US3247099A

US3247099A - Catalytic reforming

Info

Publication number: US3247099A
Application number: US185225A
Authority: US
Inventors: Stephen M Oleck; Stephen J Wantuck
Original assignee: Socony Mobil Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1962-04-05
Filing date: 1962-04-05
Publication date: 1966-04-19
Anticipated expiration: 1983-04-19

Description

United States Patent 3,247,099 CATALYTIW REFORMING Stephen M. Qleck, Moorestown, and Stephen J. Wantuck, West Collingswood, N.Il., assignors to Socony Mobil Oil @ompany, Inc, a corporation of New York No Drawing. Filed Apr. 5, 1962, Ser. No. 185,225 9 Claims. (Cl. 208-138) This invention relates to an improved catalytic reforming process for obtaining gasoline of high octane number. More particularly, the present invention is directed to catalytic reformng carried out in the presence of an unusual catalyst characterized by exceptional activity and selectivity.

Reforming operations, wherein hydrocarbon fractions such as naphthas, gasolines, and kerosene are treated to improve the anti-knock characteristics thereof are well known in the petroleum industry. These fractions are composed predominately of normal and slightly branched parafiinic hydrocarbons and naphthenic hydrocarbons together with small amounts of aromatic hydrocarbons. During reforming a multitude of reactions take place ineluding isomerization, aromatization, dehydrogenation, cyclization, etc., to yield a product having an increased content of aromatics and highly-branched paraflins. Thus, in reforming, it is desired to dehydrogenate the naphthenic hydrocarbons to produce aromatics, to cyclize the straight chain paraffinic hydrocarbons to form aromatics, to isomerize the normal and slightly branched paraflins to yield highly branched chain paraffins and to effect a controlled type of cracking which is selective both in quality and quantity.

Normal and slightly branched-chain paraffinic hydrocarbons of the type contained in the above fractions have relatively low octane ratings. Highly branched-chain paraffinic hydrocarbons, on the other hand, are characterized by high octane ratings. Accordingly, one objective of reforming is to effect isomerization of the normal and slightly branched-chain parafiins to more highly branched-chain paraffins. Since aromatic hydrocarbons have much higher octane ratings than naphthenic hydro carbons, it is also an objective of reforming to simultaneously produce aromatics in good yield. The production of aromatic hydrocarbons during reforming is effected by dehydrogenation of the naphthenic hydrocarbons and dehydrocyclization of the parafiinic hydrocarbons. Aromatic hydrocarbons are also produced by isomerization of alkyl cyclopentanes to cyclohexanes which thereafter undergo dehydrogenation to form the desired aromatics.

During reforming, it is extremely important to produce as little carbon and normally gaseous product material as is possible, since such materials represent essentially an economic loss to be charged against the process. The property of the catalyst which is instrumental in effecting high yields of normally liquid product is referred to as selectivity, and this property is measured as the quantity of normally liquid product, substantially free of hydrocarbons containing four or less carbon atoms, which is produced at a given octane level. Large improvements in selectivity are not very probable, since it appears that there is a limit to the quantity of normally liquid product material which can be produced, as it is unavoidable to obtain some carbon and normally gaseous product material at the elevated temperatures employed for reforming. Consequently, any increase in selectivity to the extent of at least one-half of a percent is considered significant by reason of the difficulty in obtaining such an improvement as well as the economic advantage which results therefrom. It has been found, in accordance with the present invention, that reforming may be efiiciently accomplished in the presence of a catalytic composition comprising as an active component a rare earth metalcontaining aluminosilicate having intimately combined therewith a minor proportion of a metal of the platinum series.

In one embodiment, the present invention provides a method for reforming hydrocarbon mixtures by contacting the same under reforming conditions with a catalyst comprising at least one metal of the platinum series in intimate combination with a rare earth metal aluminosilicate, resulting from base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units with rare earth metal ions to replace at least about 75 percent of the original alkali metal content of the alkali metal aluminasilicate with said ions and to effectively reduce the alkali metal content of the resulting composite to below 4 percent by Weight, washing the base-exchanged material free of soluble salts, drying and thereafter thermally activating the product by heating at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours.

