PL87228B1 - - Google Patents

Description

*** qu * t »» j Inventor: _____ ^^. Patent holder: Universal Oil Products Company Des Plaines Illinois (United States of America) Catalyst for the conversion of hydrocarbons The subject of the invention is a catalyst for the conversion of hydrocarbons, especially isomerization, hydrocracking, hydrocarbon dehydrogenation or reforming, with exceptional activity and resistance to deactivation. In the hydrocarbon conversion process, a catalyst is required with the functions of both hydrogenation and dehydrogenation. Mixed hydrogenation-dehydrogenation and cracking catalysts are now widely used in many industries such as petroleum and petrochemical industries to expand the hydrocarbon conversion range. In general, cracking is related to the acidic nature of a porous, adsorptive, refractory, oxide-type material used as a substrate or carrier for a heavy metal, such as metals or metal compounds of Groups V-VIII of the Periodic Table of the Elements, with generally hydrogenating effect. - dehydrogenation. Mixed catalysts are used to accelerate a wide range of hydrocarbon conversion reactions such as hydrocracking, isomerization, dehydrogenation, hydrogenation, desulfurization, cyclization, alkylation, polymerization, cracking and hydroisomerization. * In many cases, such catalysts are preferably used in the processes, in which more than one $ of the above reactions are carried out simultaneously. An example of this type of process is the reforming process, in which a hydrocarbon feed stream containing paraffins and naphthenes is subjected to conditions that activate the dehydrogenation of naphthenes to aromatics, dehydrocyclization of paraffins to aromatics, isomerization of naphthenes and paraffins, hydrocracking of naphthenes and paraffins and similar reactions to produce a product richer in octane or aromatics. Another example is the hydrocracking process, in which catalysts of this type are used for the selective hydrogenation and cracking of high molecular weight hydrocarbons, unsaturated compounds, selective hydrocracking of high molecular weight compounds, and similar other reactions to make more value. Lower boiling point.2 87 228 A further example is the isomerisation process in which a hydrocarbon fraction relatively rich in straight chain paraffins is contacted with a bifunctional catalyst to form compounds. Regardless of the nature of the reaction or process, the bifunctional catalyst should not only be capable of acting in accordance with its nature, but should exhibit its maximum activity in a satisfactory, sufficiently long period of use. The value of the catalyst, which determines its catalytic ability in terms of activity, selectivity and stability, is determined on the basis of analytical tests in a specific application system. For this purpose, the above characteristics of the catalyst for a given raw material charge were determined as follows: activity is a measure of the catalytic capacity of hydrocarbons to form products at a certain level under certain conditions, i.e. at a certain temperature, pressure and contact time, in the presence of diluents such as like hydrogen; selectivity determines the amount of the desired product or products obtained in relation to the amount of converted reactants, stability determines the change in dependence on time, with specific parameters of activity and selectivity, with a smaller change showing greater stability of the catalyst. As it is known, the main reason for the observed deactivation or instability of the bifunctional catalyst when used in the hydrocarbon conversion reaction is the formation of coke on the surface of the catalyst. In the conversion of hydrocarbons, under typical conditions heavy, high molecular weight, black, solid or semi-solid carbon deposit covering the surface of the catalyst and reducing its activity by reducing the contact area. One of the major problems faced by the industry in this field is the need for more active and selective mixed catalysts, but less sensitive to the presence of charred deposits and / or capable of reducing the formation of these deposits on the catalyst. From the point of view of the process parameters, the problem comes down to obtaining a bifunctional catalyst with higher activity, selectivity and stability. Particularly in the reforming process, this problem is typically expressed in the octane yield of C6 + hydrocarbons, proportional to the activity of the catalyst. There is a known hydrocarbon conversion catalyst containing a porous refractory carrier such as alumina at 0.01-2% by weight of the group metal. of platinum metals, 0.01-2% by weight of rhenium, possibly 0.1-3.5% by weight of halogen and, optionally, 0.05-0.5% by weight of sulfur. General methods for the conversion of hydrocarbons in the presence of catalysts containing metals II-VI or II- Group VIII of the Periodic Table of the Periodic Table, preferably with the addition of halogen, is described in Polish Patent Nos. 27491, 23159, 19934 and 32078. It has now been found that the addition of 0.01-5% by weight of germanium to the above-mentioned catalyst, possibly in the form of a compound The subject of the invention is a mixed bifunctional catalyst with increased activity, selectivity and stability, suitable for use in hydrocarbon conversion, isomerization, hydroisomerization, dehydrogenization, desulfurization, denitrogenization, hydrogenation, alkylation, dealkylation, hydrodecyclization, transalkylation, cyclization, dehydrocyclization, cracking, hydrocracking, reforming