PROCEDURE FOR CATALYTIC CRACKING OF HYDROCARBONS AND CATALYST COMPOSITION AS WELL AS PASSIVATION MEANS FOR USE WITH THIS PROCEDURE

Kehlenwasserstcff raw materials, which contain höhermclekulare hydrocarbons, are gekrankt at higher temperature in the contact with a cracking catalyst, whereby distillates will receive such as Gasolin and high-simmering hydrocarbon fuels, for example kerosene, diesel, fuel oils u.ähnl. In run this procedure removes the effectiveness of the cracking catalyst however gradually. A reason for this loss of efficiency is the deposit of polluting metals, like nickel, vanadium, iron, copper and cobalt on the catalyst, which leads to an increased production of hydrogen and coke and which effectiveness of the catalyst for the Kraeken lowers. Beyond that by these metals the transformation of the hydrocarbons is lowered in Gasolin and high-simmering hydrocarbon propulsion gases. It be18 stands from there for need according to a cracking procedure or a modified cracking catalyst, with which this harmful effect the M mentioned tallverunreinigungen œ is prevented or lowered. In the Fig.l to 9 of the designs diagrams are over the relations between the weight ratio catalyst: Oil and everyone of the transformations, Gasolinausbeute, Wasserstoffund Kcksproduktion for different catalysts represented, from which some different quantities of antimony and tin exhibit, while other no antimony and no tin contain. It was surprisingly found that the harmful effects of nod! , Vanadium, iron, copper and/or cobalt or of other similarly verunrsinigenden metals on the cracking catalyst to be prevented or reduced can, if erfindungsgemäJB cracking in presence of the Kat (A) Antlmon and/or antimony connections and (B) tin and/or tin connections alysatorkomponenten are made, whereby the components (A) and (B) are present in each case in quantities, the 0.0001 to 8 Gew. - % tin and “0.0001 to 8 Gew. - Correspond to % antimony, related to the weight of the cracking catalyst before the addition of '(A) and (B]. In particular Andmon is in quantities of at least 0.005 Gew. - %, preferably of at least 0.01 Gew. - %, completely particularly prefers from at least 0.05 Gew. - %, in or on the cracking catalyst available. In similar way the amount at antimony becomes less than 8 Gew. - %, generally less than 2 Gew. - %, preferably less than i Gew. - % and in particular less than 0.8 Gew. - % amount to. In particular tin is in quantities present, those at least 0.0005, preferably at least 0.001 and completely particularly preferentially at least 0.005 Gew. - % correspond. In similar way the used quantity tin amounts to generally less than 8 Gew. - %, particularly less than 2 Gew. - %, preferably less than 1 Gew. - % and in particular less than 0.8 Gew. - %. Although each weight ratio can be used from antimony to tin, which causes an increase of the catalyst activity and/or the yield at liquid fuels and/or a Seduktion of the Koksanfall8s and/or the hydrogen formation, it lies in particular within the range of 0,01: 1 to 100: 1. A weight ratio from antimony to tin within the range of 0,05: I to 50: i is preferred in the allgemelnen. A value within the range of 2: 1 to 20: 1 is preferred more, while a value within the range of 5: I to 15: i is completely particularly preferred. With the addition according to invention from antimony and tin to the Kraekkatalysator forwards, while 0 or reached after the use an increase of the Katalysatoraktivi£ät and/or an increase of the yield at Gasolln or high-simmering hydrocarbon fuels, for example kerosene, diesel, fuel oil cd.dgl, and/or a decrease of the formation of coke and hydrogen. The subject of the invention is also a new catalyst composition, essentially containing a zeollthmodifizierten silicic acid alumina cracking catalyst and an elementary antimony and/or antimony connections (A) and thereby characterized that it contains additionally elementary tin and/or tin connections (B), whereby the components are present (A) and (B) in quantities the 0,00BI to 8 Gew. - % Antlmcn and 0.0001 to 8 Gew, - % tin, related to the silicic acid clay catalyst before the addition of and [B}, correspond. Furthermore the subject of the invention is a new passivation means for passivating cracking catalysts polluting metals, which of (A) at least a Antimonthiophosphat and (B) contain at least an organic tin connection, whereby the weight ratio from antimony to tin 0,001: I until 1000: 1 amounts to. In particular this relationship becomes within the range of 0,01: 1 to i00: i, preferably within the range of 0,05: 1 to 50: i, in particular within the range of 2: I to: 1, completely particularly preferentially within the range ven 5: l to 15: are appropriate for 1. By the term “cracking catalyst”, how it is used here, is newer to understand more unused or a cracking catalyst already used how it is used for cracking throat land on water open without additive of hydrogen. The besehriebene cracking catalyst can be a usual cracking catalyst. By the term unmodified cracking catalyst, how it is used here, is understood neither cracking catalyst, which was not modified by contact with antimony or tin. Such Katalysatormateria! everyone can be, which is usually used with catalytic cracking processes by hydrocarbons for the production of Gasolin, Metortreibstoffen, blend components and light distillates, simmering over 204°C. These usual cracking catalysts contain generally silicon dioxide or silicon dioxide alumina. Such materials are frequently associated with zeolithischen materials. With these zeelithisehen materials it can act around naturally occurring or be able to do it in well-known way in ion exchange procedures to be manufactured, in order