In another embodiment, thepresent invention provides a process for reforming. a petroleum distillate boiling within the approximate range of F. to 450 F. by contacting the same under reforming conditions with a catalyst having exceptional activity and selectivity prepared by contacting a crystalline alkali metal aluminosilicate zeolite'having uniform pore openings between 6 and 15 Angstrom units with a solution of rare earth metal ions to effect .baseexchange of at least about percent of the alkali metal ions of said zeolite with the aforesaidrare earth metal ions and to effectively reduce the content of alkali metal of the resulting composite to below.4 percent by weight, washing the base-exchanged material free of soluble salts, drying and thermally activating the washed product by heating to a temperature in the approximate range of 500 to 1500 F. to effect at least partial conversion of the metal ion introduced by base-exchange to a catalytically active state and. impregnating the resulting rare earth metal aluminosilicate with between about 0.01 and about 5 percent by weight of a metal of the platinum series.

' Another embodiment of the invention affords a process for reforming a petroleum naphtha by bringing the same into contact under reforming conditions with a' catalyst consisting essentially of a metal of the platinum series combined with a rare earth metal aluminosilicate resulting from contact with a crystalline alkali metal aluminosilicate zeolite having uniform pore openings between 6 and 15 Angstrom units with a solution of an ionizable rare earth metal compound to replace by base exchange, at least percent of the alkali metal content of the zeolite with rare earth metal ions and to effectively reduce the alkali metal content thereof below about 1 percent by weight, washing the base-exchanged material free of soluble salts, drying and thermally activating the washed product by heating to a temperature in the approximate 3 range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours.

The crystalline alkali metal aluminosilicates employed in the preparation of the catalysts described herein are zeolites. Such substances have been generally described by Barrer in several publications and in U.S. 2,306,610 and U.S. 2,413,134. These materials are essentially the dehydrated forms of crystalline, natural or synthetic hydrous siliceous zeolites containing varying quantities of alkali metal, silicon and aluminum with or without other metals. The alkali metal atoms, silicon, aluminum and oxygen in these zeolites are arranged in the form of an aluminosilicate salt in a definite and consistent crystalline pattern. The structure contains a large number of small cavities interconnected by a number of still smaller holes or channels. These cavities and channels are precisely uniform in size. The alkali metal aluminosilicate zeolite used in preparation of the catalysts described herein has a uniform pore structure comprising openings characterized by an effective pore diameter of between 6 and 15 Angstroms. A typical commercially available zeolite fulfilling the above requirements is the X type zeolite and, specifically, 13X zeolite marketed by the Linde Division of Union Carbide Corporation and described in U.S. 2,882,244.

In general, the process for preparing such alkali metal aluminosilicates involves heating, in aqueous solution, an appropriate mixture of oxides or of materials whose chemical composition can be completely represented as a mixture of oxides Na O, A1 SiO and H 0 at a temperature of approximately 100 C. for periods of 15 minutes to 90 hours or more. The product which crystallizes within this hot mixture is separated therefrom and water washed until the water in equilibrium with the zeolite has a pH in the range of 9 to 12 and, thereafter, is dehydrated by heating. Generally, an alkali metal silicate serves as the source of silica and an alkali metal aluminate as the source of alumina. An alkali metal hydroxide is suitably used as the source of the alkali metal ions and, in addition, contributes to the regulation of the pH. All reagents are preferably soluble in water. While it is contemplated that alkali metal aluminosilicates having the above-designated pore characteristics may be employed in preparation of the described catalysts, it is generally preferred to use a sodium aluminosilicate. Thus, assuming sodium as the alkali metal, the reaction mixture should contain a molar ratio of Na O/SiO of at least 0.5/1 and, generally, not in excess of 2/1. Sodium aluminate having a molar ratio of Na O/Al O in the range of 1/1 to 3/1 may be employed. The amounts of sodium silicate solution and sodium aluminate solution are such that the molar ratio of silica to alumina in the final mixture is at least 2.2/1. Preferably, the solution has a composition expressed as mixtures of oxides within the following ranges: SiO /Al O of 3 to 5, Na O/SiO of 1.2 to 1.5 and H O/Na O of 35 to 60. The reaction mixture is placed in a suitable vessel which is closed to the atmosphere in order to avoid losses of water and reagents are then heated for an appropriate length of time. A convenient and generally employed process for making the sodium aluminosilicate reactant involves reaction of aqueous solutions of sodium aluminate and sodium silicate to which may be added sodium hydroxide. While satisfactory crystallization may be obtained at temperatures from 21 C. to 150 C., the pressure being atmospheric or less, corresponding to the equilibrium of the vapor pressure with the mixture at the reaction temperature, crystallization is ordinarily carried out at about 100 C. As soon as the zeolite crystals are completely formed they retain their structure and it is not essential to maintain the temperature of the reactant any longer in order to obtain a maximum yield of crystals.

