DE1271870B - Process for the catalytic conversion of a hydrocarbon feed - Google Patents

Description

Process for the catalytic conversion of a hydrocarbon feed There are numerous catalysts for the conversion of hydrocarbons into one or several desired products are known. In the catalytic cracking of hydrocarbon oils, in the case of hydrocarbon oils with a higher boiling range in hydrocarbons with lower boiling points Boiling range are converted, especially in those in the motor fuel range boil, for example, the most commonly used catalysts consist of solid Substances that react acidic and cause the hydrocarbons to crack. One large numbers of these acidic catalysts have undesirable properties, e.g. B. lack of thermal resistance or poor mechanical strength, etc. Synthetic silica-alumina mixtures are known to be common catalysts but give limited yields on gasoline for a given coke yield and still have the disadvantage a rapid deterioration in quality and inactivation in the presence of water vapor, especially at temperatures above 538 ° C. Other less commonly used catalysts consist of clays, e.g. B. bentonite and montmorillonite treated with acids have been. Catalysts of this type are relatively cheap, but they are only moderately active and show a decrease in activity with larger numbers of transformation and regeneration cycles. Some synthetic materials, z. B. silica-magnesia complexes are more active than conventional silica-alumina catalysts and are subject to normal aging, but because of their product distribution, they have as it is indicated, for example, by a low octane number of the gasoline, only limited usability.

US Pat. No. 2,971903 discloses a process for improving the quality of hydrocarbons, in which the hydrocarbons are brought into contact at elevated temperatures with a crystalline metal aluminosilicate catalyst which has uniform pore openings between approximately 6 and 15 Å. As a catalyst, a product can be used which is obtained from sodium aluminosilicate by replacing the sodium with other metal cations, such as. B. those of magnesium, aluminum, beryllium, zirconium, cobalt, nickel, copper, calcium, chromium, iron, silver, gold, platinum, zinc, cadmium, rare earths, mercury or lead. Experiments with the preferred embodiment of a catalyst according to US Pat. No. 2,971,903 have shown, however, that this has only a limited activity and selectivity and only gives a small amount of the desired C5 + gasoline when cracked.

From US Pat. No. 2,962,435, cracking is a nitrogenous one Hydrocarbon feed in the presence of a mixture of a common cracking catalyst and a sodium aluminosilicate zeolite. The sodium zeolite is used for this as an adsorbent for nitrogen compounds, so that the cracking of the nitrogen allows freed hydrocarbon feed with the usual cracking catalyst will. Limited conversion is also achieved with this process.

The object of the invention is to create a method for catalytic Conversion of a hydrocarbon feed in the presence of a catalyst which contains an aluminosilicate exchanged with metal cations, with a high conversion of the hydrocarbons used and a catalyst is used, which has a wide range of catalytic activity.

The method according to the invention is characterized in that a catalyst is used which consists of a mixture of a porous matrix and a crystalline rare earth aluminosilicate that has been base-exchanged with rare earth metal cations, in which no more than 0.25 equivalents of alkali metal cations per gram atom of aluminum are present.

According to an advantageous embodiment, a catalyst is used, in which the porous matrix of silicon dioxide, aluminum oxide or mixtures of silicon dioxide or aluminum oxide with an oxide of at least one metal from groups 1I, III or IV of the periodic table.

The catalysts to be used according to the invention can be in proportion low concentrations are used and allow hydrocarbon conversions to be carried out with technically advantageous and controllable throughput speeds at lower Temperatures than they were previously used. In the catalytic cracking of Hydrocarbon oils range into lower molecular weight hydrocarbon products for example the achievable reaction rates per unit volume of catalyst up to thousands of times the speeds of the best ever proposed silicon-containing catalysts were achieved.

For the preparation of the catalysts to be used according to the invention no protection is claimed in the context of the invention. The manufacture of the catalyst can e.g. B. be done in that an aluminum silicate with a gaseous or liquid medium containing an ionizable compound of a rare earth metal, for a period sufficient to allow the desired introduction of such ions bring about, is brought into contact. The resulting product is washed, dried, then distributed in a porous matrix and used thermally activated.

