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US2651598A - Reforming process and catalyst - Google Patents

Reforming process and catalyst Download PDF

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US2651598A
US2651598A US216193A US21619351A US2651598A US 2651598 A US2651598 A US 2651598A US 216193 A US216193 A US 216193A US 21619351 A US21619351 A US 21619351A US 2651598 A US2651598 A US 2651598A
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catalyst
alkali metal
silica
reforming
platinum
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Frank G Ciapetta
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Atlantic Richfield Co
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Atlantic Refining Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/906—Catalyst preservation or manufacture, e.g. activation before use

Definitions

  • This invention relates generally to a process for improving low octane hydrocarbon fractions to the nre uc a inc se in ,Qe an va of such fractions. More specifically, this invention is concerned with a'process involying the use of a specialcatalyst under ffiformingp pnditions whereby low anti-knock hydrocarbon fractions can be eff ciently converted to a product possessing a higher anti-knock value.
  • Another object of the present invention is to provide an improved method of reforming hydrocarbons of low octane number'to h drocarbons of highcctane number.
  • Another object is to provide a catalyst which will have the ability to" reio'rm both high sulfur and low-sulfur content hydrocarbon fractions.
  • a still further object r this" inyentionds to provide an improved reforming catalyst contain otherwise to 2 ing amajor proportion of a cracking component anda minor proportionof both an alkali metal and a metal from the group consisting of platium and palladium.
  • the catalysts of this invention are composite materials comprising, in general, major proportions of a cracking component hereinafter indicated, a minor proportion of a chemically combined alkali metal, and a minor proportion of platinum or palladium. More particularly, the compcsited material comprises the cracking component, 0,5 to 5L0 weight percent of a chemically combined alkali metal, and .01 to 2.5 Weight percent of platinum or palladium. All weight percentages mentioned in this specification are based on the weight of the final composite.
  • cracking components shall mean a material comprising silica' and ,at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zircqn a, the composite of silica with the named o ides haying substantial activity for cracking hydrocarbons.
  • the cracking component may be derived from either naturally-occurring or synthetically produced materials.
  • Naturally-occurring materials include various aluminum silicates, particularly when acid treated to increase their activity for crackinghydrocarbons, such as Super Filtrol, etc.
  • synthetically produced cracking components include silica-alumina, silica-zirconia, silica'ealumina-zirconia, silica-magnesia, silicaalumina-magnesia, silica-alumina-thoria, etc.
  • These synthetic lilal e rials may be made in any suitable manner well known to the art, including separate, successive, or .coprecipitation methods of manufacture.
  • the preferred synthetic cracking .c omponent, silica-alumina may be manufactured by commingling an acid, such as hydrochloric acid, sulfuric acid, etc., with commercial water glass under conditions to precipitate silica, washing with acidulated water or I a 7 remove sodium ions, commingling with an aluminum salt such as aluminum chloride, aluminum sulfate, aluminum nitrate, and either adding a basic precipitant, such as ammonium hydroxide to precipitate alumina, or rming 1 6 desflfi'i oxide or oxides by thermal decompositionof the salt as the case may permit.
  • an acid such as hydrochloric acid, sulfuric acid, etc.
  • an aluminum salt such as aluminum chloride, aluminum sulfate, aluminum nitrate
  • a basic precipitant such as ammonium hydroxide
  • the preferred cracking component may contain from 20% to 95% by weight of silica with the remainder alumina, although amounts above and below this range may also be used.
  • a commercially available synthetic silicaalumina cracking catalyst is sold under the name Diakel and comprises about 87% silica and 13% alumina, prepared in general according to the method outlined above.
  • the cracking component may be in the form of beads or granules either of regular or irregular size and shape. The granules may be ground or formed into pellets of uniform size and shape by pilling, extrusion, or other suitable methods.
  • chemically combin d alkali metal refers to an alkali metal which is in true chemical combination with some other element of the catalyst and hence, does not include alkali metals in the metallic or free state, since it is clear that under the elevated temperatures employed in reforming hydrocarbons, uncombined alkali metals would vaporize or combine with hydrocarbons within the reaction chamber.
  • the alkali metal may be either sodium, potassium, lithium, cesium, or rubidium and may be composited and combined with the cracking component mentioned above in any suitable manner.
  • the preferred method is to incorporate the alkali metal on the cracking component by a simple base exchange procedure which comprises the steps of soaking the cracking component pellets in asolution of a soluble alkali metal salt, draining off the excess alkali metal salt, washing the treated material with water, and drying.
  • the alkali metal salt solution may be in the form of inorganic salts such as the carbonate, nitrate, sulfate, chloride, hydroxide, phosphate, dicarbonate, borate, aluminate, and the like, or salts of organic acids such as the acetate, propionate, and the like.
  • concentration of the alkali metal salt solution used in each particular instance will depend upon the solubility of the particular compound at the temperature of treating and upon the desired concentration of the alkali metal in the composite catalysts.
  • the desired alkali metal content may also be incorporated by other procedures.
  • One such method involves the incorporation of the desired amount of alkali metal during the preparation of the cracking component.
  • synthetic silicaalumina cracking catalysts are often prepared by dispersing a silica gel in a solution of an aluminum salt after which a basic precipitant, such as ammonium hydroxide is added to precipitate alumina on the silica gel. If an alkali metal hydroxide is employed as the basic precipitant instead of ammonium hydroxide, the resulting compound comprises an alkali metal aluminum silicate.