After formation, the crystalline zeolite is separated from the mother liquor usually by filtration. The crystalline mass is then washed, preferably with water and while on the filter until the wash water in equilibrium with the zeolite reaches a pH of 9 to 12.

The catalysts utilized in the present process are prepared by base-exchanging a crystalline alkali metal aluminosilicate such as described hereinabove having a structure of rigid three-dimensional networks characterized by a uniform pore diameter between 6 and 15 Angstrom units with rare earth metal ions and thereafter washing the base-exchanged material free of soluble salts, drying the washed composite and subjecting the same to a thermal activating treatment.

The base-exchange solutions employed may be contacted with the crystalline zeolite of uniform pore structure as formed, after washing free of soluble salts or in the form of a fine powder, a compressed pellet, extruded pellet, or other suitable particle shape. When in the form of a pellet the crystalline zeolite may be combined with a binder such as clay. It has been established that the desired base-exchange may be effected most readily for "the alkali metal aluminosilicate zeolite undergoing treatment which has not previously been subjected to a temperature above about 600 F.

Base-exchange required for introducing the aforementioned rare earth metal ions may be accomplished by contacting the alkali metal aluminosilicate zeolite for a sufiicient period of time and under appropriate temperature conditions to replace at least about 75 percent and, preferably, at least about percent of the alkali metal contained in the aluminosilicate zeolite with ions of rare earth metal to effectively reduce the content of alkali metal of the resulting composite to below 4 weight percent and preferably less than 1 weight percent.

It is contemplated that any of the readily available rare earth metal compounds may be employed for the above purpose. Generally, compounds will be used wherein the rare earth metal-containing ion is present in the cationic state. Representative rare earth metal compounds include nitrates, bromides, acetates, chlorides, iodides and sulfates of one or more of the rare earth metals including cerium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Naturally occurring rare earth minerals offer a convenient source for the rare earth metals. The natural rare earth metal-containing mineral may be extracted with an acid such as sulfuric, or rare earth oxides and related metal oxides in admixture from a natural earth may be dissolved in other solubilizing acids such as acetic. For example, monazite which contains cerium compounds as the principal rare earth metal compound present with lesser portions of thorium compounds and other rare earth compounds may be used as as a suitable source of cerium. Mixtures of rare earth metal salts, for example, chlorides of lanthanum, cerium, praseodymium, neodymium, samarium and gadolinium available commercially at a relatively low cost may be effectively employed.

While water will ordinarily be the solvent in the baseexchange solutions used, it is contemplated that other solvents, although generally less preferred, may be used; in which case, it will be realized that the above list of representative rare earth metal compounds may be expanded. Thus, in addition to aqueous solutions, alcoholic solutions, etc., of the rare earth metal-containing compounds may be employed in producing the catalyst utilized in the present process. It will be understood that such rare earth metal compounds employed undergo ionization in the particular solvent used.

The concentration of rare earth metal compound employed in the base-exchange solutions may vary depending on the alkali metal aluminosilicate undergoing treatment and on the conditions under which treatment is effected. The overall concentrations of replacing metal ions, however, is such as to reduce the alkali metal content of the original alkali metal aluminosilicate to less than 4, and preferably, less than 1 weight percent. In base-exchanging the alkali metal aluminosilicate with a solution of a rare earth metal compound generally the concentration of such compound is within the range of l to 30 percent by weight. The pH of such exchange solution is generally within the approximate range of 3.5 to 6.5 and, preferably, between about 4 and about 5.5.