In the manufacture of the rare earth aluminosilicate catalysts can be an aluminosilicate with a, non-aqueous or aqueous solution that a Contains salt of at least one rare earth metal before or after incorporation are brought into contact in the porous matrix. The rare earth metal cation may be present in the solution in an amount which varies within wide limits depending on the aluminosilicate and its silica-alumina ratio. When the aluminosilicate has a molar ratio of silica to alumina greater than 6.0, the solution can have a pH of 3 to 10.0; at a ratio between 5 and 6, the medium can have a pH of 3.5 to 10.0 and preferably 4.5 to 8.5; at a molar ratio of silica to aluminum oxide of less than 5.0 lies the pH of the solution containing the rare earth metal cations contains, ranging from 4.5 to 10.0 and preferably 4.5 to 8.5. - -The cation exchange takes place expediently until the originally present metal i cations are essentially pulled out. Elevated temperatures increase the speed of the treatment, while its duration is inversely related to the concentration of the ions changes in the solution. The temperatures used can be below the ambient Room temperature about 24 ° C up to temperatures below the decomposition temperature of the aluminosilicate. After the exchange treatment, the aluminosilicate becomes washed with water, preferably with distilled or deionized water, until the washing water running off has a pH value between 5 and 8. The received The product can then be analyzed for ion content.

The procedure practically used for the treatment of the aluminosilicate can be carried out in a discontinuous or continuous process under atmospheric, sub-atmospheric or super-atmospheric pressure. An aqueous one or non-aqueous solution of the rare earth ions can slowly pass through a fixed bed of the aluminosilicate. If necessary, a hydrothermal treatment can be used or an appropriate treatment with polar solvents are carried out, by placing the aluminum silicate and the solution in a closed vessel, which is kept under autogenous pressure.

Diverse rare earth compounds can be used as a source of rare earths Earth metal ions find application. Useful compounds include e.g. B. the chlorides, Bromides, iodides, carbonates, bicarbonates, sulfates, sulfides, thiocyanates, peroxysulfates, Acetate, Benzoate, Citrate, Fluoride, Nitrate, Formate, Propidnate, Butyrate, Valerate, Lactates, malonates, oxalates, palmitates, hydroxides or tartrates. The only limitation with respect to the particular rare earth metal salt or salts used in that they are sufficiently soluble in the solvent in which they are used must be in order to produce the necessary transfer of rare earth metal ions. The preferred rare earth metal salts are the chlorides, nitrates and sulfates.

The rare earth metals are characterized by cerium, lanthanum, praseodymium, Neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, Ytterbium, scandium, yttrium and lutetium.

The rare earth metal salts used can be either to the salt of a single rare earth metal or to salts of rare earth metal mixtures act, e.g. B. Rare earth chlorides or didymium chlorides. In the explanations below a rare earth metal chloride solution means a mixture of rare earth chlorides, which essentially consist of the chlorides of lanthanum, cerium, neodymium and praseodymium smaller amounts of samarium gadolinium and yttrium. Rare earth chloride solutions are commercially available, and the solutions referred to in the examples in detail As referred to, the chlorides contain a rare earth mixture, which is a relative composition of 48 percent by weight cerium (as Ce0.), 24 percent by weight. Lanthanum (as La.:!Os), 5 percent by weight praseodymium (as Prs0ii), 17 percent by weight Neodymium (as Nd20 ;;), 3 percent by weight samarium (as Sma0s), 2 percent by weight gadolinium (as Gd-0a) and 0.8 percent by weight of other rare earth oxides. Didymium chloride is in any case a mixture of rare earth chlorides, but a deeper one Has cerium content. It consists of the following rare earths, determined as oxides: 45 to 56 percent by weight lanthanum, 1 to 2 percent by weight cerium; 9 to 10 percent by weight Praseodymium, 32 to 33 percent by weight neodymium, 5 to 6 percent by weight Samarium, 3 to 4 percent by weight gadolinium, 0.4 percent by weight yttrium and 1 to 2 percent by weight other rare earths. It can be seen that other mixtures of rare earths in the same way for the preparation of the catalysts used according to the invention are applicable.