to insert for example metallic ions, which improve the activity of the catalyst. With zeolites modified silicon dioxide clay catalysts are particularly usable for the Erfindungsgedanken. Examples of such l (rack catalysts in or on which antimony and tin more einoder can have deposited, hydrocarbon cracking catalysts, which are by mixing a gel of of a anorganisehen oxide with a Aluminosilikat to receive became or Aluminosilikatzusammensetzungen, which as consequence of a treatment with a liquid medium, which at least a cation of a rare-earth metal and a hydrogen ion contain, or an ion, which can be replaced by a hydrogen ion. The used cracking catalysts are present generally in particle form and have a particle size within the range of approximately 10 to 200 per. Such cracking catalysts also burn PROM gates, like platinum or chrome, can contain of wishing case. Yet used cracking catalysts, how they are used according to invention, essentially do not contain no nickel, vanadium, iron, copper or cobalt. Preferably for nickel, vanadium, Eisenund the following borders exist copper content from Kraekkatalysatoren not used yet, which constitute the largest Tell according to invention used, yet not used of the cracking catalysts: Nickel 0 to 0.02 Gew. - % vanadium 0 to 0.06 Gew. - % iron 0 to 0.8 Gew. - % copper 0 to 0.02 Gew. - % these declarations of weight refer to the total weight of the cracking catalyst including the metals nickel, vanadium, iron and copper, but excluding the additions, not used yet, at antimony and tin. The content of these metals in the cracking catalyst can be determined according to usual methods, for example by atomic absorption spectroscopy or by Röntgonfluoreszenzspektroskopie. These catalytic materials can vary regarding their Porenvolumens and the surface. However generally a katalytisehes material not needed yet will have a Porenvolumen within the range of approximately 0.1 to 1 ml/g. The surface of such catalytic materials not used yet is appropriate generally in the range ven for about 50 to approximately 500 m=/g, catalyst according to invention and the modified essentially consists of a usual cracking catalyst with a modifying or passivating quantity of antimony and tin in or on the catalyst. The quantity of antimony and tin, which is particularly wünsehenswert on the catalyst, varies according to the quantity of the polluting metals in the E (atalysatcr, whereby higher values for antimony and tin are desirable if higher values of the polluting metals are present. The kind, in which the catalyst is brought with the Antimenund tin modifier in contact, is not critical. For example the modifier in fsinverteilter form with the catalyst can be mixed in usual way by rollers, vibrating, agitating or similar procedures. The modifier can be also loosened or be dispersed in a liquid, e.g. a water, hydrocarbons or aqueous acids. This depends on the respective kind of the Modifiziermlttels. The received solution or dispersion can be used for impregnating the catalyst, on which the liquid is evaporated. The modifiers can be struck down also on the catalyst from solutions, on which the solvent is removed. Wishing case can be solved the Modiflziermittel also in the hydrocarbons, which are to be submitted to the cracking process, or dispersed, whereby the hydrocarbons and the modifiers come about at the same time with the catalyst into contact. If it is wished, the catalyst can be exposed also to steams of the modifiers, in order to strike down the MitI0 tel at the catalyst. Of course also combinations of the different methods can be used, in order to reach a modification of the catalyst by the modifiers. The modifiers can be added to the catalyst at the same time or successively. The modifier can the catalyst during a first time interval directly or over the hydrocarbon raw material or the second modifier afterwards in the catalyst directly or likewise over the hydrocarbon raw material, while are added to a second time interval. The form, in which antimony in or is present on the catalyst or is used into which it for the production the antimony and tin of the containing catalyst, is not critically. Each antimony connection, which causes a passivation of of the vernnreinigenden metals, which are depressed on the catalyst, can be used. Like that are elementary antimony, inorganic antimony connections and organic antimony connections just like mixtures sources for antimony, suitable by two or several of these groups. The used term antimony refers generally to everyone of these sources of antimony. Examples of some inorganic antimony connections, which can be used, are: Antimony oxides, like antimony tri oxide, Antimontetroxyd and Antimonpentoxyd, antimony sulphides, like antimony tri sulfide and Antimonpentasulfid, Antimonselenide, like Antimontriselenid, Antimontelluride, like Antimontritellurid, antimony sulfates, how antimony tri sulfate, antimony uren, like Metaantimonsäure, 0rthoantimonsäure and Pyroantimonsäure, Antimonhalide, like antimony tri fluoride, antimony tri chloride, antimony tri bromide, antimony tri iodide, Antimonpentafluorid and Antimonpentachlorid, Antimonylhalid, like Antimonylchlorid and Antimonyltrichloaa rid, Antimonide, like indium antimonide u.ähnl. Such, which do not contain halogen, are preferred by the inorganic antimony connections. Although for the production that antimony tin containing the catalysts contain of used organic Antimonverhindungen, for economic reasons and for reasons of the easy receipt barness, preferably 3 to 54 C-atoms, lying organic antimony connections can be used also outside of the range. So can also organic polymers, which contain antimony, when organic antimony connections are used. Additionally to carbon and hydrogen an organic antimony connection can contain also the elements oxygen, sulfur, nitrogen, phosphorus od.