The temperature at which base-exchange is effected may vary widely, generally ranging from room temperature to an elevated temperature below the boiling point of the treating solution. The volume of base-exchange solution employed in any instance may vary widely. Generally, however, an excess is employed and such excess is removed from contact with the crystalline aluminosilicate zeolite after a suitable period of contact. The time of contact between the base-exchange solution and crystalline zeolite in any instance is such as to effect substantial replacement of the alkali metal ions thereof with rare earth metal ions. It will be appreciated that such period of contact may vary widely depending on the temperature of the solution, the nature of the alkali metal aluminosilicate used and the particular rare earth metal com-- pounds employed. Thus, the time of contact may extend from a brief period of the order of a few hours for small particles to longer periods of the order of days for largepellets. The exchange may also be carried out with several batches of solution wherein contact time per batch of said anions. The washed product is then dried, generally in air to remove substantially all of the water therefrom. While drying may be effected at ambient temperature, it is generally more satisfactory to facilitate the removal of moisture by maintaining the product at 21 temperature between about 150 and about 600 F. for 4 to 48 hours.

The dried material is then essentially subjected to an activating treatment which entails heating the dried material generally in air to a temperature within the approx-' imate range of 500 F. to 1500 F. for a period of be tween 1 and 48 hours. The resulting product has a surface area within an approximate range of 50 to 600 square meters per gram and generally contains between about 0.1 and about 30 Weight percent of rare earth metal, between about 0.1 and about 4 weight percent al-' kali metal, between about 25 and about 40 weight percent alumina and between about 40 and about 60 weight percent silica.

The above rare earth metal aluminosilicate is intimately combined with a metal of the platinum series. Such metals include platinum, palladium, osmium, rhodium, ruthenium and iridium, as well as combinations of these metals, A- particularly desirable combination is one of about 0.01 to about 5 weight percent of platinum intimately combined with the above-described rare earth metal aluminosilicate such as by being impregnated thereon.

Combination of one or more of the metals of the platinum series with the rare earth metal aluminosilicate may take place in any feasible manner, for example, by impregnating the rare earth metal aluminosilicate by contacting the same with solutions containing ions of the appropriate platinum series metal which it is desired to introduce. In this manner, the platinum metal can be introduced by deposition of the incoming metal on the rare earth metal exchanged aluminosilicate, after removal of the impregnating solution from the rare earth metal aluminosilicate carrier, either before or after drying and thermally activating the latter. One feasible method is to admix particles of the rare earth metal aluminosilicate with an aqueous solution of an acid of the platinum metal,

for example, chloroplatinic or chloropalladic acid or the ammonium salt of the acid of suitable concentration. It will be understood that any other suitable source of platinum metal may be used. Chloroplatinic acid generally is preferred because it is more readily available. Solutions of other feasible platinum-containing compounds include those of platinum amine chlorides, trinrethylbenzyl ammonium platinum chloride, tetraaminoplatino chloride, platinum amine nitrate, dinitro diamino platinum and the like. The particles of rare earth metal aluminosilicate impregnated with a platinum metal compound are then dried and treated with hydrogen at elevated temperatures to reduce the platinum metal compound to the metal and to activate the catalyst. The platinum metal component may also be combined with the rare earth metal aluminosilicate by utilizing a mixed base technique wherein the base containing the platinum metal component, for example, platinum on alumina, is admixed in finely divided form with the rare earth metal aluminosilicate. In such mechanical mixtures, the particle size of each of the components making up such mixture is generally less than about microns in diameter. Another method of introducing the platinum metal component involves its exchange into the aluminosilicate structure. Other means for combining the rare earth metal exchanged aluminosilicate with the platinum metal component are feasible such as, for example, the addition of the latter component to a slurry of the aluminosilicate.