and other forms of platinum group components rhenium and germanium embedded in a porous, refractory carrier. Such a catalyst can be used particularly advantageously in the reforming of hydrocarbons fractions in the range of gasoline boiling point to produce a high-octane reforming product. In the reforming process, the main advantages of using the new catalyst according to the invention lie in the stability of the catalyst used under constant conditions of use, high efficiency under severe process conditions, eg, low pressure reforming process, producing a reformer product with a high Cs + hydrocarbon content and an octane number of about 100 µl. It has been shown that the addition of germanium and rhenium as components to a bifunctional hydrocarbon conversion catalyst containing a platinum group component significantly improves the catalyst properties discussed above. As a catalyst carrier according to the invention, a porous, refractory material such as inorganic oxide is used, the catalyst components being containing germanium, rhenium and a metal from the platinum group, are usually used in relatively small amounts, causing the conversion of hydrocarbons to the corresponding hydrocarbons. The catalyst according to the invention contains as components platinum, rhenium and germanium deposited on alumina as a carrier, in amounts of 0.01 -2% by weight of platinum, 0.01-2% by weight of rhenium and 0.01-5% by weight of germanium, calculated as elements. The catalyst may also contain halogen in an amount of preferably 0.1-3.5% by weight of , converted to the square root. It may also contain sulfur in an amount of 0.05-0.5 wt.%. 87 228 3 The catalyst composition is reduced with hydrogen under anhydrous conditions before being used to convert hydrocarbons. Sulfur in an amount of 0.05-0.5% by weight, based on free sulfur, may be introduced into the previously reduced catalytic mixture. As stated above, the catalyst according to the invention comprises a porous support containing catalytically effective amounts of a platinum component, rhenium, and germanium, and preferably also as a halogen component. It is preferred that the carrier used has a high adsorption capacity with a developed surface area of -500 m 3 / g. The porous carrier should be refractory under the conditions of hydrocarbon conversion and may be a carrier traditionally used in the hydrocarbon conversion process with dual-purpose catalysts such as: activated carbon, coke or charcoal; silica or silica gel, silicon carbide, clays, and synthetic and natural silicates possibly treated with acid, such as attapulgite, kaolin, diatomite, Fuller earth, kaolin clays, silica, ceramics, porcelain, crushed refractory brick, bauxite; refractory inorganic oxides such as alumina, titanium oxide, zirconium dioxide, chromium oxide, zinc oxide, magnesium oxide, thorium oxide, boron oxide, silica alumina, chromaluminum oxide, boraluminum oxide, silicirconium oxide; crystalline aluminosilicates, such as naturally occurring or synthetically produced modernites and / or faujasites in the form of hydrogen or after treatment with multivalent cations, and: combinations of major groups. Preferred porous supports are refractory inorganic oxides obtained from crystalline aluminum oxides in the form of gamma, eta or theta, with gamma or eta alumina giving the best results. Additionally, in some embodiments, the alumina may contain in small amounts other known rugged inorganic oxides such as silica, zirconium oxide, and magnesium oxide, however, the preferred substrate is pure gamma lab eta alumina. Preferred carriers have a bulk density of 0.3-0.7 g / ml and a specific surface with a pore diameter of 20-300 A, a pore volume of 0.1-1 ml / g and a specific surface area of 100-500 m2 / g. Excellent results are achieved with gamma - aluminum oxides as a carrier, in the form of spherical particles with a relatively small diameter, e.g. about 1.6 mm and a bulk weight of about 0.5 g / ml, pore volume about 0.4 ml / g and a specific surface of about 175 m2 / g The preferred carrier may be synthetically or naturally produced alumina. Each alumina should be activated by one or more treatments, including drying, calcining or steaming before it is used, and it may also be used in the form of known activated alumina, in porous or gel form. The alumina support can be prepared, for example, by adding a suitable alkaline reagent such as ammonium hydroxide to an aluminum salt such as aluminum chloride or aluminum nitrate to form a gel aluminum hydroxide which, after drying and calcining, is converted to an aluminum oxide. aluminum. The alumina can be produced in any form, e.g. spherical, pellets, cakes, extruded shapes, powders or granules of any size, with a spherical form being particularly preferred. Spherical alumina may be produced in a known continuous manner, e.g. by dripping, consisting in the production of alumina hydrosol, combining the hydrosol with a suitable gelling agent and dropwise addition of the obtained mixture to an oil bath maintained at an elevated temperature. The droplets remain in the oil bath until the hydrogel is formed into balls. After washing, the spheres are dried and calcined to give gamma alumina crystalline spheres. One of the essential components of the catalyst according to the invention is germanium. This component may be