  • This compound can then be washed with a calculated quantity of a mineral acid to remove only a part of the alkali metal so that the desired critical amount of alkali metal will remain combined with the silica-alumina.
  • the aluminum salt may be partially precipitated with an alkali metal hydroxide (to incorporate the necessary amount of alkali metal) following which the precipitation of the aluminum salt is completed with ammonium hydroxide and the composite calcined to remove ammonia.
  • the platinum or palladium may be composited with the cracking component and chemically combined alkali metal by any suitable method known to the art.
  • the preferred method is to admix an aqueous solution of chloroplatinic acid or chloropalladic acid of suitable concentration with the cracking component containing the alkali metal.
  • the mixture is then dried and treated with hydrogen at elevated temperatures to reduce the chloride to the metal and to activate the catalyst.
  • the alkali metal salt solution to the carrier prior to impregnation with platinum or palladium, such addition might instead be made after the impregnation with platinum or palladium.
  • EXAIVIPLE I 250 grams of fresh silica-alumina cracking catalyst (87% silica-13% alumina) pellets was soaked in an excess of demineralized water for 30 minutes, and thereafter centrifuged to give: 410 grams of a wet catalyst. To this wet catalyst. was added 220 cc. of 1.44 N sodium carbonate: solution and the mixture was allowed to soakv for 30 minutes. The solid material was then drained to remove the excess salt solution and. washed continuously with 2000 cc. of demineral-- ized water. When tests of the wash water indi-- cated that no sodium ions were present, thetreated cracking component was dried at 212 F- for 16 to 18 hours.
  • this dried material was treated. with 146 cc. of a .0174 molar chloroplatinic acid solution. After this solution became absorbed. on the surface of the treated cracking component, the material was dried in an oven for 16 hours: at 212 F. for 2 hours at 450 F. in the presence: of nitrogen, and then reduced at 450 F. for 6' hours in an atmosphere of hydrogen. Upon. analysis, this catalyst was found to contain 1.3- weight percent of sodium and .27 weight percent; of platinum.
  • EXALEPLE H water showed that potassium ions were no longerpresent, the treated silica-alumina was dried at 212 F. for 16 to 18 hours.
  • the above examples illustrate howthe'instant catalyst may" be" prepared bybinglor multiple batch type procedures.
  • the" catalyst can be equally well prepared by 'acontinuous percolation of the alkali metal salt solution over platinum and 2.3
  • Composite catalysts containing cesium, lithium, and rubidium may be prepared in a similar manner.
  • The'present invention entails the use of the catalyst described above in a reforming process.
  • the process is conducted at: pressures from 100.to 1000p. s. i. and preferably.
  • reaction may be carried out in'the presence of hydrogen in amounts from 1 to 20 mols of hydrogen per mol of hydrocarbon.
  • the hydrocarbons to be treated in the invention comprise petroleum-distillate fractions, including naphthas, gasoline, and. kerosene, and
  • the gasoline fraction may be a. full boiling range gasoline having an initial boiling point within the-range of' about 50 F. to about 90 F. and a final boiling.
  • naphtha r commonly referred to as naphtha r and generally. having an initial boiling point of from 150-? to about 250 F. and a final boiling point within the the catalyst is suspended by the gaseous hydrocarbon stream or the moving bed' type process in which the catalyst and hydrocarbon are passed either concurrently or countercurrently to each other. After reforming, the products may be fractionated toseparate excess hydrogen and to recover the desired-fractions of'reformed'product.
  • reactivatethecatalyst After a periodof service, it may be desirable to reactivatethecatalyst, and this may be readily accomplished by passing air or other oxygencontaining gasestherethroughin order to burn carbonaceous deposits from the catalyst.
  • 'A particularly suitable method of. regeneration comprises effecting the regeneration at a temperature of about 900 F.” to 050 F., starting with a gas containing about 2%. oxygen or less and gradu ally-increasing the oxygen concentration so that at the-end of theregeneration period, pureair. is beingjpassed over thecatalyst. .However, it is important that the temperature of regenera-' tion should notexceed' 1000 F.,' as it has been found thattemperatures'in excess of 1000 F. tend to impair the reforming activity'of the cat-'- alyst.
  • Table l comprises'a series of reforming runs whereby a vaporized East Texas charge stock having the following specifications:
  • the only method of comparing the reforming ability of two reforming catalysts is by comparing the yield-octane relationship obtainable from each. In order to make these relationships truly comparable, it is necessary to reform aliquot portions of the identical charge stock with each catalyst. If the same charge stock is not used in each case, no valid comparison of yield-octane results can be made since each different charge stock is composed of different components and consequently, each different charge stock varies in its ability to be reformed. Also, in order to make a valid comparison of the yield-octane results, it is necessary that the productsv be condensed at the same temperature and compared at the same Reid vapor pressure.
  • the amounts of platinum or palladium should range between 0.01% by weight to 2.5% by weight of the final composite. Amounts less than 0.01% result in too low reforming activity, i. e., negligible octane improvements, amounts greater than 2.5% are likewise undesirable for the reason that such catalysts result in excessive cracking.
  • a further highly advantageous property of the silica-alumina-platinum-alkali metal catalyst resides in its ability to reform hydrocarbon charge stocks containing large amounts of sulfur compounds.
  • charge stocks containing even small amounts of sulfur compounds are much more difficult to reform than sulfur-free charge stocks.