As the aluminosilicates, both natural and synthetic ones which have an amorphous, a crystalline or a combination of crystalline and amorphous structure can be used. However, it has been found that unusually superior catalysts can be obtained when the starting aluminosilicate has either a crystalline or a combination of crystalline and amorphous structure and contains at least 0.5 and preferably 0.8 to 1.0 equivalents of exchangeable cations per gram atom of aluminum. The aluminosilicates can be described as a three-dimensional framework of Si0, - and A104 tetrahedra, in which the tetrahedra are cross-linked by the simultaneous membership of oxygen atoms, the ratio of the total aluminum and silicon atoms to the oxygen atoms being 1: 2. In their hydrated form, the aluminosilicates can be represented by the following formula: Here, M denotes at least one cation which balances the electrovalence of the tetrahedra, n denotes the valence of the cation, w are the moles SiO2, and y are the moles H20. The cation can consist of one or more ions from a number of exchangeable ions, depending on whether the aluminosilicate has been produced synthetically or occurs naturally.

Typical cations include sodium, lithium, potassium, silver, magnesium, Calcium, zinc, barium. Iron, nickel, cobalt and manganese. Albeit the proportions of the inorganic oxides in the silicates and their spatial arrangements vary can, so that certain properties in the aluminosilicate are influenced, The main property of these materials is their ability to cause dehydration without significantly affecting the SiO.1 and A10 "framework.

Aluminosilicates falling under the above formula are known and include synthetically produced aluminosilicates, natural aluminosilicates and certain caustic clays. Preferred aluminosilicates include the zeolites A, Y, L; D, R, S, T, Z, E, F, Q, B, X, heulandite, clinoptilolite, faujasite, Chabazite, gmelinite, mordenite and certain caustic clays, e.g. B. Montmorillonite and kaolin families. The aluminosilicates, the pore diameters, are particularly preferred of at least about 4 angstrom units.

Other synthetically made crystalline aluminosilicates include the substances designated as ZK-4 and ZK-5.

The ZK-4 zeolite can be represented by the following molar ratios of the oxides A1203: 2.5 to 4.0 SiO2: y 1120; herein, R is a member selected from the group consisting of methyl ammonium oxide, HGO, and mixtures thereof, M is a metal cation of valence ir, and y is any value from about 3.5 to 5.5. In the synthesized form, zeolite ZK-4 are presented primarily sodium cations and can be prepared by the following unit cell formula Na7,5 t2 H2 t0.5 9 1 includes: 2A1 L 02-15 ± 2 Si 021st

The material ZK-4 can be prepared by adding a mixture of the oxides Na20, Al20; 3, Si0.2, H.20 and tetramethylammonium ions in an aqueous solution at a temperature of about 100 ° C for periods in the range from 15 minutes to 90 Heated for hours or more. The composition of the reaction mixture, expressed as the molar ratios of the oxides, falls within the following ranges: SiO2 / A1203 from about 2.5 to 11. from about 0.05 to 0.25. from about 25 to 50.

Na 2 O + [(CH34N] 20 from about 1 to 2. The crystallizing product is separated from the mother liquor and then washed and heated in activated in an inert atmosphere.

The material ZK-5 is characteristic of another crystalline aluminosilicate which is produced in the same way as zeolite ZK-4, with the exception that N, N'-dimethyltriethylenediammonium hydroxide is used instead of tetramethylammonium hydroxide. The material ZK-5 can be prepared from an aqueous sodium aluminosilicate mixture which has the following composition, expressed as molar ratios of the oxides: SiO2 / A1203 from about 2.5 to 11. from about 0.01 to 0.25. 25 to 50. 1 to 2.

The N, N'-dimethyltriethylenediammonum hydroxide used in the manufacture of ZK-5 can by methylating 1,4-diazabicyclo- (2,2,2) -octane with methyl iodide or dimethyl sulfate followed by conversion to the hydroxide by treatment with silver oxide or barium hydroxide.

When using the N, N'-dimethyltriethylenediamonium hydroxide in the preparation of ZK-5, the hydroxide can be used as such, or it can be further with a source of silica, e.g. B. silica gel treated and then reacted with aqueous sodium aluminate in a reaction mixture, the chemical composition of which corresponds to the oxide molar ratios listed above is equivalent to. When heated to temperatures of about 200 to 600'C, the methylammonium ion converted into a hydrogen ion.

Other aluminosilicates that can be used are with caustic treated clays.

The aluminosilicate active component prepared in the above manner is combined with a porous matrix in such proportions, dispersed therein or otherwise intimately mixed so that the resulting product is about 1 to 95 percent by weight, and preferably about 2 to 80 percent by weight of the aluminosilicate contains in the final composition.