in metallic form or in a chemical compound, such as an oxide, sulphide, halide, oxychloride or aluminate. Best results are obtained, for example, when germanium is present as an oxide component in the catalytic mixture instead of the pure metal. The best results are obtained when the composition contains 0.05-2% by weight germanium. Germanium may be incorporated into the catalytic mixture by any means, e.g. by co-precipitation or co-gelation with a porous carrier, ion exchange with a gelled carrier, or by saturation of the carrier before or after drying and calcining it. One way to introduce germanium into the carrier is to co-precipitate it, preferably with aluminum oxide as the carrier. In this process, a soluble germanium compound, such as germanium tetrachloride, is added to the alumina hydrosol, combined with a suitable gelling agent, and the resulting mixture is then dropped into the oil bath and left in the bath to mature. The resulting germanium-impregnated carrier beads are washed, dried and calcined. The obtained catalytic mixture contains homogeneously mixed oxides of aluminum and germanium. An also preferred method is to incorporate germanium into the catalytic mixture by using a soluble, degradable germanium compound to saturate the porous carrier. In general, the solvent used in this impregnation step is a solvent capable of dissolving the germanium compound, preferably an aqueous acidified solution. For this purpose, germanium is added to the carrier by mixing the carrier with an aqueous acidified solution of a suitable germanium salt or a suitable compound thereof, for example germanium tetrachloride, germanium difluoride, germanium tetrafluoride, germanium diiodide, germanium monosulfide or the like. A particularly preferred saturation solution is a solution of metallic germanium dissolved in chlorine water to obtain germanium monoxide. Germanium as an ingredient can be supplied simultaneously with other ingredients or after their addition to the carrier, with excellent results being achieved when germanium as an ingredient is used for saturation simultaneously with other metal ingredients. A preferred saturating solution is an aqueous solution containing chloroplatinic acid, hydrogen chloride, perrhenic acid and germanium oxide dissolved in chlorine water. After the impregnation step, the resulting composition is dried and calcined. It is preferable to distribute the germanium evenly throughout the medium, which is achieved by keeping the pH of the saturating solution at 1-7 and diluting the impregnating solution to an excess of the volume of the impregnated medium. The ratio of volume of impregnating solution to volume of carrier is preferably at least 1.5: 1, especially 2-10: 1 or more. The saturation time also applies! It is suitably long, preferably 0.2S-0.05 hours or more, and then excess solvent is removed prior to drying. This is made possible by a good dispersion of germanium on the support, an aging process is preferably used in the impregnation step. The second essential component of the catalyst according to the invention is a component from the platinum group, preferably platinum, but may be other metals from this group, e.g. palladium, ruthenium. , osmium or iridium. In a mixed catalyst the platinum group component may be present in the form of a compound such as an oxide, sulphide, halide or as a metallic element. In general, the amount of the platinum group component in the catalyst is small compared to the other components in the catalyst and is typically 0.01-2 wt% of the metallic component, with excellent results being obtained when the catalyst contains 0.05- 1% by weight of platinum group metal. The platinum group component may be introduced into the catalytic mixture in any suitable manner, for example by co-precipitation or co-gelation with a suitable carrier, ion exchange or saturation. A preferred method is to impregnate the carrier with a soluble and degradable platinum group compound. In this case, the platinum group component can be incorporated into the resin by mixing with an aqueous solution of chloroplatinic acid. Other water-soluble pyatin compounds may also be used, for example, ammonium chloroplatinate, bromoplatinic acid, pyatin dichloride, platinum tetrachloride hydrate, platinum dichlorocarbonyl dichloride or diaminoplatinum diamine. Chloroplatinic acid is preferably used as the chloride-platinum compound since this facilitates the incorporation of both platinum and the preferred halogen in one step. In general, hydrogen chloride is also added to the impregnation solution to facilitate incorporation into the catalyst as a halogen. In general, impregnation of the carrier is preferably carried out after calcination in order to reduce the risk of washing away the valuable platinum group metals. However, in some cases it is preferable to impregnate the gel in the medium. The saturated carrier is dried and then calcined or oxidized at high temperature. Another essential component of the catalyst of the invention is rhenium, incorporated in a metallic form or in a chemical compound such as an oxide, sulfide or halide, or in physical or chemical combination with a porous carrier and / or other catalyst components. Rhenium is preferably used in an amount of 0.01-2% by weight, based on rhenium metal, in particular 0.05-1% by weight, based on the weight of the catalyst. Rhenium can be incorporated into the catalyst mixed in a suitable