ähnl. Examples of some organic antimony connections, which can be used during the production that antimony/tin containing catalysts, are: Antimony carboxylates, like antimony tri formate, Antimontrioetoat, antimony triac budget, Antimontridodecanoat, Antimontrioctadecanoat, Antimontribenzoat and antimony trichloroethylene (cyclohex ancarboxylate); Antimonthiocarbexylate, like antimony trichloroethylene (thioacetat), antimony trichloroethylene [dithioacetat) and antimony trichloroethylene (dithiopentanoat); Antimonthiocarbonate, like antimony trichloroethylene (O-propyldithiocarbonat]; Antimony carbonates, like antimony trichloroethylene [ethyl carbonate); Trihydrocarbylantimonverbindungen, like Triphenylantimon; Trihydrocarbylantimonoxyde, like Triphenylantimonoxyd: Antimony salts of phenolic connections, like Antimontriphenoxyd; Antimony salts of thiophenolischen connections, like antimony trichloroethylene (thiophenoxyd); Antlmonsulfenat, like antimony trichloroethylene (benzolsulfonat) and antimony trichloroethylene (p-toluolsulfonat); Antimonoarbamate, like antimony trichloroethylene (diäthylcarbamat); Antimonthiocarbamate, like antimony trichloroethylene (dipropyldithiocarbamat), antimony trichloroethylene (phenyldithiocarbamat) and antimony trichloroethylene [butylthiocarbamat); Antimonphosphite, like antimony trichloroethylene (diphenylphosphit); Antimony phosphates, like AntimonSe of trichloroethylene (dipropylphosphat]; Antimonthiophosphate, like antimony trichloroethylene (O, O-dipropylthiophosphat) and antimony trichloroethylene (O, O-dipropyldithiophosphat) u.ähnl. The latter connection is also as antimony trichloroethylene (O, O-dlpropylphosphordithionat) admits and because of their Lösliohkeit in hydrocarbons and because of their preservation borrowingness in the trade is preferred. Also mixtures of two or more mentioned above antimonhaltigen connections can be used. The form, in which tin in or on the catalyst is present or one uses for the production of the Anttmon and tin containing catalysts, is not critical. Each tin connection, which promotes the Pa sivierungseffekt from antimony, can be used. Like that are elementary tin, inorganic tin connections and organic tin connections just like their mixtures suitable sources for tin. The term tin used here covers everyone of these sources of tin mentioned. Examples of some inorganic tin connections, which can be used are: Zlnnoxyde, like tin Ilund tin iv-oxide; Zinnsulfide, like tin IIund tin iv-sulfide; Zinnselenide, like tin IIund tin IV selenid; Zinntelluride, as tin II tellurid; Tin sulfates, like tin IIund tin iv-sulfate; Tin acids, like Metazinnsäure and Thiczlnnsäure; Zinnhalide, like tin ii-fluoride, - chloride, - bromide and - jcdid, tin iv-fluoride, - chloride, - bromide and - iodide; Tin phosphates, like tin iv-phosphate; Zinnoxyhalide, as tin II oxychlorid and tin IV oxychlorid; u.ähnl. Such, which do not contain halogen or silicon, are preferred by the inorganic tin connections. Although the organic tin connections for the production that preferably contain antimony and tin of containing catalysts for reasons of the economics and perceptibleness 2 to 48 C-atoms, lying, organic tin connections can be used also outside of this range. So for example organic, tin containing polymers can be used as organic tin connections. To carbon and hydrogen the organic tin connections can contain also oxygen, sulfur, nitrogen, phosphorus and similar elements of “examples of organic tin connections, which can be used for the production that antimony and tin containing catalysts, are additional: Tin carboxylates, like tin -, tin ii-acetate Ii-formlat, tin II butyrat, tin II octoat, tin II decanoat, tin ii-oxalate, tin II benzoat and tin ii-cyclohexane carboxylate; Zinnthiocarbcxylate, as tin II thioacetat and tin II dithioacetat; Dihydrocarbylzinnbis (hydrocarbylmercaptoalkanoat) e, as Dibutylzinn to (isooctylmercaptoacetat) and Dipropylzinnbis (butylmercaptoacetat); Zinnthiocarbonate, as tin II o - äthyldithiocarbonat; Zinncarbcnate, as tin II propylcarbonat; Tetrahydrocarbylzinnverbindungen, like Tetrabutylzinn, Tetraoctylzinn, Tetradodecylzinn and Tetraphenylzinn; Dihydrocarbylzinnoxyde, like Dipropylzinnoxyd, Dibutylzinnoxyd, Dioctylzinnoxyd and Diphenylzinnoxyd; Dihydrocarbylzinn to (hydrocarbylmercaptid) e, as Dibutylzinn to (dodecylmercaptid); Zinnsalze of phenolic connections, as tin II thlophenoxyd; Zinnsulfonate, as tin II benzolsulfonat and tin II PI toluolsulfonat; Zinncarbamate, as tin II diäthylcarbamat; Zinnthiocarbamate, as tin - Ii-propylthiocarbamat and tin II diäthyldithiocarbamat; Zinnphosphite, as tin II diphenylphosphit; Tin phosphates, as tin II dipropylphosphat; Zinnthiophosphate, like tin II o, O-dipropylthiophosphat, tin II o, O-dlpropyldithiophosphat and tin IV o, O-dipropyldithiophosphat; Dihydrocarbylzinnbis [O, O - dihydrocarbylthiophosphat] e, like Dibutylzinnbis (O, O - dipropyldithicpho chamfer); and ähnI. Also mixtures of two can be used or more these materials. Dibutylzinnbis (isooctylmercaptoacetat) and tin! V-O, O-dipropyldithiophosphat because of their solubility in hydrocarbons and its compatibility with antimony trichloroethylene (O, O-dipropyldithiophosphat) is preferred. A further advantage is that Dibutylzinnbis isooctylmercaptoacetat) in the trade preservation lich is. Since the principal purpose of Antimcn and tin consists on the cracking catalyst of it, the otherwise arising unwanted effects by polluting metals, in particular the rise Wasserstoffund coke formation and the decrease of the yields at