  • the vast majority of reforming catalysts known heretofore are deleteriously affected by a sulfur-containing feed with the result that the activity and life of these catalysts are impaired.
  • the hydrocarbon charge should be desulfurized so as to make it practically sulfur-free.
  • Various desulfurization processes are known, but their use entails additional equipment and considerable expense.
  • the instant catalysts are not deleteriously affected by sulfur-containing charge stocks, but to the contrary are capable of reforming sulfur-containing charge stocks with the same degree of success as sulfur-free charge stocks.
  • This. highly advantageous property results in increased economy of operation by eliminating the'necessity for an expensive pre-desulfurization step.
  • Table 3 The results tabulated in Table 3 below illustrate that the present catalysts are highly emcient for reforming a hydrocarbon charge stock containing sulfur compounds.
  • the data shown in Table 3 was obtained by passing a West Texas Permian charge stock having the following properties:
  • a catalyst consisting essentially of a cracking component, 0.01 to 2.5 weight percent of a metal from the group consisting of platinum and palladium, and 0.5 to 4.0 Weight percent of a chemically combined alkali metal, said cracking component comprising silica and at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zirconia.
  • the catalyst consists essentially of 0.01 to 2.5 weight percent of platinum, 0.5 to 4.0 weight percent of chemically combined alkali metal and a cracking component comprising silica and alumina.
  • the catalyst consists essentially of 0.01 to 2.5 weight percent of platinum, 0.5 to 4.0 weight percent of chemically combined sodium, and a cracking component comprising silica and alumina.
  • a catalyst consisting essentially of a cracking component, 0.01 to 2.5 weight percent of a metal from the group consisting of platinum and palladium, and 0.5 to 4.0 weight percent of a chemically combined alkali metal, said cracking component comprising silica and at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zirconia.
  • a catalyst consisting essentially of 0.01 to 2.5 weight percent of platinum and 0.5 to 4.0 weight percent of a chemically combined alkali metal, and a cracking component comprising silica and at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zirconia.
  • a catalyst consisting essentially of 0.01 to 2.5 weight percent of platinum, 0.5 to 4.0 weight percent of chemically combined sodium, and a cracking component comprising silica and alumina.

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Description

P 3, 1953 F. G. CIAPETTA 2,651,593
REFORMING PROCESS AND CATALYST Filed March 17, 1951 3 2 a a a 5 2 a i 1 X s E E 8 3 E E it 2 Q} g b poqgayyqunasag-lmagp .zaqulnN 92122200 ATTEST INVENTOR.
FRANK G. CMPETTA BY W 5 Patented Sept. 8, 1953 Frank G. Cia'p'etta,
Llanerch, Pa., assignor to The Atlantic :R'efining Company, Philadelphia, Pa., a corporation of Pennsylvania Application March 17, 1951, SerialNo. 216,193
(01. m an 6 Claims. .1 V I a This invention relates generally to a process for improving low octane hydrocarbon fractions to the nre uc a inc se in ,Qe an va of such fractions. More specifically, this invention is concerned with a'process involying the use of a specialcatalyst under ffiformingp pnditions whereby low anti-knock hydrocarbon fractions can be eff ciently converted to a product possessing a higher anti-knock value.
It is well known that an increase in the antiknock properties of hydrocarbons may be accomplished bycatalytic' reforming under specific operating conditions. These processes generally involve the 'steps of passing a hydrocarbon fraction with or withdut added hydrogen over a reforming catalyst. Although may theories have been advanced as to' the exact nature of the reactions which occur during reforming, it is generally believed that reforming involves a number of simultaneously-occurring reactions, such as isomerization, dehydrogenation, selective cracking, and aromatization. In recent years, a mult d o a ts hav been P p ed r t reforming of low anti-knock gasolines. These catalysts include a majority of the elements of the periodic table in various combinations. While a number of these catalysts have been found to be effective, at least to some extent, in reforming hydrocarbon fractions, only a few of these catalytic agents are of sufficient imporfiance o r c e en i e' t on fo comm rc operation since even when an eiiectivecatalyst is found, its use will not be commercially adopted unless it displays in addition to a high yieldoctane relationship, the highly desirable andnecessary qualities such as a long life, immunity to poisoning, and ease of regeneration. The mere fact that such a large number of reforming catalysts havebeen suggested the prior art is an indication of the dijfficulty involved finding a proper combination of chemical compounds which will have these desired properties.
It is an object of the present invention to provide a reforming catalyst which produces high yield-octane relationships, has a long life, is ifnmune to poisoning, and is easily regenerated.
Another object of the present invention is to provide an improved method of reforming hydrocarbons of low octane number'to h drocarbons of highcctane number.
Another object is to provide a catalyst which will have the ability to" reio'rm both high sulfur and low-sulfur content hydrocarbon fractions.
A still further object r this" inyentionds to provide an improved reforming catalyst contain otherwise to 2 ing amajor proportion of a cracking component anda minor proportionof both an alkali metal and a metal from the group consisting of platium and palladium.
Numerous other objects will hereinafter appear from the disclosures of the specification and the appended claims, all taken in conjunction with the accompanying drawing, which portrays diagrammatically the superiority of the n tan invention The catalysts of this invention are composite materials comprising, in general, major proportions of a cracking component hereinafter indicated, a minor proportion of a chemically combined alkali metal, and a minor proportion of platinum or palladium. More particularly, the compcsited material comprises the cracking component, 0,5 to 5L0 weight percent of a chemically combined alkali metal, and .01 to 2.5 Weight percent of platinum or palladium. All weight percentages mentioned in this specification are based on the weight of the final composite.