convenient manner and at any stage of its preparation. In general, it is desirable to include rhenium in the impregnation step of the carrier after forming the porous carrier in order to avoid loss of this metal during washing and cleaning of the carrier during its processing, however any convenient method may be used to introduce rhenium. Typically, a degradable rhenium salt such as ammonium perrhenate, sodium perrhenate, potassium perrhenate and / or rhenium halide solutions, e.g. rhenium chloride, is used as the impregnating solution. A preferred saturating solution is an aqueous solution of perrenonic acid. The porous carrier is impregnated with the rhenium component before, simultaneously with or after being impregnated with the other components mentioned previously, but the best results are usually obtained when impregnating with rhenium together with the other metallic components. Preferably, a one-step solution saturation process is used, using an aqueous solution of chloroplatinic acid, perrenic acid, hydrochloric acid and germanium oxide dissolved in chlorine water. The quality of the catalyst is advantageously influenced by its presence as a halogen component. The chemistry of linking the halogen to the carrier is not fully known so far, and usually the halogen component is introduced into the catalyst by impregnating the carrier, either directly or with other catalyst components. The halogen can be fluorine, chlorine, iodine, bromine or a mixture thereof, preferably using fluorine, in particular chlorine. The halogen can be added at each stage of the preparation of the carrier or optionally after its calcination, 87228 as an aqueous acid solution, e.g. hydrogen fluoride , hydrogen chloride, hydrogen bromide. The halogen component may be combined with the carrier during its impregnation with platinum group components, or in a mixture with other components, e.g. by using a mixture of chloroplatinic acid and hydrogen chloride. The alumina hydrazol used to form the preferred alumina carrier may also include halogen and thus at least a portion of the halogen component is included in the mixed catalyst. In the reforming process, halogen is introduced into the carrier in an amount corresponding to 0.01-3.5% by weight, preferably 0.5-1.3% by weight, based on the halogen element. In the catalytic isomerization or hydrocracking process, in general, correspondingly higher amounts of halogen, in the order of up to about 10% by weight of halogen based on the halogen element, preferably 1-5% by weight. The amount of the metal components in the catalyst according to the invention is preferably determined as a function of the sum of rhenium and germanium to the platinum group component. For this purpose, the amount of rhenium is chosen so that the ratio of rhenium to the platinum group metal in the catalyst is 0.1-3: 1 and the amount of germanium in the atomic ratio of germanium to platinum group metal is 0.25-6: 1. an important parameter of the catalyst according to the invention is the total content of metals in the mass of the catalyst, being the sum of the metal components of the platinum group, rhenium and germanium, calculated as metallic elements. Good results are obtained by the catalyst according to the invention containing 0.134% by weight of di, and in particular 0.3- 2% by weight of the total metal content. A particularly preferred mixed catalyst comprises platinum, rhenium, germanium and a halogen on alumina carrier in an amount of 0.5-1.5% by weight halogen! 0.05-1 wt% platinum, 0.05-1 wt% rhenium and 0.05-2 wt% germanium. Examples of particularly preferred mixed catalyst sets are given in Table I, the concentrations converted to metallic elements. Table 1 Catalyst No. 1 2 J 4 6 German 0.5 | 0.1 0.375 0.2 0.5 1.0 Rhenium 0.5 0.1 0.375 0.1 0.25 0.5 Platinum 0.75 0.1 0.375 0.5 0.25 0.5 In the catalysts mentioned in Table 1, the preferred carrier is alumina, all catalysts containing 0.5-1.5% by weight of halogen based on the metallic element. The mixed catalyst is prepared ready for use by drying usually at 93 ° C. 316 ° C for 2-24 hours or more, followed by calcination at 371 ° C-593 ° C in an air atmosphere for 0.5-10 hours to convert the metallic components to the oxide form. best results are achieved if halogen is introduced during the calcination step by introducing the halogen or halogen-containing compound into the air atmosphere during treatment. If chlorine should be present in the catalyst, then preferably, at least in part of the calcination stage, water and hydrogen chloride are introduced in a molar proportion of 20-100: 1, determining the chlorine content in the catalyst in the final phase of the calcination 0.5-1.5% by weight * Preferably is to subject the mixed catalyst to anhydrous reduction prior to use in the conversion of hydrocarbons to ensure uniform dispersion of the metallic components throughout the carrier. The reducing agent used is preferably pure and dry halogen with a water content of not more than 20 ppm by volume. The reducing agent is introduced during the catalyst calcination process at 427 ° C-649 ° C for 0.5-10 hours or more to reduce platinum and rhenium to a metallic form. The reduction process can be carried out in situ as an initial step during the catalyst life process! after prior drying of the plant and the use of anhydrous hydrogen. In some cases, the reduced catalyst is preferably subjected to a preliminary sulfurization operation