high-simmering Kohlenwasserstcfftreibstoffen, like kerosene, diesel, to prevent or reduce fuel oil, which are caused for poisoned stable by this, should be essentially free the used and in or on the catalyst stored Antimonund sources of tin by such polluting metals. Used Antimonund sources of tin should from there essentially none nods! , no vanadium, no iron, no copper and no cobalt or other harmful, polluting metals contain. That antimony and tin containing catalyst can be manufactured by Inkontaktbringen of a usual Kreckkatalysators with an admixture consisting of an antimony treatment means and a Zinnbshandlungsmittel. In addition, the usual cracking catalyst can with the antimony treatment means and the tin treatment means separately, in different process steps, with or without Zwlschenbehandlung, how heating and distance of the solvent up are e.g. brought, in contact. So a usual Rrackkatalysator can be brought with the two treatment means at the same time or first with the one and then with the other treatment means in contact. Forwards or during the use in the cracking procedure that is heated up antimony and tin containing catalyst on a higher temperature, for example within the range from 427 to 816°C in oxidizing or reducing atmosphere. Such a heating can in the catalytic l< rack plant, in the regenerator for the catalyst or in a separate boiler to be made. That antimony and tin containing catalyst can thus from a used or preferably from a still unused usual l< raekkataI0 lysator to be manufactured by admixture of the antimony treatment means or the tin treatment means, separately or in the mixture, in present or absence from diluent, with distance of this diluent, if such were used, with or without heating on higher temperatures. The received catalyst can be added aIs make-up catalyst for the cracking process, whereby preferably the addition of this make-up catalyst takes place into the KataIS lysatorregenerator. With a preferential procedure the antimony treatment means and the tin treatment means can be preferably solved separately in the mixture or preferably as such or or be added dispersed in a suitable liquid to the ÖI raw material, if this is fed into the catalytic cracking plant. It is preferred less adding Antimonund tin treatment means directly to a river of the catalyst during the cracking process. It is desirable that the cracking catalyst is brought with the tin in situ in the cracking reactor system in contact. If the tin component is added to the cracking catalyst outside of the cracking reactor system, it is desirable, such with tin treated catalyst within short time to keep for example within five day to use during the cracking process and possible effects of the aging of tin as small as possible on the Kraekkatalysator. The re-establishment of used cracking catalysts takes place via passivation of the polluting metals nickel, vanadium, iron, copper and cobalt, whereby the polluted Kraekkatalysator is brought with a Antlmonbehandlungsmittel and a tin treatment means at increased temperature in contact. The time, during which the catalyst is brought with the two treatment means in contact, is not critical. Generally the time for a chargenweise treatment of the I&lt amounts to; atalysatnrs outside of the reaction about 0.1 to 300 min. during a preferential execution both treatment means continuously in the Hrackreaktor over e ne feed into the raw material is measured out. Wishing case can one of the treatment means directly on the catalyst be applied and the other treatment means over the raw material be introduced. By the term used here antimony treatment means is to be understood elementary antimony or one of the connections specified above. In similar way tin treatment means elementary tin or one of the tin connections specified above is to be understood by the term. Vorteilhafterwelse are added raw material to the entering the Rrackzone with the cracking procedure according to invention Antimonund tin treatment means, into which them with the cracking catalyst into contact to come. With this procedure the Inkontaktbringen of the cracking catalyst and the treatment means is made as well as the initial treatment under increased Ternperatur under the conditions predominantly reducing in the catalytic cracking plant. The cracking procedure, with which antimony tin containing l< rack catalysts to be used, an improvement of the iIblichen cracking procedures is fundamental, with which admitted cracking catalysts alone or either with antimony or with tin are modified used. Although that can be used antimony and tin containing Rrackkatalysator with the catalytic cracking procedure in a fixed bed, it is particularly appropriate to use him in a kind of eddy. With preferential training of the cracking procedure according to invention a cyclischer river of the Katalysator6 is used from the cracking zone to a Regenerlerzone. With this procedure a coal landing on water EFF raw material, which contains polluting metals such as nickel, vanadium or iron, is brought in the cracking zone on cracking conditions in absence of added hydrogen with an antimony and a tin containing cracking catalyst in contact. The gekrankte product is received and removed. The cracking catalyst comes of the KracRzone into efne Begenerationszone. In this the catalyst is regenerated by contact with a free, oxygen containing gas, preferably air. The coke deposited during the cracking process on the catalyst is at least partially burned down thereby. The regenerated catalyst is led back into the cracking zone, furthermore with which execution erfindungsgemäf of the EN Kraokverfahrens a part of the cracking catalyst replaced by a still unused cracking catalyst continuously