. and antimony, such amphoteric oxide forming and gas providing hydrogen at a 3:1 ratio of hy drogento the hydrocarbon, the catalyst being a 40 element and other oxide forming element in the contact-mass being "50-90 mol per cent and 1-30 co-precipitated catalyst of 1 per cent of tin oxide, mol per cent respectively. '79 per cent of ‘aluminum oxide and 20 per cent of 5. In a process of aromatizing, subjecting hy chromium oxide, a yield of 81.5 per cent con drogen’and a hydrocarbon of four carbon atoms densate having a Kattwinkel test corresponding : 'anda normally liquid no'n-benzenoid hydrocar to61 per cent-aromatics and unsaturated hydro bonpatelevated pressure and a temperature of carbons is obtained. In an analogous run with a 800-1200° to the action of an oxide contact catalyst of co-precipitated character involving 1 mass formed from co-precipitation from ’ dis per cent of antimony oxide, '79 per cent of alu solved salts of chromium and an amphoteric oxide minum oxide and 20 per cent of chromium oxide, ‘a liquid yield of 80 per cent having a Kattwinkel 50 forming‘element from the group consisting of beryllium and aluminum, and another oxide test ‘of '60 per cent was obtained. forming element from the group consisting of tin This application is a continuation, in part, and and antimony, such amphoteric' oxide forming as to common subject matter, of our application element and other oxide forming'element in the "Serial'No. 228,005, ?led Sept. 1.1938. Other modes of applying the principle of the 55 contact-‘mass being 50-90'mol per cent and 1-30 invention ‘may be employed, change being made as regards the details described, provided the ‘features stated in any of the following‘claims, or the equivalent of such, be employed. mol-per cent respectively. ‘ROBERT E.'BURK. EVERETT C.’ HUGHES.