to introduce into the catalyst 0.05-0.5 wt% sulfur based on the element. The sulfurization process is preferably carried out in the presence of hydrogen and a suitable sulfur-containing compound, such as hydrogen sulfide, lower molecular weight mercaptans or organic sulfides. The sulfurization process consists in reducing the catalyst with a sulfurizing gas such as a mixture of hydrogen and hydrogen sulfide containing about moles of hydrogen per mole of hydrogen sulfide, under suitable conditions, usually at a temperature of 10-593 ° C. In general, as practice shows, the sulfurization process should be carried out in anhydrous conditions. Hydrogen and hydrocarbon streams in the hydrocarbon zone are contacted with a catalyst of the type described above, on a fixed bed, in a moving bed, in a fluidized bed or in a batch process, however, in order to avoid losses of the catalyst due to mechanical abrasion, a solid bed process is preferably used. In this system, a gas containing hydrogen and hydrocarbon is preheated at a predetermined reaction temperature and introduced into a conversion zone containing a fixed catalyst bed. The conversion zone may be an arrangement of one or more reactors suitably linked to ensure the correct conversion temperature in a particular reactor. Contact of the reactants with the catalyst bed can be. obtained by introducing them through the bed layer from the top, bottom or radius in the bed layer, the latter method being more preferred. The reactants can be passed through the catalyst in a liquid phase, a mixed liquid-vapor phase or a vapor phase, the best results being obtained in the vapor phase. In the reforming process, the catalyst according to the invention is used in a system of one or more fixed bed reactors equipped with with suitable heating devices to compensate for heat losses due to the endothermic nature of the reaction in the catalyst bed. The hydrocarbon stream supplied in the reforming process consists of hydrocarbon fractions containing naphthenes and paraffins with the boiling point of gasoline. Hydrocarbons consisting essentially of naphthenes and paraffins are preferably used in the reforming process, although aromatic compounds may also be present. A preferred group of reformed hydrocarbons are straight distillate gasolines, raw gasolines, catalytic or thermal cracking gasolines or their high boilers or mixtures thereof. The reformed gasoline may be all its fractions in the initial boiling point range of -66 ° C and the final fractions in the boiling range of 163 ° C-219 ° C, as well as selected fractions of gasoline from thermal or catalytic cracking, or it may be a selected fraction with a higher the boiling point is usually called heavy kerosene, for example kerosene with an initial boiling point ranging from the boiling point of C7 hydrocarbons to 204 ° C. In some cases, it is also advantageous to introduce into the process pure hydrocarbons or mixtures of post-extraction hydrocarbons from distillation processes, for example straight-chain paraffins, which are converted into aromatic hydrocarbons in the reforming process. Preferably, the hydrocarbons introduced are catalytically pretreated by conventional methods, such as hydrotreating, simple hydrotreatment, or desulfurization with hydrogen to remove all contaminants with sulfur, nitrogen and water and saturate all olefins. Hydrocarbons containing paraffinic hydrocarbons rich in C4 - C8 normal paraffins, n-butane, n-alkyl aromatic hydrocarbons, such as hexane, a mixture of xylene isomers or naphthenic hydrocarbons are processed in the hydrocracking process. gas oil or heavy oil from the cracking process. Similarly, pure hydrocarbons can be converted into more valuable products by using the catalyst of the invention in any of the known hydrocarbon conversion processes which use dual-function catalysts. Reforming is sometimes preferably stacked The new catalyst was mixed in an anhydrous environment. Achieving this condition in the reforming zone requires controlling the water content in the hydrocarbon feed stream and in the hydrogen stream into the reaction zone. The best results are obtained when the water content, expressed in terms of weight of the reaction mixture introduced into the conversion zone from any source, does not exceed SOppm, preferably 20 ppm. The reaction mixture may be dried by using any conventional solid selective water adsorbent, e.g. crystalline sodium or calcium aluminosilicates, silica gel, activated alumina, molecular sieves, anhydrous calcium sulphate, sodium with a developed surface, etc. Also, the water content can be adjusted by column fractionation ¬ not fractionating or in a similar device, and in some cases, a combination of adsorption and distillation may be used. Preferably the reaction mixture is dried to a water content of less than 20 ppm, it is generally preferred to dry the hydrogen stream introduced into the conversion zone to 10 ppm water or less, conveniently by contacting a suitable dehydrating agent. In the reforming process, the stream exiting the reaction zone is introduced through a cooling system, to a separation zone, maintained at a temperature of -4 ° C to 66 ° C, in which the hydrogen-rich gas is separated from the high-octane liquid product, usually called unstabilized reformed product. the hydrogen-rich gas is withdrawn from the separation zone and passed over a selective water adsorbent. The resulting anhydrous hydrogen stream