Ihe term cracking components," as hereinafter used, shall mean a material comprising silica' and ,at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zircqn a, the composite of silica with the named o ides haying substantial activity for cracking hydrocarbons.
The cracking component may be derived from either naturally-occurring or synthetically produced materials. Naturally-occurring materials include various aluminum silicates, particularly when acid treated to increase their activity for crackinghydrocarbons, such as Super Filtrol, etc. synthetically produced cracking components include silica-alumina, silica-zirconia, silica'ealumina-zirconia, silica-magnesia, silicaalumina-magnesia, silica-alumina-thoria, etc. These synthetic lilal e rials may be made in any suitable manner well known to the art, including separate, successive, or .coprecipitation methods of manufacture. The preferred synthetic cracking .c omponent, silica-alumina, may be manufactured by commingling an acid, such as hydrochloric acid, sulfuric acid, etc., with commercial water glass under conditions to precipitate silica, washing with acidulated water or I a 7 remove sodium ions, commingling with an aluminum salt such as aluminum chloride, aluminum sulfate, aluminum nitrate, and either adding a basic precipitant, such as ammonium hydroxide to precipitate alumina, or rming 1 6 desflfi'i oxide or oxides by thermal decompositionof the salt as the case may permit.
The preferred cracking component, silica-alumina, may contain from 20% to 95% by weight of silica with the remainder alumina, although amounts above and below this range may also be used. A commercially available synthetic silicaalumina cracking catalyst is sold under the name Diakel and comprises about 87% silica and 13% alumina, prepared in general according to the method outlined above. The cracking component may be in the form of beads or granules either of regular or irregular size and shape. The granules may be ground or formed into pellets of uniform size and shape by pilling, extrusion, or other suitable methods. l V
The term chemically combin d alkali metal, as used herein and in the appended claims, refers to an alkali metal which is in true chemical combination with some other element of the catalyst and hence, does not include alkali metals in the metallic or free state, since it is clear that under the elevated temperatures employed in reforming hydrocarbons, uncombined alkali metals would vaporize or combine with hydrocarbons within the reaction chamber.
The alkali metal may be either sodium, potassium, lithium, cesium, or rubidium and may be composited and combined with the cracking component mentioned above in any suitable manner. Several illustrations are given below, but it must be understood that the recitation of these methods does not limit the invention to catalysts prepared according to these methods. The preferred method is to incorporate the alkali metal on the cracking component by a simple base exchange procedure which comprises the steps of soaking the cracking component pellets in asolution of a soluble alkali metal salt, draining off the excess alkali metal salt, washing the treated material with water, and drying. The alkali metal salt solution may be in the form of inorganic salts such as the carbonate, nitrate, sulfate, chloride, hydroxide, phosphate, dicarbonate, borate, aluminate, and the like, or salts of organic acids such as the acetate, propionate, and the like. The concentration of the alkali metal salt solution used in each particular instance will depend upon the solubility of the particular compound at the temperature of treating and upon the desired concentration of the alkali metal in the composite catalysts.
Although the preferred method of incorporating the alkali metal is by base exchange means as outlined above, the desired alkali metal content may also be incorporated by other procedures. One such method involves the incorporation of the desired amount of alkali metal during the preparation of the cracking component. For instance, as described above, synthetic silicaalumina cracking catalysts are often prepared by dispersing a silica gel in a solution of an aluminum salt after which a basic precipitant, such as ammonium hydroxide is added to precipitate alumina on the silica gel. If an alkali metal hydroxide is employed as the basic precipitant instead of ammonium hydroxide, the resulting compound comprises an alkali metal aluminum silicate. This compound can then be washed with a calculated quantity of a mineral acid to remove only a part of the alkali metal so that the desired critical amount of alkali metal will remain combined with the silica-alumina. Alternatively, the aluminum salt may be partially precipitated with an alkali metal hydroxide (to incorporate the necessary amount of alkali metal) following which the precipitation of the aluminum salt is completed with ammonium hydroxide and the composite calcined to remove ammonia.
It is also possible to obtain the desired amount of alkali metal by total absorption on the cracking components of a measured quantity of an alkali metal salt having a volatilizable or decomposable anion followed by drying and calcining.
The platinum or palladium may be composited with the cracking component and chemically combined alkali metal by any suitable method known to the art. The preferred method is to admix an aqueous solution of chloroplatinic acid or chloropalladic acid of suitable concentration with the cracking component containing the alkali metal. The mixture is then dried and treated with hydrogen at elevated temperatures to reduce the chloride to the metal and to activate the catalyst. Although it has been found preferable to add the alkali metal salt solution to the carrier prior to impregnation with platinum or palladium, such addition might instead be made after the impregnation with platinum or palladium.
The preparation of the composite catalyst by a simple base exchange procedure will be illustrated in the following examples. It should be understood, however, that the examples are given for the purpose of illustration and the invention in its broader aspects is not limited thereto.