The amount of platinum metal component with the rare earth metal aluminosilicate may vary widely and will depend on the charge stock undergoing reforming as Well as on the particular platinum metal utilized. Generally, the amount of platinum series metal will range from about 0.01 to about 5 weight percent and preferably between about 0.1 and about 2 weight percent. It will be understood that in any instance, the amount of platinum metal component present will be such as to afford a resulting composite in combination with the rare earth metal aluminosilicate of a reforming catalyst characterized by unusual activity and selectivity.

The process of this invention may be carried out in any equipment suitable for catalytic operations. The process may be operated batchwise. It is preferable, however, and generally more feasible to operate continuously. Accordingly, the process is adapted to operations using a fixed bed of catalyst. Also, the process can be operated using a moving bed of catalyst wherein the hydrocarbon flow may be concurrent or countercurrent to the catalyst flow. A fluid type of operation wherein the catalyst is carried in suspension in the hydrocarbon charge is well adapted for use with the present catalyst.

Reforming, in accordance with the present invention, is generally carried out at a temperature between about 700 F. and 1000 F. and preferably at a temperature between about 800 F. and about 975 F. The pressure during reforming is generally within the range of about 100 to about 1000 pounds per square inch gauge and preferably between about 200 and about 700 pounds per square inch gauge. The liquid hourly space velocity employed, i.e., the liquid volume of hydrocarbon per hour per volume of catalyst is between about 0.1 and about 10 and preferably between about 0.5 and about 4. In general, the molar ratio of hydrogen to hydrocarbon charge employed is between about 1 and about 20 and preferably between about 4- and about 12.

Hydrocarbon charge stocks undergoing reforming in accordance with this invention comprise mixtures of hydrocarbons and, particularly, reformer hydrocarbon charge stocks such as petroleum distillates boiling Within the approximate range of 60 F. to'450" R, which range includes naphthas, gasolines and kerosene. The gasoline fraction-inay be a full boiling range gasoline. It is, however, preferred to use a selected fraction, such as naphtha having an initial boiling point of between about 150 F. and about 250 F. and an end boiling point of between about 350 F. and about 425 F.

The following examples will serve to illustrate the invention hereinabove described without limiting the same:

Example 1 A crystalline sodium aluminosilicate having a uniform pore structure comprising openings characterized by an effective pore diameter in the range of 6 to 15 Angstroms was prepared by the addition of 199 parts by weight of an aqueous solution of sodium aluminate, containing the equivalent of 43.5 weight percent alumina (A1 and 30.2 weight percent sodium oxide (Na O) to 143 parts by weight of an aqueous sodium silicate solution, containing the equivalent of 26.5 weight percent silica (SiO and 8.8 weight percent sodium oxide (Na O). The gel which formed on mixing'the two above solutions was broken by vigorous mixing. The entire mass was mixed thoroughly to a cream-like consistency and, thereafter, heated without agitation for 12 hours at 205 F. At the end of this; period, there was found to have formed a flocculant precipitate beneath a clear supernatant liquid. The precipitate was filtered and washed with water at room temperature until the pH of the filtrate was 11.0. The resulting aluminosilicate crystalline product, upon analysis, was found to contain 21.6 mole percent Na O, 22.6 mole percent Al O and 55.8 mole percent SiO based on the dried product.

The above crystalline sodium aluminosilicate was contacted at 150 F. with 1500 cc. of an aqueous solution having a pH of 4 and containing 1.0 pound of the chlorides of a rare earth metal mixture consisting principally of cerium, lanthanum, praseodymium, neodymium, together with smaller amounts of other rare earths. The mixture was continuously agitated andafter 24 hours, the solid was filtered, washed and contacted with freshrare earth metal chloride solution as above. The above operation, during which sodium of the aluminosilicate was exchanged by rare earth metal, was repeated a number of times until the sodium content of the aluminosilicate had been reduced to 1.1 weight percent, corresponding to a replacement of 92 percent of the original sodium content of the crystalline aluminosilicatewith rare earth metal ions. The exchanged aluminosilicate material had a rare earth metal content of 27 percent by weight, calculated as the oxides.