is then directed back to the reforming zone. The liquid phase from the separating zone is withdrawn and fractionated to adjust the concentration of butane and the volatility of the resulting reformed product. The parameter conditions used in many forms of hydrocarbon conversion are similar to those commonly used in particular types of processes such as isomerization, alkyl aromatics and paraffins. Convenient parameters for the mentioned conversion processes are as follows: temperature 0 ° C-538 ° C, preferably 24 ° C- 316 ° C, pressure from atmospheric to about 100 atmospheres, molar ratio of hydrogen or hydrocarbon 0.5-20: 1, volumetric speed liquid flow per hour (LHSC) 0.2-10, calculated as the ratio of the sum of the equivalent volume of liquid flowing in 1 hour through the catalyst bed to the volume of the catalyst. The dehydrogenation conditions are as follows: temperature 371 ° C-677 ° C, pressure 0 , 1-10 atmospheres; hourly volume speed of liquids; expressed as the ratio of the volume of liquid flowing in an hour through the volume of the catalyst (LHSV) 1 - 40 and the molar ratio of hydrogen to hydrocarbon 1 - 20: 1. Hydrocracking conditions are as follows: pressure 35 - 205 atmospheres; temperature 204-482 ° C; LHSV 0.1-10 and the quantitative ratio of the introduced hydrogen to the introduced liquid reaction mixture 178-1780 Nm3 / m3. In the reforming process, the pressure is from atmospheric to 69 atmospheres, preferably 4.4 atm - 24.8. Particularly good results are obtained. at low pressure, especially 6.1 - 14.6 atmospheres. The use of the catalyst according to the invention makes it possible to carry out the process at lower pressures than those previously used in so-called "continuous" reforming systems, i.e. reforming in the flow of reactants in a cycle of 5.2-70 m3 of reaction mixture per 1 kg of catalyst without regeneration. enables the continuous reforming process to be carried out at lower pressure with the same or even better catalyst life than previously achieved with conventional catalysts at higher pressures, i.e. 28.2 - 41.8 atmospheres. The temperature required in the reforming process is generally lower than in a similar the reforming process, using the high-quality catalyst used hitherto. This advantageous feature is the consequence of the catalyst selectivity according to the invention in the octane upgrading reactions of conventional reforming processes. The starting process temperature is an essential function of the obtained octane number in the product obtained. In general, during the process, in order to maintain a constant octane reformed product the temperature in the reaction zone should be slowly increased to compensate for the inevitable deactivation that occurs as it progresses through the run. The advantage of using the catalyst according to the invention is that the range of temperature rise to maintain the product at a constant octane number is lower than the temperature difference for a reforming catalyst produced in the same way but containing no rhenium and germanium. With the same temperature rise necessary to keep the octane number constant, the catalyst according to the invention achieves a higher yield of C5 + hydrocarbons than with the reforming catalyst hitherto used. In addition, the amount of hydrogen produced is substantially higher. In the reforming process, sufficient hydrogen used is 1-20 moles per mole of hydrocarbon fed into the reaction zone, with excellent results being obtained with 5-10 moles of hydrogen per mole of hydrocarbon, while the LHSV value is about 0.1-10, preferably 1-5 N m3 / m3. As can be seen from the above, a further advantage of the process carried out in the presence of a catalyst according to the invention is that a higher LHSV value is obtained and, with a small temperature difference, a longer cycle of stability is obtained. higher octane number in the reforming product due to the maintenance of a higher catalyst efficiency compared to the hitherto known and used high quality catalysts. The following examples illustrate the invention and the use of the catalyst according to the invention in hydrocarbon conversion processes, without limiting the scope of the invention. Preparation of the catalytic mixture. Aluminum oxide as a carrier, in the form of a granule Here, with an average diameter of 1.6 mm, it was prepared by molding a sol of hydroxyaluminum chloride, dissolving pure aluminum pellets in hydrochloric acid solution, and adding hexamethylene tetraamine to the obtained sol, and gelling the obtained solution by dropping it into an oil bath to produce spherical aluminum hydrogel particles. , maturing and washing the particles obtained, and then drying and calcining to obtain spherical gamma alumina particles containing about 0.3% by weight of chloride. A detailed description of this method is given in US Patent No. 2,620,314.8 87,228. The measured amount of crystalline germanium dioxide was placed in a porcelain ice-cream cup and reduced with pure hydrogen at a temperature of about 650 ° C for 2 hours. The resulting black-gray solid product was dissolved in chlorine water to give an aqueous solution of germanium monoxide. An aqueous solution was then prepared containing chloroplatinic acid, perrenic acid and hydrochloric acid. Both solutions were mixed thoroughly and used to saturate the gamma-alumina particles until the finished product had percentages by weight of 0.1% rhenium, 0.2% Ge and 