EXAIVIPLE I 250 grams of fresh silica-alumina cracking catalyst (87% silica-13% alumina) pellets was soaked in an excess of demineralized water for 30 minutes, and thereafter centrifuged to give: 410 grams of a wet catalyst. To this wet catalyst. was added 220 cc. of 1.44 N sodium carbonate: solution and the mixture was allowed to soakv for 30 minutes. The solid material was then drained to remove the excess salt solution and. washed continuously with 2000 cc. of demineral-- ized water. When tests of the wash water indi-- cated that no sodium ions were present, thetreated cracking component was dried at 212 F- for 16 to 18 hours.
200 grams of this dried material was treated. with 146 cc. of a .0174 molar chloroplatinic acid solution. After this solution became absorbed. on the surface of the treated cracking component, the material was dried in an oven for 16 hours: at 212 F. for 2 hours at 450 F. in the presence: of nitrogen, and then reduced at 450 F. for 6' hours in an atmosphere of hydrogen. Upon. analysis, this catalyst was found to contain 1.3- weight percent of sodium and .27 weight percent; of platinum.
EXALEPLE H water showed that potassium ions were no longerpresent, the treated silica-alumina was dried at 212 F. for 16 to 18 hours.
180 grams of this dried material was treated. with 132 cc. of .0172 molar chloroplatinic acid solution. After the solution had been absorbed EXAMPLE III 350 cc. of a 2 N NazCOa solution (93 grams NfiZCO3-H20') in 750 cc. of H was poured over 250 grams of fresh silica-alumina crackingcatalyst and the mixture allowed to stand for hour. The supernatant liquid was poured-off and another 350 cc. portion of 2 N NazCOc solution added. After standing for minutes, the excess liquid was drained off and the solids washed 10 times with 350 cc. batches of water; The solids" were dried overnight in" an oven at 230 F. and' calcined at 900 F. for 1 hour. The resulting composite, after treatment with chloroplatinic acid as outlined in Examples I and II, wasfound' to contain .16 weight" percent Weight percent of sodium.
The above examples illustrate howthe'instant catalyst may" be" prepared bybinglor multiple batch type procedures. However, the" catalyst can be equally well prepared by 'acontinuous percolation of the alkali metal salt solution over platinum and 2.3
the silica-alumina until the desired amount of alkali metal has been incorporated therewith.
Composite catalysts containing cesium, lithium, and rubidium may be prepared in a similar manner.
The'present invention entails the use of the catalyst described above in a reforming process. The generalprocedure in reforming-involves mixing the hydrocarbon fraction to be treated with hydrogen and passing the admixture in contact with the reforming catalyst. In carrying out reforming in accordance with this invention, temperatures in the range of 600 F. to.1000'F; .and'
preferably 700 F. to. 1000 F. may be used, depending upon the particular hydrocarbon feed employed andthe particular catalyst composition ratio being used: Ithas been foundipreferable,
tov preheat both the charge and the catalyst to these temperatures to achieve best results-,-.al-fthough either the charge or the catalyst alone: could be so heated. The process is conducted at: pressures from 100.to 1000p. s. i. and preferably.
from 500 to 800 p. s. i. Hourly liquidspace veloc-- ities (meaning the liquid volume of hydrocarbon per hour per volume of catalyst) may be in the;
range of 0.1'to 10, preferablyin the range of 0.5 to 4.0. The reaction may be carried out in'the presence of hydrogen in amounts from 1 to 20 mols of hydrogen per mol of hydrocarbon. Un-
der these circumstances, using the instant-novel'- catalyst, it is possible to obtain from petroleum distillate fractions, particularly gasoline frac-- tions, excellent yields of high octanev gasoline.
The hydrocarbons to be treated in the invention comprise petroleum-distillate fractions, including naphthas, gasoline, and. kerosene, and
particularly gasoline fractions The gasoline fraction may be a. full boiling range gasoline having an initial boiling point within the-range of' about 50 F. to about 90 F. and a final boiling.
point within the range of about 375 F. toabout 425 F., or it may be a selected fraction thereof whichusually will be a higher boiling fraction,
commonly referred to as naphtha r and generally. having an initial boiling point of from 150-? to about 250 F. and a final boiling point within the the catalyst is suspended by the gaseous hydrocarbon stream or the moving bed' type process in which the catalyst and hydrocarbon are passed either concurrently or countercurrently to each other. After reforming, the products may be fractionated toseparate excess hydrogen and to recover the desired-fractions of'reformed'product.
In one manner ofio'peration of the process,- sufficient hydrogen willbe produced in the reformingreaction to maintaina hydrogen partialpressure sufficient to saturate the hydrocarbon frag-'- ments formed therein. However, hydrogen from an extraneous source is added at the beginning of the operation and' usually itis desirable to recycle hydrogen withinthe process after the starting operation in order to assure'asuflicient hydrogen atmosphere in the reaction zone; I-Iy'drogen serves to maintain thecatalyst activity by reducing or: preventing carbon deposition. Also, if desired, the hydrocarbon may be treated to remove sulfur prior to reformingathough such removal-is not necessary, and in fact, the us of the instant reforming catalyst produces equally good results with'or' without sulfur removal.
After a periodof service, it may be desirable to reactivatethecatalyst, and this may be readily accomplished by passing air or other oxygencontaining gasestherethroughin order to burn carbonaceous deposits from the catalyst. 'A particularly suitable method of. regeneration comprises effecting the regeneration at a temperature of about 900 F." to 050 F., starting with a gas containing about 2%. oxygen or less and gradu ally-increasing the oxygen concentration so that at the-end of theregeneration period, pureair. is beingjpassed over thecatalyst. .However, it is important that the temperature of regenera-' tion should notexceed' 1000 F.,' as it has been found thattemperatures'in excess of 1000 F. tend to impair the reforming activity'of the cat-'- alyst.