The term "porous matrix" includes organic and / or inorganic Compositions with which the aluminosilicate is incorporated, dispersed or can be intimately mixed in another way, the matrix being active or inactive can be. It can be seen that the porosity of the compositions used as the matrix either to be inherent in the particular material or by mechanical or chemical means Funds may have been introduced. Typical matrix materials that are used are metals and their alloys, sintered metals and sintered glass, Asbestos, silicon carbide, pumice stone, firebrick, diatomaceous earth, activated carbon, organic Resins e.g. B. polyepoxides, polyamines, polyesters, vinyl resins, phenolic resins, amino resins, Melamines, acrylic resins, alkyd resins, epoxy resins, and amorphous inorganic oxides. from Inorganic oxide gels such as silicon dioxide, Alumina, clay, because of its superior porosity, and abrasion resistance Stability under reaction conditions, especially under such reaction conditions as they occur in the cracking of gas oil, are particularly preferred.

The aluminosilicate and inorganic oxide gel catalysts can be prepared by various methods, wherein the aluminosilicate is comminuted to a particle size of less than 40 microns, preferably within the range of 1 to 10 microns, and intimately mixed with an inorganic oxide gel, while the latter is in one water-containing state is present, e.g. In the form of a hydrosol, hydrogel, wet gelatinous precipitate, or a mixture thereof. So finely divided active aluminosilicates can be mixed directly with a silica-containing gel, which is obtained by hydrolyzing a basic solution of alkali silicate with an acid, e.g. B. hydrochloric acid, sulfuric acid, has been formed. Mixing of the two components can be carried out in any desired manner, e.g. B. in a ball mill or in other types of mixing or kneading devices. The aluminosilicates can also be dispersed in a hydrosol obtained by reacting an alkali silicate with an acid or an alkaline coagulant. The hydrosol is then in mass to a hydrogel solidified which desired then dried and in pieces form is broken or dispersed by conventional spray drying methods dried or through a nozzle into a bath of 01 or another water-miscible solvent to approximately spherically shaped "beads Catalyst particles as described in U.S. Patent 2,384,946. The mixture of aluminosilicate and silicon-containing gel obtained in this way is washed free of soluble salts and then dried and / or calcined, as is desired. The total alkali metal content of the resulting catalyst, including alkali metals that may be present in the aluminosilicate as an impurity, is less than about 4 percent, and preferably less than about 3 percent by weight of the total composition. If an inorganic oxide gel matrix is used which has too high an alkali metal content, the alkali metal content can be reduced either before or after drying by treatment with the above-mentioned gaseous or liquid solvents.

In the same way, the active aluminosilicate can be converted into a matrix which contains an aluminum-containing oxide. Such gels and hydrous Oxides are known and can be produced, for example, by adding ammonium hydroxide, Ammonium carbonate or the like to an aluminum salt, e.g. B. aluminum chloride, aluminum sulfate, Aluminum nitrate, added in sufficient quantity to form aluminum hydroxide, which is converted into aluminum oxide during drying. The aluminosilicate can be incorporated into the aluminous oxide, while the latter is in the form of a Hydrosols, hydrogels, wet gelatinous precipitates or hydrous oxides is present.

The porous matrix can also consist of a semi-plastic or plastic Consist of clay mineral. The aluminosilicate can be incorporated into the clay by you simply mix the two ingredients and the mixture to the desired shape processed. Suitable clays are e.g. B. attapulgite, kaolin, sepiolite, polygarskite, Kaolinite, plastic ball clays, bentonite, montmorillonite, illite, chlorite etc.

The porous inorganic oxide matrix can also consist of a multiple gel which has a predominant amount of silicon dioxide in combination with one or more metals or their oxides from groups 1 B, 1I, 111, IV, V, VI, VII and VIII of the periodic table . Particularly preferred are Mehrfachgele of silica with metal oxides of Groups A 1I, 111, and IV A of the Periodic Table, in particular wherein the metal oxide of magnesium oxide, aluminum oxide, zirconium oxide, titanium oxide, beryllium oxide, thorium oxide, or combinations thereof. The preparation of such gels is known and is generally either a separate precipitation or a mixed filling procedure in which a suitable salt of the metal oxide is added to an alkali silicate and an acid or base, as required, is added to make the appropriate one To precipitate oxide. The silicon dioxide content of the silicon-containing gel matrix which can be considered according to the invention is generally within the range from 55 to 100 percent by weight, the metal oxide content being in the range from 0 to 45 ° (o. Small amounts of promoters or other materials that may be present in the catalyst, are e.g. cerium, chromium, cobalt, tungsten, uranium, platinum, lead, zinc, calcium, magnesium, barium, lithium, nickel and their compounds as well as silicon dioxide, aluminum oxide, silicon dioxide-aluminum oxide or other silicon-containing oxide combinations as fine particles in quantities in the range from 5 to 40 percent by weight, based on the finished catalyst.