0.5% Pt. In order to ensure an even distribution of the metallic components in the carrier, the impregnation process was carried out with constant stirring, and the volume of the solution was used in relation to the carrier 2: 1. The saturated mixture was left for about 0.5 hours at a temperature of about 21 ° C. The temperature was then increased to approximately 107 ° C and the excess solution was evaporated for approximately 1 hour. The obtained dried particles of the mixture were calcined at a temperature of about 496 ° C. in an air atmosphere for about 1 hour. The calcined spheres were then contacted with a stream of air containing about 40: 1 H 2 O and HCl for 4 hours at a temperature of about 524 ° C to adjust the halogen content of the catalyst particles. The obtained catalyst particles were analyzed, and they found, in percent by weight, based on the elements, about 0.5% of platinum, about 0.2% of germanium, about 0.1% of rhenium and about 0.85% of chlorine. of the catalyst was pre-dry-reduced with a pure stream of hydrogen with a water content of less than 20 ppm, at a temperature of about 558 ° C and a slightly elevated pressure, at a volumetric speed and a hydrogen stream flow of about 720 gas volumes / catalyst volume / hour, over a period of about 1 hour. An appropriate amount of spherical particles, obtained as described above, was loaded into the machine on a small industrial scale solid bed reforming process. In this device, a mixture of heavy Kuwait petroleum gasoline and hydrogen was continuously contacted under the following conditions: LHSV 1.5 N m3 / m3, pressure 7.8 atm, molar ratio of hydrogen to hydrocarbons 8: 1 and temperature sufficient for the continuous production of the reformer product Cs + 102 Fl, i.e. under extremely stringent process conditions. Kuwait's heavy petroleum gas had a relative density of 0.7374 (15.6 ° C / 15.6 ° C), initial boiling point 84 ° C, 80% distillate to a boiling point of 125 ° C and a final boiling point of 182 ° C. In addition, the naphtha used had a volumetric ratio of about 8% aromatics, 71% paraffins, 21% naphthenes, 0.5 ppm sulfur and 5-8 ppm water, with a Fl octane number of 40.0. The solid bed reformer was a reactor containing catalytic converter, hydrogen separation zone, butane removal towers and appropriate additional equipment such as heating, pumping, cooling and control and measurement devices. The recycle stream of hydrogen and the introduced hydrocarbons were mixed, heated to the appropriate temperature, and the resulting mixture was fed downstream through the reactor containing the catalyst in a solid bed. The effluent stream was withdrawn from the bottom of the reactor, cooled to a temperature of about 13 ° C, and introduced into a separation zone in which the hydrogen-rich gas phase was separated from the hydrocarbon liquid phase. Part of the gas phase was passed through a wide surface sodium scrubber and the discharged sulfur-free hydrogen stream was returned to the reactor to replenish the hydrogen feed, while excess hydrogen beyond the amount needed to maintain proper pressure in the plant was drained as excess gas. The hydrocarbon liquid phase from the hydrogen separation zone was passed through conventional butane separation towers, from which the forehead fractions were withdrawn from the column head as butane-containing gas and the hydrocarbon stream after C5 + reforming was withdrawn from the bottom of the column. The life of the catalyst was tested continuously after passing through the column. a layer of about 7 m3 of liquid per 1 kg of the catalyst used, and it was found that the activity, selectivity and stability of the catalyst according to the invention were much higher than the catalysts used so far in the reforming process. The results obtained with the use of the catalyst according to the invention exceeded the results with the platinum-containing catalysts used so far, in terms of the amount of hydrogen produced, the efficiency of C5 + hydrocarbons, determining the octane number, and gave a smaller range of temperature difference for the same quantitative production cycle, necessary to maintain at the appropriate level of octane content in the reformer product. Example II. In order to compare the catalyst according to the invention with the catalyst used hitherto containing platinum and rhenium, different trials were carried out by using germanium as an additional catalyst component. The catalyst was prepared as described in example 1, but without germanium, to obtain a mixed reforming catalyst containing 0.5% by weight of platinum, 0.1% of rhenium and 0.85% chloride with aluminum oxide as carrier. 