The product so obtained was washed, dried at 240 F., pelleted to x inch particles and calcined to 1000 F., in dry air. The calcined rare earth metal-exchanged aluminosilicate was then steam treated for hours at 1200 F. and a pressure of'15 p.s.i.g.

A 132 gram sample of the above pellets was then evacuated to a pressure of about 10 millimeters of mercury and contacted with 67 cc. of an aqueous solution of chloroplatinic acid containing 0.012 gram of platinum per cc. at room temperature. The impregnated pellets were then removed from their evacuated state and held in a semisealed container for 16 hours at 240 F. The pellets were thereafter dried at 240 F., heated. in nitrogen to 450 F., reduced in hydrogen at 450 F. for 2 hours and thereafter at 950 F. for 2 hours. The resulting product was found to contain 0.6 weight percent platinum.

The platinum on rare earth metal-exchanged aluminosilicate pellets resulting f-rom the above preparation were employed in reforming a Mid-Continent naphtha having the following properties:

Gravity, API 54.9 Sulfur, p.p.m. 17 Aromatics 9.2 ASTM dist, F.:

IBP 186 10% vol. 221

8: 50% vol. 280 90% vol. 334 13.19. 366 CFRR octane:

Clear 45.0 +3 ml. TEL 63.3

Evaluation was carried out employing a cc. sample of the above pellets as catalyst, a 10 to 1 hydrogen to naphtha mole ratio, a pressure of 500 p.s.i.g., a reactor inlet temperature of 875 F. and a liquid hourly space velocity of 2.0. The product distribution and quality of products for this catalyst are set forth and compared with those for presently available commercial platinum on alumina reforming catalyst and platinum on silica-alumina reforming catalyst in Table I below:

As will be evident from the foregoing data, the activity of the platinum on rare earth aluminosilicate catalyst was about 81 F. better than the commercial platinum on alumina catalyst and afforded a 6 percent higher yield of (3 product at the same octane quality. It also was about 70 F. more active than the commercial platinum on silica-alumina catalyst with approximately the same yield of C product. It will further be noted that the iso-component of the C fraction (desirable because of its high octane quality and the need for producing better balanced gasolines) is equally high for each of the three catalysts while that of the 0.; fraction was appreciably higher with the platinum on rare earth aluminosilicate catalyst.

It will accordingly be seen from the foregoing that improved reforming is achieved in the presence of a catalyst comprising an intimate combination of a platinum metal with an initially crystalline alkali metal aluminosilicate having a uniform pore structure with openings in the range of 6 to 15 Angstrom units and base exchanged with a rare earth metal. It will thus be understood that the above description is merely illustrative of preferred embodiments of the invention of which many variations may be made by those skilled in the art without departing from the spirit thereof.

We claim:

1. A process for reforming a normally liquid hydrocarbon mixture boiling within the approximate range of 60 F. to 450 P. which comprises contacting the same under reforming conditions with a catalyst comprising as an active component between about 0.01 and about 5 weight percent of a metal of the platinum series in intimate combination with a rare earth aluminosilicate resulting from base-exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units with rare earth metal ions to replace at least about 75 percent of the original alkali metal content of the alkali metal aluminosilicate with said ions and to effectively reduce the alkali metal content of the resulting composite to below 4 percent by weight, washing the base exchanged material free of soluble anions, drying and thermally activating the product by heating at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours to effect at least partial conversion of the rare earth metal ion introduced by base exchange to a catalytically active state.

2. A process for reforming a normally liquid hydrocarbon mixture boiling within the approximate range of 60 F. to 450 F. by contacting the same under reforming conditions with a catalyst consisting essentially of a crystalline metal aluminosilicate having uniform pore openings between 6 and 15' Angstrom units and containing between about 0.1 and about 30 weight percent of rare earth metal introduced into said aluminosilicate by base exchange, between about 0.1 and about 4 weight percent alkali metal, between about 25 and about 40 weight percent alumina and between about 40 and about 60 weight percent silica and having intimately combined therewith between about 0.01 and about percent by weight of a metal of the platinum series said catalyst having been thermally activated by heating at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours.