The catalyst can be used in an inert atmosphere close to that for the Conversion eligible temperatures are thermally activated, he can but also activated initially during use in the conversion process will. Generally, the catalyst is used at a temperature between about 65% and 316 ° C and then by calcination in air or an inert atmosphere from nitrogen, helium, exhaust gas or some other inert gas at temperatures in the range from about 260 to 815 ° C for periods ranging from 1 to 48 hours or more thermally activated. It can be seen that the active aluminosilicate is also present the incorporation into the inorganic oxide gel can be activated.

According to the invention it has also been found that catalysts with improved selectivity and other favorable properties for some hydrocarbon conversions, z. B. the gas oil cracking, can be obtained by using the catalyst product of a subjected to mild steam treatment at elevated temperatures of 427 to 815'C (800 to 1500 F) and preferably at temperatures of about 538 to 760 ' C (1000 to 1400 'F). Treatment can be in an atmosphere from 10011 / o water vapor or in an atmosphere consisting of water vapor and a for the aluminosilicate there is essentially an inert gas. The steam treatment apparently creates beneficial properties in the aluminosilicate compositions and can be carried out before, after or in place of the calcination.

A particularly preferred embodiment for the production of Catalysts used according to the invention lies in the aluminosilicates vop the treatment described above with the solution or solutions in the porous matrix to incorporate. For this purpose, the aluminosilicate is distributed in a porous matrix, and the resulting catalyst is made with a rare earth metal cation containing Solution treated until the originally present metallic cations are practical are pulled out.

As indicated above, these are the useful ones Catalysts for carrying out the invention include aluminosilicates, the rare earth metal cations contained, which are intimately dispersed in a porous matrix. With exception; lhmc \ 'on AIhaIImel @ lllhalll @ llen, which may be present as impurities, metallic cations other than rare earth metal cations are not associated with the catalyst united.

Within the definition given above, it is preferred that essentially no cations of alkali metals are associated with the aluminosilicate are. The presence of alkali metal cations tends to have catalytic properties depressing or restricting; as a general rule, the activity takes with it an increasing content of alkali metal cations. The amount of alkali metal cations, which can be tolerated in the aluminosilicate obviously depends on the particular catalytic use from which the aluminosilicate is fed. General became found that no more than 0.25 equivalents of alkali metal cations per gram atom Aluminum can be combined with the aluminosilicate.

Further, it is preferred that the aluminosilicate that comes with the solution is treated, 0.5 to 1.0 and, more desirably, 0.8 to 1.0 equivalents contains exchangeable cations per gram atom of aluminum. It has been found that aluminosilicates, which have this high equivalence or substitutability have particular advantages for the cracking of gas oil, especially if the rare earth metal cation of lanthanum, praseodymium, neodymium, samarium, gadolinium or mixtures of rare earth metal cations, which is a preponderant amount of one or more of these particular rarities - Earth metal - containing cations, is formed.

The utility of aluminosilicate catalysts for hydrocarbon conversion will be discussed below in connection with the cracking of a representative hydrocarbon feed illustrated. In the examples given below, the one used was the one used Comparative catalyst made from a conventional "pearl" type silica-alumina cracking catalyst. The silica-alumina catalyst contained about 10 weight percent A120 :; and the remainder Si0z. In some cases it also contained a trace amount of Cr-, O: 3, d. H. about 0.15 percent by weight.