Table l below comprises'a series of reforming runs whereby a vaporized East Texas charge stock having the following specifications:
Reid vapor pressure 1.0 Percent sulfur .008 Octane number, clear (Research Method,
A. S. T. M. D-908-49T) 54.0 A. S. T. M. Distillation:
Qverpoint F 185 50% F 262 l F 334' Endpoint F 367 A. P; I. Gravity at 60 F 55.5
was-mixed with hydrogen (10 mo1s of hydrogen per'mol of hydrocarbon) at a pressure of 500' p. s. i.', a liquid space velocity of 1.0 (ccjof liquid percc." of catalyst per hour) and contacted with I a silica-alumina-platinum-alkali metal catalyst havingthe'we'igh't percent of alkali' metal and platinum'indicated; at the tempertu'res' shown. These catalysts "vvi'are'prepared according" to the 7 methods set forth in Examples I and II. The volume percent recovery and clear research method octane results were tabulated on the basis of a 4 pound Reid vapor pressure and plotted as carbonfeed nor is it limited to the yield-octane results obtained. The relationship of yield-octane results shown in Figure 1 for the two catalysts as been found to hold true for all feed curve A in Figure 1. V 5 stocks tested. Other charge stocks used with 7 Table 1 I Alkali Metal Sodium Sodium 'Sodlum Potassium Potassium Cesium AlkaliMetal (Wt. 2.9 2.3 1.3 -'2.4- 1.4 3.6
Platinum (Wt. Percent) .12 .25 .27 22. .18 .24
Temperature(F.) 850 920 850 920 850 920 .850 .920 s50 e 920 Yield (Vol. Percent of charge) 99.8 93.2 97.3 90.4 85.5 72.8 97.5 89.5 81.3 70.0 78.4
Research Octane (Clear) 69.9 80.0 68.0 76.4 83.8 04.2 66.9 80.7 85.6 95.2 90.0
As hereinbefore set forth, a multitude of reforming catalysts have been suggested in the prior art. Among these, the combination of platinum or palladium with a cracking component com prising silica and one or more metal oxides from the group consisting of alumina, magnesia, thoria, and zirconia havebeen mentioned, and particularly the combination of silica, alumina, and platinum. In order to clearly show the marked superiority of the instant catalysts over a silica-alumina-platinum catalyst not containing an alkali metal, many comparative tests were conducted.
The only method of comparing the reforming ability of two reforming catalysts is by comparing the yield-octane relationship obtainable from each. In order to make these relationships truly comparable, it is necessary to reform aliquot portions of the identical charge stock with each catalyst. If the same charge stock is not used in each case, no valid comparison of yield-octane results can be made since each different charge stock is composed of different components and consequently, each different charge stock varies in its ability to be reformed. Also, in order to make a valid comparison of the yield-octane results, it is necessary that the productsv be condensed at the same temperature and compared at the same Reid vapor pressure.
Therefore, to produce a silica-alumina-platie num catalyst for purposes of comparison, the
steps of Examples I and II were carried out with the exception that the alkali metal treating step was omitted. This catalyst was then used to reform the identical East Texas hydrocarbon charge stock employed in the runs of Table 1 and under the same operating conditions. The results are tabulated in Table 2 below and plotted in curve B of Figure 1.
A comparison of Tables 1 and 2 and the corresponding curves A and 13" of Figure 1 shows the striking superiority of the silica-alumina platinum-alkali metal catalyst over a silica-aluminaplatinum catalyst containing no alkali metali Figure 1, attached hereto, is presented primariy to show the comparative values of the abovementioned catalyst and. is not intended to limit applicants invention to this particular hydrothe instant catalysts may give higher yields and higher octane values, yet the relative improvement evidenced by the instant catalyst will'generally the same.
It has heretofore been mentioned that the amounts of alkali metal which can be composited with the cracking component and platinum lies between optimum limits. If amounts less than 0.5% are used, the final catalyst will show yieldoctane relationships falling in the neighborhood of the curve B" in Figure 1, i. e., these catalysts are similar to silica-alumina-platinum having no alkali metal composited therewith and therefore are inferior. The upper limit of 4.0% was selected for the reason that catalysts having amounts of alkali metal in excess of this amount were too inactive, that is, they gave negligible octane improvement. However, in the case of cesium and rubidium, which have higher atomic weights, amounts somewhat in excess of 4.0% may be used without obtaining an inactive catalyst.
It has also been mentioned that the amounts of platinum or palladium should range between 0.01% by weight to 2.5% by weight of the final composite. Amounts less than 0.01% result in too low reforming activity, i. e., negligible octane improvements, amounts greater than 2.5% are likewise undesirable for the reason that such catalysts result in excessive cracking.
A further highly advantageous property of the silica-alumina-platinum-alkali metal catalyst resides in its ability to reform hydrocarbon charge stocks containing large amounts of sulfur compounds. As is well-known in the art, charge stocks containing even small amounts of sulfur compounds are much more difficult to reform than sulfur-free charge stocks. In addition, the vast majority of reforming catalysts known heretofore are deleteriously affected by a sulfur-containing feed with the result that the activity and life of these catalysts are impaired As a consequence, in early been specifically pointed out that the hydrocarbon charge should be desulfurized so as to make it practically sulfur-free. Various desulfurization processes are known, but their use entails additional equipment and considerable expense. The instant catalysts, however, are not deleteriously affected by sulfur-containing charge stocks, but to the contrary are capable of reforming sulfur-containing charge stocks with the same degree of success as sulfur-free charge stocks. This. highly advantageous property results in increased economy of operation by eliminating the'necessity for an expensive pre-desulfurization step.