3. A process for reforming a normally liquid hydrocarbon mixture boiling within the approximate range of 60 F. to 450 F. by contacting the same under reforming conditions with a catalyst comprising as an active component between about 0.01 and about 5 weight percent of a metal of the platinum series in intimate combination with a rare earth metal aluminosilicate resulting from base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units with rare earth metal ions to replace at least about 90 percent of the original alkali metal content of the alkali metal aluminosilicate with said ions and to effectively reduce the alkali metal content of the resulting composite to below 1 percent by weight, washing the base exchanged material free of soluble salts, drying and thermally activating the product by heating at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours to effect at least partial conversion of the rare earth metal ion introduced by base exchange to a catalytically active state.

4. A process for reforming a normally liquid reformer hydrocarbon charge stock boiling within the approximate range of 60 F. to 450 F. by contacting the same under reforming conditions with a catalyst comprising as an active component between about 0.01 and about 5 percent by weight of a metal of the platinum series in intimate combination with a crystalline aluminosilicate, at least 75 percent of the metal cation of which is rare earth metal introduced by base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units, the alkali metal content of the resulting base exchanged composite being below 4 percent by weight, said base exchanged aluminosilicate having been thermally activated at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours, to effect at least partial conversion of the rare earth metal ion introduced by base exchange to a catalytically active state.

5. A process for reforming a petroleum distillate boiling within the approximate range of 60 F. to 450 F. which comprises contacting the same under reforming conditions with a catalyst consisting essentially of between about 0.01 and about 5 weight percent of a platinum metal deposited on a rare earth metal aluminosilicate resulting from base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings be tween 6 and 15 Angstrom units with rare earth metal ions to replace at least about 75 percent of the original alkali metal content of said aluminosilicate with rare earth metal ions and to etfectively reduce the alkali metal content of the resulting composite to below 4 percent by weight, washing the base exchanged material free of soluble matter, drying and thermally activating the product by heating at a temperature in the approximate range l0 of 500 F. to 1500 F. for a period of between about 1 and about 48 hours.

6. A process for reforming a petroleum distillate boil ing within the approximate range of 60 F. to 450 F. which comprises contacting the same at a temperature between about 700 F. and about 1000 F. at a liquid hourly space velocity between about 0.1 and about 10 in the presence of hydrogen under a pressure between about 100 and about 1000 pounds per square inch gauge and a molar ratio of hydrogen to hydrocarbon between about 1 and about 20 with a catalyst comprising a crystalline aluminosilicate, at least percent of the metal cation of which is rare earth metal introduced by base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units, and having intimately combined therewith between about 0.01 and about 5 percent by weight of platinum, the alkali metal content of the base exchanged crystalline aluminosilicate being below 4 percent by Weight, said crystalline aluminosilicate having been thermally activated at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours to effect at least partial conversion of the rare earth metal ion introduced by base exchange to a catalytically active state.

7. A process for reforming a petroleum distillate boiling within the approximate range of 60 F. to 450 F. which comprises contacting the same at a temperature between about 700 F. and about 1000 F. at a liquid hourly space velocity between about 0.1 and about 10 in the presence of hydrogen under a pressure between about 100 and about 1000 pounds per square inch gauge and a molar ratio of hydrogen to hydrocarbon between about 1 and about 20 with a catalyst consisting essentially of between about 0.01 and about 5 percent by weight of platinum deposited on a base of a rare earth metal aluminosilicate resulting from base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units with rare earth metal ions to replace at least about 75 percent of the original alkali metal content of the alkali metal aluminosilicate with said ions and to effectively reduce the alkali metal content of the resulting composite to below 4 percent by weight, washing the base exchanged material free of soluble anions, drying and thermally activating the product by heating at a temperature in the approximate range of 5 00 F. to 15 00 F. for a period of between about 1 and about 48 hours to eifect at least partial Conversion of the rare earth metal ion introduced by base exchange to a catalytically active state.