or intermittently. Generally becomes about 0.5 to 6 Gew. - l&lt % of the entire Kraekkatalysators daily by a freshness; more rackkatalysater replaces. The actual quantity of the replaced catalyst depends vDn the kind of the used raw material. The make-up quantity of the cracking catalyst can be added in each place of the process. Preferably however the cookie UP - catalyst is introduced to the Begsnerator of a cyclischen cracking procedure. From the used, ven the Krackzcne coming catalyst, are removed before the entering the regenerator all liquid or gaseous hydrocarbons. In similar way the regenerated catalyst can be released from all oxygen, before it is transferred into the cracking zone, this treatment generally with steam is made. The spezleiIen procedural conditions in Krackund the regeneration zone are not critical and depend on different parameters, like the used raw material, the catalyst and the final products desired. Generally prevail in Krackund Begenerationszone in the following Zueammenstellung stated conditions. Cracking zone temperature time pressure catalyst: Oil relationship 427 - 649°C1 -40 s subatmosphärisch up to 207 bar (3000 psig) of 3: 1 to 30: l (Gew. - Parts) of Regeneratlonszone temperature 538 - 816°C time 2 - 40 min pressure subatmosphärisch up to 207 bar (3000 psig) of air with 16°C and I without 6,2 - 15, ö m /kg coke according to invention the raw materials used with the Kraekverfahren contain polluting metals such as nickel, vanadium, iron, copper and/or cobalt u.ähnl. The raw materials are used übllcherweiee in the cracking procedure for the production of Gasolin and light distillate parliamentary groups from heavy hydrocarbon raw materials. The Ausgangsmaterialieh knew generally an initial boiling point above for instance 204°C and for example to be: Gas oils, Heiz61e, rotating oils, mud oils, distillation residues, shale oils, oils from tar ends, oils from coal and mixtures of two or several of these components. By distillation residues the 01e is understood, which results at the ground of a Roh61fraktionators. Gewünschtenfa] is can consist the entire raw material or a Tell of it of one {IL, from which a part was removed the metal contents by a preceding treatment, for example by a water treatment or solvent extractions. According to invention usually the raw materials used with the procedure contain one or more metals nickel, vanadium and iron in the borders indicated in the following composition. Metal content the output metal of the material, ppm (1) i, nickel vanadium iron Gesamtmetall 0.02 - lO0 0.02 - 500 0.02 - 500,0.2 -1100 (2) [i) the metal content in ppm 1 Gew refers to the used raw material and means. - Part on 1 million Gew. - Parts. (2) the total metal content in this composition and everywhere in the description refers to the sum of nickel, vanadium and iron in the raw material, which causes an effective Verunrelnigung of the catalyst. The total metal content can in well-known procedures, e.g. by atomic absorption spectroscopy, to be determined. One of the most important aspects of the invention is based in a Sehwerölkrackverfahren. With the s Schwerölkr admitted “ckverf “hren can fuel oils with a metal content from to approximately 80 ppm at totaleffective metals, d.s. metals in each form, which are harmful for the procedure, be processed, economic limit values become with the processing of oils with 40 to ppm at totaleffective metals to receive. According to invention fuel oils with a total metal content from 40 to 100 ppm and also such from approximately 100 to 200 can be converted ppm and over it in the Krackl0 muddled in absence of admitted hydrogen using the catalyst according to invention to Gasolin and other fuels and fuel mixture components. Thus fuel oils with a total metal content can be gekrankt from 80 to 300 ppm, which could not be used so far directly for the fuel production and in particular for Gasolin and high-simmering hydrocarbon fuels, according to invention. The erfindungsget5 would measure procedures leads to a yield at Gasolin and high-simmering hydrocarbon fuels, like kerosene, diesel and fuel oils. The concentration of antimony and tin in or on the according to invention, antimony and tin containing cracking catalyst preferably depends home cracking oils with high metal content on the average content of effective metals in the raw material, as this is to be inferred from the following compilation. Effective Gesamtmetalls, in the antimony + tin concentration raw material (ppm) (2) in the catalyst Gew. - % (1) i Nr.374468 i - - 100,100 - 200,200 - 300,300 - 800 0.0001 - 0.6 0.05 - 0.8,0.1 - 1 0.15 - 1.5,0.2 -2 (i) related to the weight of the catalyst before the addition of the Antlmon and tin of containing modifier. (2) under the term “effective Gesamtmetalls” is to be understood: The sum of the vanadium concentration. the katalyrische iron concentration, the quadruple nickel concentration, the quadruple copper concentration and the product of the concentration of all other polluting metals and their respective relative activity. The invention is more near described on the basis the following examples, dia. preferential AuefOhrungen to describe, but the invention not to limit not be supposed. Example i " a commercial cracking catalyst from amorphous silicon dioxide and alumina, nationalized begun with zeolithischem material, which in a usual cracking unit one used and one regenerated afterwards in the laboratory, in a set of attempts, which together polluted the effectiveness of antimony and tin with the improvement one of metals, used cracking catalyst showed. The characteristics of the used up cracking catalyst before the recovery in the laboratory are indicated