The results tabulated in Table 3 below illustrate that the present catalysts are highly emcient for reforming a hydrocarbon charge stock containing sulfur compounds. The data shown in Table 3 was obtained by passing a West Texas Permian charge stock having the following properties:
Reid vapor pressure (lbs) .5 Percent sulfur .32 Octane number, clear (Research Method,
A. S. T. M. D-908-49T) 48.9 A. S. T. M. distillation:
Overpoint F 193 50% F 275 90% F 334 Endpoint F 384 A. P. I. gravity (at 60 F.) 53.2
in admixture with hydrogen mols of hydrogen per mol of hydrocarbon) at a pressure of 500 p. s. i., a liquid space velocity of 1.0 (cc. of liquid per cc. of catalyst per hour) over a silicaalumina-platinum-alkali metal catalyst having the weight percent of alkali metal and platinum indicated, and at the temperatures shown in Table 3 below. These catalysts were prepared according to the methods set forth in Examples I, II, and III. The volume percent recovery and research method octane results were tabulated on the basis of a 4 pound Reid vapor pressure product.
Table 3 Alkali Metal Sodium Sodium Sodium Alkali Metal (Wt. percent) 2.3 2.9 1.35 Platinum (Wt., percent) .16 .25 .25
Temperature (F.) 850 920 850 920 850 920 Yield (Vol. percent of Charge) 99.4 91. 99.7 94.7 92.0 79.2 Research Octane (Clear)... 68.5 79.1 68.1 78.0 76.7 90.2
to increase the anti-knock value thereof which comprises admixing hydrogen with said fraction and passing said admixture at reforming conditions including a temperature within the range of 600 F. to 1000 F. and a pressure of from to 1000 p. s. i. over a catalyst consisting essentially of a cracking component, 0.01 to 2.5 weight percent of a metal from the group consisting of platinum and palladium, and 0.5 to 4.0 Weight percent of a chemically combined alkali metal, said cracking component comprising silica and at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zirconia.
2. The process according to claim 1 wherein the catalyst consists essentially of 0.01 to 2.5 weight percent of platinum, 0.5 to 4.0 weight percent of chemically combined alkali metal and a cracking component comprising silica and alumina.
3. The process according to claim 1 wherein the catalyst consists essentially of 0.01 to 2.5 weight percent of platinum, 0.5 to 4.0 weight percent of chemically combined sodium, and a cracking component comprising silica and alumina.
4. A catalyst consisting essentially of a cracking component, 0.01 to 2.5 weight percent of a metal from the group consisting of platinum and palladium, and 0.5 to 4.0 weight percent of a chemically combined alkali metal, said cracking component comprising silica and at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zirconia.
5. A catalyst consisting essentially of 0.01 to 2.5 weight percent of platinum and 0.5 to 4.0 weight percent of a chemically combined alkali metal, and a cracking component comprising silica and at least one metal oxide from the group consisting of alumina, magnesia, thoria, and zirconia.
6. A catalyst consisting essentially of 0.01 to 2.5 weight percent of platinum, 0.5 to 4.0 weight percent of chemically combined sodium, and a cracking component comprising silica and alumina.
FRANK G. CIAPETTA.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,249,337 ViSser et al July 15, 1941 2,317,683 Greensfelder Apr. 27, 1943 2,474,440 Smith et al June 28, 1949 2,478,916 Haensel Aug. 16, 1949 2,550,531 Ciapetta Apr. 24, 1951

Claims (1)

1. A PROCESS FOR REFORMING A GASOLINE FRACTION TO INCREASE THE ANTI-KNOCK VALUE THEREOF WHICH COMPRISES ADMIXING HYDROGEN WITH SAID FRACTION AND PASSING SAID ADMIXTURE AT REFORMING CONDITIONS INCLUDING A TEMPERATURE WITHIN THE RANGE OF 600* F. TO 1000* F. AND A PRESSURE OF FROM 100 TO 1000 P.S.I. OVER A CATALYST CONSISTING ESSENTIALLY OF A CRACKING COMPONENT, 0.01 TO 2.5 WEIGHT PERCENT OF A METAL FROM THE GROUP CONSISTING OF PLATINUM AND PALLADIUM, AND 0.5 TO 4.0 WEIGHT PERCENT OF A CHEMICALLY COMBINED ALKALI METAL, SAID CRACKING COMPONENT COMPRISING SILICA AND
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US2750329A (en) * 1953-05-05 1956-06-12 Atlantic Refining Co Platinum-containing reforming catalysts
US2773011A (en) * 1951-08-30 1956-12-04 Universal Oil Prod Co Hydrogen refining hydrocarbons in the presence of an alkali metal-containing platinum catalyst
US2779742A (en) * 1952-09-18 1957-01-29 Gulf Research Development Co Composite materials and processes for making the same
US2857337A (en) * 1955-05-10 1958-10-21 Du Pont Method of preparing hydrogenation catalysts
US2884382A (en) * 1955-10-05 1959-04-28 Socony Mobil Oil Co Inc Reforming catalyst