8. A process for reforming a petroleum distillate boiling within the approximate range of 60 F. to 450 F. which comprises contacting the same at a temperature between about 800 F. and about 975 F. at a liquid hourly space velocity between about 0.5 and about 4 in the presence of hydrogen under a pressure between about 200 and about 700 pounds per square inch gauge and a molar ratio of hydrogen to hydrocarbon between about 4 and about 12 with a catalyst consisting essentially of between 0.1 and about 2 percent by weight of platinum deposited on a rare earth metal aluminosilicate resulting from base exchange of a crystalline alkali metal aluminosilicate having uniform pore openings between 6 and 15 Angstrom units with rare earth metal ions to replace at least about percent of the original alkali metal content of the alkali metal aluminosilicate with said ions and to effectively reduce the alkali metal content of the resulting composite to below 1 percent by weight, washing the base exchanged material free of soluble salts, drying and thermally activating the product by heating at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours to effect at least partial conversion of the rare earth metal ion introduced by base exchange to a catalytically active state.

9. A process for reforming a normally liquid hydrocarbon charge boiling within the approximate range of 60 F. to 450 P. which comprises contacting the same under reforming conditions with a catalyst comprising a crystalline aluminosilicate, at least 75 percent of the metal cation of which is rare earth metal introduced by base exchange of a crystalline alkali metal aluminosilicate have ing uniform pore openings between 6 and 15 Angstrom units and having intimately combined therewith between about 0.01 and 5 weight percent of a metal of the platinum series, the alkali metal content of the base exchange crystalline aluminosilicate being below 4 percent by weight, said crystalline aluminosilicate having been thermally activated at a temperature in the approximate range of 500 F. to 1500 F. for a period of between about 1 and about 48 hours to effect at least partial con.-

version of the rare earth metal ion introduced by base exchange to a catalytically active state.

References Cited by the Examiner UNITED STATES PATENTS 2,148,129 2/1939 Morrell et al. 208-135 2,971,903 2/1961 Kimberlin et al. 208119 2,971,904 2/1961 Gladrow et al. 208-138 2,976,232 3/1961 Porter et al. 208138 3,002,921 10/1961 Gladrow et al. 208-138 3,009,871 11/1961 Komarewsky 208135 DELBERT E. GANTZ, Primary Examiner.

ALPHONSO D. SULLIVAN, PAUL M. COUGHLAN, Examiners

Claims

1. A PROCESS FOR REFORMING A NORMALLY LIQUID HYDROCARBON MIXTURE BOILING WITHIN THE APPROXIMATE RANGE OF 60*F. TO 450*F. WHICH COMPRISES CONTACTING THE SAME UNDER REFORMING CONDITIONS WITH A CATALYST COMPRISING AS AN ACTIVE COMPONENT BETWEEN ABOUT 0.01 AND ABOUT 5 WEIGHT PERCENT OF A METAL OF THE PLATINUM SERIES IN INTIMATE COMBINATION WITH A RARE EARTH ALUMINOSILICATE RESULTING FROM BASE-EXCHANGE OF A CRYSTALLINE ALKALI METAL ALUMINOSILICATE HAVING UNIFORM PORE OPENINGS BETWEEN 6 AND 15 ANGSTROM UNITS WITH RARE EARTH METAL IONS TO REPLACE AT LEAST ABOUT 75 PERCENT OF THE ORIGINAL ALKALI METAL CONTENT OF THE ALKALI METAL ALUMINOSILICATE WITH SAID IONS AND TO EFFECTIVELY REDUCE THE ALKALI METAL CONTENT OF THE RESULTING COMPOSITE TO BELOW 4 PERCENT BY WEIGHT, WASHING THE BASE EXCHANGED MATERIAL FREE OF SOLUBLE ANIONS, DRYING AND THERMALLY ACTIVATING THE PRODUCT BY HEATING AT A TEMPERATURE IN THE APPROXIMATE RANGE OF 500*F. TO 1500*F. FOR A PERIOD OF BETWEEN ABOUT 1 AND ABOUT 48 HOURS TO EFFECT AT LEAST PARTIAL CONVERSION OF THE RARE EARTH METAL ION INTRODUCED BY BASE EXCHANGE TO A CATALYTICALLY ACTIVE STATE.