in table I. t0 table I surface 74.3 m=/g Porenvolumen 0.29 ml/g composition, aluminum 21.7 Gew. - % silicon 24.6 Gew. - % nickel Q, 38 Gew. - % vanadium 0.66 Gew. - % iron 0.90 Gew. - % cerium 0.40 Gew. - % sodium O, 39 Gew. - % carbon 0.06 Gew. - %, the commercial catalyst with above characteristics, already used, in the laboratory by heating up in the fluid bed with air on 649°C was then regenerated, whereby this treatment was long accomplished in the fluid bed 30 min. The catalyst was cooled down then ambient temperature, about 25°C, and held with nitrogen in the fluid bed. In such a way regenerated catalyst, in the following as catalyst 0 designation, was then re-used as follows. A part of the catalyst 0 became then for the production of a catalyst composition with 0,5 Gew. - Parts antimony and 0.6 Gew. - Parts tin, for each 10Q Gew. - Parts catalyst uses. This became by dry mixing of 35 Gew. - Parts catalyst 0 with 0,357 Gew. - Reaches parts Dibutylzinnoxyd of a Teilohengröf e of 0.04 mm. The received mixture became then with a solution of 27 Gew. - Parts of Gyclohexan and 1.61 Gew. - Parts of a mineral oil solution, which about Gew, - % Antfmontrls (O, O-dipropylphcsphordithionat) contains, mixed. The mixture was then dried by heating up on 260°C on a hot plate to a fine powder. The catalyst with antimony and tin, received above, was then further-treated in the following way. The catalyst was then brought into a quartz reactor in laboratory size and heated up in the fluid bed with nitrogen by ambient temperature [for instance 25°0) on 482°0. Subsequently, s it was heated up in the fluid bed with hydrogen of 482 on 649°C. At this temperature the catalyst 5 min with nitrogen and afterwards 15 min with air in the fluid bed was held. Then the catalyst was through aged by 10 cycles, whereby each cycle was accomplished in the following way. The catalyst was held held for 2 min with hydrogen in the fluid bed with 482°C in the fluid bed with nitrogen 1 min, then 510°0 heated up and held then at this temperature 1 min with nitrogen in the fluid bed and heated up then 649°C and left 10 min with air in the fluid bed. The catalyst was then cooled down on 482°C and 1/2 min with air was whirled. After these 10 ageing cycles the catalyst became ambient temperature (about 25°C) cooled down and with nitrogen in the fluid bed held. This catalyst is called in the following catalyst RK, a further portion of the catalyst 0 became for the production of a catalyst composition with 0,63 Gew. - Parts tin for each 10D Gew. - Parts catalyst 0 uses. This happened through dry tables of 35 Gew. - Parts of the regenerated catalyst 0 with 0,47 Gew. - Parts of Dibuty! - sense oxide, which grind on a particle size of 0.04 mm was. The mixture was then further-treated and aged, as this is descriptive with the catalyst RK above. In such a way received catalyst was called catalyst T. A third portion of catalyst D became for the production of a catalyst composition with 0,5 Gew. - Parts antimony on 100 Gew. - Parts catalyst 0 uses. This was done via mixture of the catalyst 0 with a cyclohexane mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordlthioat), which contains 0.0147 g antimony ever ml solution. Cyclohexane and mineral oil 2S were removed by heating up on a hot plate and the received mixture was processed, aged and cooled on ambient temperature, as this became to besohrieben with catalyst RK. The received catalyst is called catalyst A. The catalysts RK, T, most important thing were used in four series of tests in cracking regeneration cycles using a distillation residue of west Texas crude oils as raw material. Except, where it is differently indicated in table III, in each cycle the cracking stage get 510°C and with atmospheric pressure 0.5 min accomplished. The regeneration was accomplished with 649°G, atmospheric pressure about 30 min in the fluid bed using air. Before and after the cracking stage the reactor with nitrogen was cleaned. The characteristics of the distillation residue of west Texas crude oil, used for the cracking procedure, are aforementioned in table II. - II - Nr°374488 table II spec. Gewiaht with 16 " C (1) distillation, “C (2) point of initial LED 10% 20% 3O% 40% 5O% C3) Kohl enstoffr ücks edge, Rare6, elementary analysis S Ni V Fe setting point (4) kinematic viscosity (5) with 82°G with 99°C Brechungskoeffizient with 670C (6) (1} ASTM D 287-67 (4] ASTM D 97-66 C2) ASTM D i160-61 (5) ASTM D 445-65 (3) ASTM D 524-64 (6] ASTM D 1747-62 0.925 291°C 428°C 468°C 498°C 5280C 555°C 5.5 Gew. - % 1.2 Gew. - % 5.24 ppm 5.29 ppm,29 ppm 27°C 0,555.10m=/S 0,321.10m=/S 1.5 with the catalysts the RK, T, most important thing accomplished cracking procedure are summarized in table III. Table III cracking test (i) I 2 3 (2) 4 6 7 (3) 8 (3) 1 2 x (4) i (5) 1 (8) catalyst RK RK RK RK RK RK RK RK T T A A o catalyst: Oil Gew. - Verh. 7,5,7.5,7.6,7.5,8.5,9.3,7.7,7.4,7.4,8.6,7.6,7.4,7.7 transformation VOL. - % D. Raw material 79.8 80.3 68.4 75.8 76.9 76.1 72.6 74.7 74.5 81.6 73.4 75.8 74.9 yield coke Gew. - % D. Ausgangsmat. 14,3 12.6 i0, I 11.6 ii, i 12.9 12.3 12.5 14.0 15.5 10.9 12.1 17.6 H2, i/i umgew. Ausgangsmat. 71 61 62 Gasolin VOL. --°% 61 62 67 59 121,120 66 59 159 D. Ausgangsmat. 