The usefulness of the catalyst is further illustrated by its ability to catalyze the conversion of a mid-continent gas oil with a boiling range of 232 to 510 "C to gasoline with a final boiling point of 210" C. Vapors of the gas oil are passed through the catalyst at temperatures of 468 or 482 "C and essentially atmospheric pressure at a feed rate of 1.5 to 8.0 volumes of liquid oil per volume of catalyst per hour for 10 minutes. The test method was as follows to compare various product yields obtained with such a catalyst with the yields of the same products given by the conventional silica-alumina catalyst at the same conversion level and temperature. The differences given below (1-values ) mean the yields given by the catalyst of the invention minus the yields given by the conventional catalyst. In these tests, the catalysts were tested as cracking catalysts at about 538 (': Il.ti \ errt. The catalyst compositions used according to the invention find extensive use in a Variety of hydrocarbon conversion processes including cracking, isomerization, dealkylation, alkylation, disproportionation, hydration of olefins, amination of olefins, hydrocarbon oxidation, dehydrogenation, dehydration of alcohols, desulfurization, hydrogenation, hydroforming, reforming, hydrocracking, oxidation and polymerization. The catalysts are exceptionally durable and are particularly useful in those of the aforementioned processes which are carried out at temperatures in the range of 21 to 760 ° C, including processes in which the catalyst is periodically regenerated by burning off combustible deposits. Because of their high catalytic activities, the catalysts are particularly useful for carrying out various hydrocarbon conversion processes, e.g. B. the alkylation, at relatively low temperatures with small amounts of catalyst and where they result in a minimum of undesirable side reactions and operating costs.

For example, the dehydrogenation of hydrocarbons, such as Propane, butylene, butane, pentane, cyclopentane, cyclohexane, methylcyclohexane and the like, at temperatures ranging from about 149 to 552 ° C below atmospheric or superatmospheric Pressures with a space velocity (LHSV) of 0.2 to 5000 can be performed. Metals and oxides of metals such as platinum, palladium, Rhodium, tungsten, iron, copper or nickel, as promoters in conjunction with the active aluminosilicate can be used.

For the hydrogenative desulfurization of hydrocarbons can the oxides and sulfides of such metals as cobalt, molybdenum, tungsten, chromium, Iron, manganese, vanadium, copper, platinum group metals and mixtures thereof in combination find application with the aluminosilicate. The desulfurization of shale distillates and the like can occur at temperatures between about 316 and 538 ° C below atmospheric or superatmospheric pressures with space velocity (LHSV) between 0.2 and 50 are performed. The special conditions within these areas depend on the feedstock to be desulphurized and the desired one Product.

The catalysts can also be used for the hydrogenation of unsaturated aliphatic hydrocarbons, e.g. B. monoolefins, diolefins, are used, to form the corresponding saturated hydrocarbons; the same goes for for the hydrogenation of unsaturated cyclic hydrocarbons. For hydrogenation reactions the temperature can be at a pressure of about 0.7 to 210 kg / cm- or more and one Space velocity (LHSV) ranges from about 0.5 to 50 up to 38'C. The promoters, those normally used with the aluminosilicate include the oxides of Nickel, copper and iron, and platinum group metals.

The hydrocracking of heavy residual petroleum oils, cycle oils can be carried out with active aluminosilicates which contain about 0.05 to 10 percent by weight of a platinum metal such as platinum, palladium, rhodium, osmium, iridium and ruthenium, or oxides or sulfides of metals such as cobalt, molybdenum, Tungsten, chromium, iron, copper, contained as a promoter. The petroleum feed is cracked in the presence of the catalyst at temperatures between 204 and 440 ° C using molar ratios of hydrogen to hydrocarbon feed ranging between 2 and 80. The pressure applied is between 0.7 and 176 atmospheres, and the space velocity is between 0.1 and 10.

The catalysts can also be used for the alkylation of aromatic Hydrocarbons or phenols and the conversion of olefinic, acetylenic and naphthenic hydrocarbons can be used. The alkylation of aromatics and phenols can be used at temperatures between about -9 and 454 ° C under pressures of about 0 to 70 atmospheres can be carried out. The aromatization reaction can take place at temperatures between about 177 and 593 ° C under atmospheric or elevated pressures will. Other reactions for which the catalysts are useful include Isomerization, polymerization, hydrogen transfer, and oxidation.

The following examples are used to carry out the invention further explained: Example 1 25 parts by weight of one identified as zeolite 13X synthetic crystalline aluminosilicate were contained in 75 parts by weight of a silica-alumina matrix dispersed, which consisted of 94 percent by weight SiO-2 and 6 percent by weight A1203. The resulting composition was made over twelve contacts of 2 hours each with a 2 weight percent aqueous solution of rare earth metal chlorides treated. The aluminosilicate composition was then washed with water until the effluent contained no chloride ions, dried and then at 648 ° C for 24 hours treated with steam at 1.05 atmospheres; a catalyst resulted with a Rare earth content, determined as rare earth oxides, of 15.5% and a sodium content of 0.28%.