87 228 9 The three-metal catalyst according to the invention and the double-metal catalyst were carefully tested separately in order to determine their activity and selectivity in the reforming process, using gasoline, which is a heavy Kuwait crude oil, as processed raw product. All studies used the same crude output product of gasoline with the following characteristics: relative density / 15.6 ° C / 15.6 ° C / - 0.7374 initial boiling point, ° C - 85% distillate boiling point, ° C - 95 50% d estylate - boiling point, ° C - 124 90% of distillate boiling point, ° C - 161 final boiling point, ° C - 182 sulfur ppm, weight - 0.5 nitrogen ppm, weight - 0.1 aromatic compounds%. volume - 8% paraffin, volume - 71% naphthene, volume - 21 water, ppm, weight - 5.9 octane number, F-l - 40.0 The test was carried out in completely anhydrous conditions under set conditions enabling quick determination of the catalyst performance in the reforming process. The tests were carried out in continuous cycle periods of 6 hours, and then during 10 hours of the process at a constant temperature and during this time the product was collected from the C5 + reforming. The tests were carried out in a laboratory-scale reformer, containing a reactor with a catalyst, a hydrogen separation zone, butane removal towers, and appropriate additional equipment such as heating, pumping, cooling, etc.. The recirculating hydrogen stream and the introduced hydrocarbons were mixed and heated, and then fed downstream through a reactor containing a solid bed catalyst. The effluent stream was withdrawn from the bottom of the reactor, cooled to a temperature of about 13 ° C, and introduced into a separating zone in which the hydrogen-rich gas phase was separated from the liquid phase. A portion of the gas phase was passed through a sodium scrubber with a wide surface area and the resulting anhydrous hydrogen stream was returned to the reactor, while excess hydrogen in excess of that required to maintain proper pressure in the apparatus was drained as excess gas. The liquid phase from the hydrogen separation zone was withdrawn and fed to a butane separation tower, from which the forehead fractions were discharged from the head of the column and the hydrocarbon stream after C5 + reforming was removed from the bottom of the column. The process conditions were as follows: Constant temperature around 517 ° C in the first three periods, then a constant temperature of around 536 ° C in the remaining three periods, LHSV 3.0 Nm3 / m3, pressure at the reactor inlet 7.8 atmospheres and the molar ratio of hydrogen to hydrocarbons at the reactor inlet 10: 1. in two levels of process temperature, the aim was to obtain two points of the octane yield curve for individual catalysts. The conditions used were selected experimentally to better characterize the tested catalyst under the stringent process conditions. The results of separate tests carried out on the catalyst according to the invention and on a reference catalyst free of germanium are presented for each test period in Table II, in the respective process parameters given in Table II. 10 87 228 Table II Test No. 1 2 3 4 6 1 2 3 4 6 Temperature at the reactor inlet ° C 517 517 517 536 '* 536 536 517 517 * 517 536 536 536 Amount of gases discharged from the separator m3 / m3 283 280 278 311 310 303 281 260 250 279 274 266 Number of gases 1 Ratio of the quantity of discharged gases from the tower to the deuthanized m3 / m3 to the quantity introduced into the tower. Octane number Fl Trimetallic catalyst with 0.2 wt. germanium | 10 0.033 97.2 1 9 9 11 11 11 0.033 0.033 0.034 0.035 0.035 97.2 | 96.8! 99.8 1 99.4 1 99.1! Double metal catalyst without germanium j 12 0.042 97.1] 12 13 16 0.045 0.049 0.050 0.051 0.055 95.3 94.1 98.0 97.3 96.6 The comparison of the results from Table II shows that germanium as a component in the catalyst gives much better effect on a platinum-rhenium catalyst not containing germanium, both in terms of activity and selectivity. As already mentioned above, the activity index of the catalyst in the reforming process is the octane number of the reforming product produced under the same conditions. On this basis, the catalyst of the invention was more active than the reference catalyst when tested at two process temperature levels. However, the activity of the catalyst is only part of the problem and the%: the combination of selectivity can be a measure of quality. A measure of selectivity in the reforming process is the direct yield of C5 + hydrocarbons, and indirectly it may be an index of the yield of gases discharged from the separator, roughly proportional to the hydrogen produced as products in the reaction process. The amount of gas produced from the butane stripper is a measure of the roughly unfamiliar hydrocracking reaction which should be limited as much as possible by a highly selective catalyst. The results presented in the table and the selectivity criteria show that the mixed catalyst according to the invention is superior to the catalysts used hitherto not only in terms of activity, but also more selective. PL

Claims (4)

Claims 1. A catalyst for the conversion of hydrocarbons, especially for isomerization, hydrocracking, dehydrogenation or reforming of hydrocarbons, containing a porous refractory carrier such as alumina, 0.01-2% by weight of a platinum group metal, 0.01- 2% by weight of rhenium, optionally 0.1-3.5% by weight of halogen, or 0.05-0.5% by weight of sulfur, characterized in that it additionally contains 0.01-5% by weight of geranium, optionally in the form of a compound chemical. 2. Catalyst according to claim The process of claim 1, containing 0.05-2% by weight of germanium. 3. Catalyst according to claim 2. The process of claim 1, wherein the rhenium contains rhenium in an atomic ratio to the platinum group metal of 0.25: 1 6: 1 and germanium in an atomic ratio to the platinum group metal of 0.25: 1 6: 1. 4. Catalyst according to claim The process of claim 1, wherein substantially all of the platinum group component and rhenium are pure metal, and germanium has an oxidation state higher than that of pure metal. cTTiV - .. * lA "Sklad-Prac. Poligraf. UP PRL Druk WOSJ" Wspólna Sprawa "Formjt / \ Naklul 120 * 13. She PLN 10 PL