68, i 69.2 57.6 " 58.2 55.8 59.2 56.7 61.0 55.0 55.3 59.9 63.4 54.6 104,101 97.7 95.0 92.9 96.7 95.9 97.4 96.5 95.0 96.1 100.7 (i) dia. numbering erfolg% in the order, in which the tests with the individual catalysts were accomplished. (2) test 3 about 9 months after test 2 was accomplished. (3) the preceding recovery of the catalyst were long accomplished with approximately 704 “C about 1/4 h. (4) although the used catalyst already before in three cracking tests with other catalyst: ÖI conditions uses de, was essentially invariably after the use in these relative it in the appearance few shitting regeneration cycles. (5) the test was not actually accomplished. The values became of flat curves for a constant catalyst: Oil relationship read off from 7,4. The curves were manufactured after nice ones, which likewise came from flat curves, those after data, those with many runs with varying catalyst: Oil relationship were received, provided. (6) although the used catalyst in new tests before was assigned, those at temperatures between 510 and 549°C and with different catalyst: Öi conditions were accomplished, was the catalyst after this limited consumption essentially in the outside unchanged. I I - A cm such as table III shows, is well suitable with everyone the Kraektests, in which a catalyst modified with antimony and tin was used, this catalyst for a cracking procedure in presence of polluting metals. In particular with first two cracking tests were reached protruding results. In these two tests the extent, to which the catalyst at Krackund regeneration conditions was subjected after the incorporation by antimony and tin, was not large and was smaller than with the following tests with this catalyst. In these first two tests with the modified catalyst the conversion of the raw material was higher than in other tests with a comparable catalyst oil relationship. This shows a larger catalyst activity and also the yield at Gasolin was much larger than in one of the other tests. In these two first tests also Wasserstoffund cookie formation was substantially smaller than in the tests, in which catalysts were used, which had been treated either only with antimony or only with tin. How IIl can be taken from the table, the tests 3 to 8 substantially lower conversions of the raw material and a substantially smaller yield show at Gasolin than the tests 1 and 2 of the same series from the eight cracking tests, which were accomplished with the catalyst RK. These smaller values for the conversion and the Gasolinausbeute are attributed to a deactivation of the catalyst, which could possibly have entered on aging following after the tests 1 and 2 with storing by 9 months by a reaction of the tin with silicon. Example 2: This example, which was calculated, is to show the application of the invention in the labriksmäßigen yardstick. In an industrial cracking plant with 181 t cracking catalyst daily 3.868.700 is cracked l/Tag oil with a spei weight by 16°/16°C, 0.929. Around a content of 0,5 Gew. - (related to untreated catalyst) both at antimony and at tin in the catalyst to maintain, both Antimontrls (O, O-dipropylphosphordithioat) and Dibutylzinnoxyd in quantities of 20 are added ppm antimony or tin to the raw material 17 days long or for each 3fl ppm antimony and tin the raw material 10 days long. Around the content of antimony and tin in each case on 0,5 Gew. - to hold, the addition at antimony and tin must amount to per 10 ppm, if 7.2 t of the catalyst are taken off daily from the reactor and replaced by an untreated catalyst. If only 5.4 t of the catalyst are daily replaced, above addition is enough, around the content of antimony and tin in the catalyst system on in each case 0.65 Gew. - to hold, in absolute numbers this means that 985 kg of a mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordithioat), the 11 the Gew. - % Antimcn and 226.35 kg Dibutylzinnoxyd the raw material daily by I0 contains days to be long added must (for 17 days 652.5 kg and 150.75 kg) and that 326.25 kg of this mineral oil solution of antimony trichloroethylene (O, O-dipropylphospherdithioat] and 75.6 kg von Dibutylzinnoxyd the raw material to be added to have, around the desired content of antimony and tin with ever 0.5 Gew. - to maintain in the catalyst. Example 3: A commercial cracking catalyst from amorphous silicon dioxide and alumina, nationalized with zeolithischem material, which in a usual Kraekanlage one used and one regenerated afterwards in the laboratory, was used for the production of cracking catalysts with different contents at antimony, tin and Antlmon and tin. The source for Antimen was antimony trichloroethylene (O, O-dipropylphosphordlthioat) and the source for tin was Dibutylzinnoxyd, which grind on a particle size of 0.04 mm was. The characteristics of the used cracking catalyst before the recovery in the laboratory are indicated in table I in example 1. During the recovery in the laboratory the catalyst in the fluid bed with air on 6490C was heated up and left 0.5 to 2 h. The catalyst was then cooled down on ambient temperature, about 25°G, in the fluid bed with nitrogen. The received, regenerated catalyst, which is called catalyst X, was then further-treated as follows. A portion of the catalyst X was used for the production of Katalysatorzusammsnsetzungen, per 100 the Gew. - Parts catalyst X, 0.05 Gew. - Parts antimony and 0.05 Gew. - Parts tin and/or 0, i0 Gew. - Parts antimony and 0.01 thread - part tin (two compositions) and/or. 0.01 Gew. - Part antimony and 0, I0 Gew. - Parts tin and 0.50 Gew. - Parts antimony and 0.50 Gew. - Parts tin exhibited. With each these five compositions became the computed quantity of Dibutylzinnoxyd, which should guarantee the desired tin content, with the catalyst X drying ge - 14 - NR, 374488 mixes, according to which the computed quantity of the mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordlthioat) with a content of 10,9 Gew. - % antimony as well as cyclohexane with the received mixture for the reaching of the desired antimony content was mixed. The mixture was then dried on a hot plate. Another portion of the catalyst X was used for the production of catalyst compositions, those