The table below shows the cracking values of the catalyst when it was tested for cracking gas oil at 482 = C. Cracking values Conversion, percent by volume ...... 65.9 flow rate, LHSV 4 gasoline, 10 RVP, volume percent .... 52.9 excess C.1, percent by volume ..... 13.4 Cs + gasoline, percent by volume ...... 50.8 total C.1, percent by volume. . . . . . . . 15.5 dry gas, weight percent ..... 7.7 coke, weight percent. . . . . . . . . . . 4.2 H "weight percent.............. 0.04 1-advantage gasoline, 10 RVP, volume percent .... +5.3 excess C.4, volume percent ..... -2.7 C5 + gasoline, percent by volume ...... +5.3 total C-1, percent by volume ..... ... -2.6 dry gas, percent by weight ..... -1.1 coke , Weight percent........... -1.5 Example 2 The procedure of Example 1 was repeated with the exception that a 2 percent strength by weight aqueous solution of lanthanum chloride was used in place of the rare earth chloride solution The resulting catalyst contained 0.35 weight percent sodium and 14.9 weight percent lanthanum, determined as lanthanum oxide, and had the cracking values listed in the table below: Cracking values conversion, volume percent ....... 68 flow rate, LHSV .. 4 gasoline, 10 RVP, percent by volume .... 57.1 excess C_I, percent by volume ...... 13.1 C., + gasoline, percent by volume ....... 54.6 total C_I, percent by volume...... ... 6.9 dry gas, weight percent ...... 3.8 H-2 , Weight percent .......... . . . . . 0.002 (- advantage gasoline, 10 RVP, volume percent .... +8.3 excess C1, volume percent ..... -4.1 C; + gasoline, volume percent ...... +7.9 total CI, Volume percent .... .... -3.6 dry gas, weight percent ..... -2.3 coke, weight percent........... -2.4 Example 3 The procedure of Example 1 was repeated except that a 2 weight percent aqueous solution of cerium chloride was used in place of the rare earth chlorides The resulting catalyst contained 0.29 weight percent sodium and 15.3 weight percent cerium, determined as ceria, and had those in the table below listed cracking values: Cracking values conversion, volume percent ....... 63 flow velocity, LHSV .. 4 gasoline, 10 RVP, volume percent ..... 53.1 excess CI, volume percent ...... 11.4 C; + Gasoline, percent by volume ....... 50.9 total C-1, percent by volume......... 13.7 dry gas, percent by weight ...... 6.5 coke, percent by weight ... ... 3.7 H- "weight percent. . . . . . . . . . . . . . 0.03 (- advantage gasoline, 10 RVP, value percent .... +6.8 excess CI, volume percent ..... -3.5 C5 + gasoline, volume percent ...... +6.8 total C4 , Volume percent........ -3.3 drying gas, weight percent ..... -1.7 coke, weight percent ...... ... ... -1.4 Example 4 The procedure according to example 1 was repeated except that a 2 weight percent aqueous solution of didymium chloride was used in place of the rare earth chloride solution, and the resultant catalyst had a sodium content of 0.32 weight percent and a rare earth content of 15.4 weight percent, and it showed the cracking values given in the table below: Cracking values conversion, volume percent ... .... 61.4 flow rate, LHSV ... 4 gasoline, 10 RVP, volume percent ..... 49; 3 excess CI, volume percent .... .. 12.2 C5 + gasoline, percent by volume ....... 47.1 total CI, percent by volume......... 14.4 dry gas, percent by weight ...... 6.8 coke, Weight percent........... . . 4.2 Hz, weight percent. . . . . . . . . . . . . . . 0.16 (- advantage gasoline, 10 RVP, volume percent .... +3.8 excess CI, volume percent ..... -2.1 C5 + gasoline, volume percent ...... +3.7 total C. .4, volume percent........ -2.2 drying gas, weight percent ..... -1.1 coke, weight percent ..... ....... -0.5 Example 10 parts by weight of a Caustic McNamee tones were dispersed in 90 parts of a silica-alumina matrix and the resulting composition was treated with a 2% by weight aqueous solution of lanthanum chloride over two contacts for 24 consecutive hours each, and the resulting composition was washed with water until the effluent contained no chloride ions, dried and then treated for 24 hours at 648 ° C. with steam at 1.05 atmospheric pressure; a catalyst with a lanthanum content, determined as lanthanum oxide, of 10.6 percent by weight was obtained.