US2916443A (en) * 1955-08-08 1959-12-08 Texaco Inc Process for desulfurizing petroleum distillates using a spent platinum reforming catalyst
US2930763A (en) * 1956-03-05 1960-03-29 Universal Oil Prod Co Hydrocarbon conversion catalyst
US2930765A (en) * 1956-03-02 1960-03-29 Distillers Co Yeast Ltd Production of a supported catalyst
US2930766A (en) * 1956-03-06 1960-03-29 Distillers Co Yeast Ltd Production of a supported catalyst
US2939894A (en) * 1956-11-19 1960-06-07 Pure Oil Co Isomerization of light petroleum distillates employing catalyst comprising iron-group metal on lithium-modified acidic mixed oxides support
US2962536A (en) * 1958-04-09 1960-11-29 Atlantic Refining Co Production of polycyclic aromatic hydrocarbons from high molecular weight paraffins
US2968632A (en) * 1958-07-14 1961-01-17 Pure Oil Co Isomerization catalyst
US2972644A (en) * 1956-11-14 1961-02-21 British Petroleum Co Dehydrogenation or dehydrocyclization of non-aromatic hydrocarbons
US2987560A (en) * 1957-11-04 1961-06-06 British Petroleum Co Production of aromatics and catalysts therefor
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US3926779A (en) * 1974-01-21 1975-12-16 Texaco Inc Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst
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US3126426A (en) * 1964-03-24 Hydrogfcnation
US2773011A (en) * 1951-08-30 1956-12-04 Universal Oil Prod Co Hydrogen refining hydrocarbons in the presence of an alkali metal-containing platinum catalyst
US2779742A (en) * 1952-09-18 1957-01-29 Gulf Research Development Co Composite materials and processes for making the same
US2750329A (en) * 1953-05-05 1956-06-12 Atlantic Refining Co Platinum-containing reforming catalysts
US2857337A (en) * 1955-05-10 1958-10-21 Du Pont Method of preparing hydrogenation catalysts
US2916443A (en) * 1955-08-08 1959-12-08 Texaco Inc Process for desulfurizing petroleum distillates using a spent platinum reforming catalyst
US2884382A (en) * 1955-10-05 1959-04-28 Socony Mobil Oil Co Inc Reforming catalyst
US2930765A (en) * 1956-03-02 1960-03-29 Distillers Co Yeast Ltd Production of a supported catalyst
US2930763A (en) * 1956-03-05 1960-03-29 Universal Oil Prod Co Hydrocarbon conversion catalyst
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US2972644A (en) * 1956-11-14 1961-02-21 British Petroleum Co Dehydrogenation or dehydrocyclization of non-aromatic hydrocarbons
US2939894A (en) * 1956-11-19 1960-06-07 Pure Oil Co Isomerization of light petroleum distillates employing catalyst comprising iron-group metal on lithium-modified acidic mixed oxides support
US3003974A (en) * 1957-02-05 1961-10-10 Socony Mobil Oil Co Inc Isomerization catalyst
US2987560A (en) * 1957-11-04 1961-06-06 British Petroleum Co Production of aromatics and catalysts therefor
US2962536A (en) * 1958-04-09 1960-11-29 Atlantic Refining Co Production of polycyclic aromatic hydrocarbons from high molecular weight paraffins
US2968632A (en) * 1958-07-14 1961-01-17 Pure Oil Co Isomerization catalyst
US3065284A (en) * 1959-12-08 1962-11-20 Pure Oil Co Isomerization of normal paraffins
US3082099A (en) * 1960-02-26 1963-03-19 Horizons Inc Inorganic fibers and method of preparation
US3260679A (en) * 1962-05-25 1966-07-12 Standard Oil Co Method of preparing a catalyst composition consisting of sodium, sodium carbonate and iron oxide on alumina and the product thereof
US3679773A (en) * 1968-10-22 1972-07-25 Ashland Oil Inc Dehydrogenation-type reactions with group viii catalysts
US3926779A (en) * 1974-01-21 1975-12-16 Texaco Inc Upgrading of paraffinic gasoline blending components by cyclization with a platinum/magnesium oxide alumina matrix catalyst
US4171286A (en) * 1977-01-10 1979-10-16 Engelhard Minerals & Chemicals Corporation Catalytic cracking
US4329258A (en) * 1979-05-22 1982-05-11 Compagnie Francaise De Raffinage Catalysts for the hydrotreatment of hydrocarbons and use thereof in the reforming and isomerization of hydrocarbons in the presence of hydrogen
US4363721A (en) * 1979-05-22 1982-12-14 Compagnie Francaise De Raffinage Method of using catalysts for reforming or isomerizing hydrocarbons in the presence of hydrogen
US4214978A (en) * 1979-05-29 1980-07-29 Engelhard Minerals & Chemicals Corporation Catalytic cracking
US5053377A (en) * 1988-08-22 1991-10-01 Solvay & Cie (Societe Anonyme) Catalytic compositions, process for obtaining them and process for hydrogenation of 1,1,2-trichloro-1,2,2-trifluoroethane by means of these compositions
US5387729A (en) * 1988-08-22 1995-02-07 Solvay (Societe Anonyme) Catalytic compositions, process for obtaining them and process for hydrogenation of 1,1,2-trichloro-1,2,2,-trifluoroethane by means of these compositions

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