The table below shows the cracking values of the catalyst at its investigation for the cracking of gas oil at 482 C.

Cracking values conversion, percent by volume ....... 59.3 flow rate, LHSV .. 4 gasoline, 10 RVP, percent by volume ..... 51.3 excess C1, percent by volume ...... 9.7 C; + Gasoline, percent by volume ....... 48.6 total C_ (, percent by volume......... 12.4 dry gas, percent by weight ..... 6.1 coke, percent by weight.. ... . ...... 2.4 H._ "Weight percent.............. 0.02 (-Advantage gasoline, 10 RVP, volume percent .... +6.8 excess Ci, percent by volume ..... -3.9 C; + gasoline, percent by volume ...... +6.3 total C.4, percent by volume ..... ... -3.3 dry gas, percent by weight . -1.5 .............. coke, percent by weight. -2.0 Comparative tests to a comparison of the rare earth aluminosilicate catalyst according to the invention with the catalysts according to the USA. Patent 2 971903, samples of the catalyst were prepared in accordance with U.S. Patent 2 971903 in accordance with Example 1 of that patent, and the aluminosilicate thus obtained, which was in the sodium form, was then prepared using the procedure of U.S. Example 5 . Patent. Example 5 of this The patent is directed to the catalyst preferred according to this patent, namely a crystalline magnesium-sodium-aluminosilicate.

The catalyst according to US Pat. No. 2,971,903 was then compared with catalysts which were used in accordance with the invention and which contained crystalline rare earth aluminosilicates dispersed in a matrix. For this purpose, the catalysts were tested for their catalytic activity under the same conversion conditions. In each case, a mid-continent gas oil with a boiling range of 232 to 510 "C was cracked to gasoline with an end boiling point of 210" C by the vapors of the gas oil at a temperature of 482 ° C using a feed rate of 4 volumes of liquid DI per volume of catalyst per hour were passed through the catalyst at essentially atmospheric pressure. The tested catalysts were stabilized by treatment with steam at atmospheric pressure at 662 ° C. for 20 hours prior to the investigation. This treatment leads to an identical or comparable state with regard to the different degrees of aging that exist in catalytic converters under technical operating conditions.

The results of the comparative tests are summarized in the table below. Catalyst type conversion C5 -i- gasoline Volume percent Volume percent Catalyst according to the crystalline Mg-Na-Alumino-10.7 8.5 U.S. Patent 2 971903 Silicate (no matrix) (Example 5) Catalyst according to the 25% crystalline rare - 57.7 44.6 Invention (A) Earth aluminosilicate in a matrix Catalyst according to the 10% crystalline rare 55.2 44.5 Invention (B) Earth aluminosilicate . in a matrix It can be seen from the results that the catalysts provided in the process according to the invention, which contain a crystalline rare earth aluminosilicate dispersed in a matrix, have an exceptionally high convertibility. The catalysts provided according to the invention are far superior to the catalyst according to US Pat. No. 2,971,903 in terms of activity and selectivity.

Furthermore, it is clear from the test results in the table that the catalyst provided according to the invention, even when very extensively diluted by a matrix material, has excellent activity and excellent selectivity and significantly larger amounts of gasoline, ie the product primarily desired in a cracking treatment, yields as the preferred catalyst according to U.S. Patent 2,971,903.

Claims (2)

Claims: 1. Process for the catalytic conversion of a hydrocarbon feed in the presence of a catalyst which is an aluminosilicate exchanged with metal cations contains, characterized in that a catalyst is used, which consists of a Mixture of a porous matrix and a base-exchanged with rare earth metal cations, crystalline rare earth aluminosilicate in which no more than 0.25 equivalents of alkali metal cations are present per gram atom of aluminum. 2. The method according to claim 1, characterized in that a catalyst is used in which the porous matrix of silicon dioxide, aluminum oxide or mixtures of silicon dioxide or aluminum oxide with an oxide of at least one metal from groups II, III or IV of the periodic table is hesteht_ Considered publications: German Auslegeschriften No. 1050 477, 1060 076; French Patent Specification No. 1267 749th; U.S. Patent Nos. 2,962,435, 3,039,953; 2971903.