on 100 Gew. - Parts catalyst X in each case 0.01, 0, i, 0.5 and 1.0 Gew. - Parts tin contained. With each these four compositions the computed quantity of Dibutylzinnoxyd drying with the catalyst X was mixed. The mixture was dampened with cyclohexane and dried on a hot plate. A further portion of the catalyst X was used for the production of a catalyst composition, those on i00 Gew. - Parts catalyst X in each case 0.05, 0, I, 0.25, 0.5 and 1.0 Gew. - Parts antimony contained. With each these five compositions became the computed quantity of the mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordithioat), the I0,9 Gew. - Antimony contains, in cyclohexane with the catalyst X mixed and the received mixture on a hot i5 plate dried. Each of these 14 Katalysatorzusammcnsetzungen was further-treated in the following way. The catalyst was brought into a quartz reactor by laboratory size and by Raumtemperatut (about 25°C) in the fluid bed with nitrogen heated up on 482°C. Further heating up on 649°C was accomplished in the fluid bed with hydrogen. At this temperature the catalyst was then treated 5 min in the fluid bed with nitrogen, on which a fluid bed treatment with air of to 20 min followed. The catalyst was then aged in 10 cycles, whereby each cycle was accomplished as follows. [3er catalyst was cooled about 1/2 min long in the fluid bed with air and nitrogen on approximately 482 “C. At this temperature it was treated a further hour with nitrogen and heated up then on 649°C and treated 2 min with nitrogen and hydrogen in the fluid bed. At this temperature a further minute was treated with nitrogen in the fluid bed and treated then 8 to 94 min with 649°C with air in the fluid bed. After these 10 ageing cycles the catalyst on ambient temperature, about 25°C, in the Wlrbelbett with nitrogen was cooled. The 14 aged catalysts, which were descriptive manufactured above as, and which catalyst X (two samples) became in 15 series of a cracking regeneration cycle assigned. The cracking stage became within a range from catalyst: ÖI conditions accomplished, whereby about 4 to 40 g of the catalyst in a fluid bed in a quartz reactor was used and gas oil as raw material for the cracking stage was used. In each cycle the cracking stage was long accomplished with 510°C and with atmospheric pressure 0.5 min. The regeneration took place with 649°C and with atmospheric pressure approximately 30 min long in a fluid bed with air. The reactor was rinsed before and after the cracking stage for cleaning with nitrogen. The characteristics of the used gas oil in this example are indicated in table IV. - I5 - Table IV Nr.374488 API density with 16°C (i) 25.8 spec. Weight 0.8996 BMCI (2} 41.1 distillation, (3) 2% 259°C 5% 276°C 10% 297°C 20% 327°C 30% 354°C 40% 379°C 50% 404°C 60% 426°C 70% 450°C 80% 479°C g0% 523°C 95% 564°C Kohlenstoffrflckstand, RAM (4) 0.87 Gew. - % sulfur 0.40 Gew. - % basic ticking EFF 0.025 Gew. - % total nitrogen 0.07 Gew. - % (1) ASTM D 287-67 (2) Vth A. Kalichevsky and K.A. Kobe, “petroleum Refining with chemicals”, Elsevier Publishing CO., New York, N.Y. , S. 6 (3) ASTM D 1160-61 14) ASTM D 524-64 the results of these cracking attempts, which would separate with [len catalyst: ÖI conditions were accomplished, are summarized in table V. All attempts accomplished with a given catalyst were seized, with exception of those, which completely obviously wrong results, because of errors of the arrangement or human error resulted in. In particular those attempts were let go away, with which itself a material remainder outside of the range from 100 + - 5% resulted in. These attempts were stated with a given catalyst in the order, in which they were accomplished. With the catalysts treated with tin the attempts, with exception of the series M, became N and O, not longer than four days after the manufacture day of the catalyst durchgeI0 lead. Also the gap between two attempts did not amount to any more than four days, including the attempts, which were incorrect for the reasons stated above. With the series M, N and O applied about in each case 34, 35 and 22 days between the production of the catalyst and the execution of the first attempt, show the Fig.1 to 7 of the designs in graphic form of comparisons of attempts selected from the table V. A series of at least five attempts with a given catalyst and different catalyst: To oil conditions a curve was adapted and resulted in the represented flat curve. Two or three attempts with a given catalyst and constant catalyst became; Oil conditions as individual point represented. Each of these points represents the average of the values, on which it is based. - 16 - NR, 374488 table V A 2A • 3A 4/= 5a 6A 7A 8A 9A IOA llA lB 28 38 “8 58 08 78 88 98 10B IC 2C 3C 4C 5C 1D lE 2E 3E 4E 5E 1F 2F 3F 4F 5F catalyst addition in Gew, - Sn (2)] o 0 o o o o 0 o o o o O, O1 0.01 O, O1 O, Ol O, O1 0.01 O, Ol 0,0! O, O1 0.01 0.10 0.10 0.10 0.10 0.10 0.50 0.50 0.50 0.50 0.50 l, O0 1.00 t, O0 1, OO! , 00 0 O 0 0 0 self-service (3) 0 0 o 0 o 0 0 0 0 0 o 0 o 0 0 0 o 0 o o 0 0 o 0 o 0 o 0 o o 0 0 o 0 0 o 0.05 0.05 0.05 0.05 0.05 catalyst: Öt Gewlcbtsverbältn {s 6.04 7.87 9.51 7.00 8.99 7.07 9.91 8.02 8.02 9.02 0.00 7,7! 9,04 9.07 6.50 9.99 8.07 6.99 6.03 9.99 tons, 17 7.06 7.96 5.94 9.99 9.09 transformation V “l. - D. From an9smat. 6,94 7.94 9.09 9.98 6.02 7,01! 0,06 9.05 8.09 10.64 9,9! 0,07 6.5 7.75 8, ö3 59.0 66.3 68.3 61.1 69.1 61.2 68.9 62.9 67.0 64.2 59.9 64.1 67.2 70.6 60.6 67.0 62.6 6t, 6 59.8 62.4 67.8 60.8 5! , 7 56.8 62.3 65.4 61.3 62.7 65.0 64.2 57.8 56.7 63.5 63.5 62.6 71.0 66.0 67.0 B1,3 62.6 67.6 7.2,9.2,9.4,7.1,8.4,7.5,9.0,7.5,8.4,8.2,6.7 10.3 10.8 RST! 7,7,0.7,8.3,6.9,5.6,8.2,9.4 7.68.8 6.2,8.3,7.8,6.3,6.0,7.5,8.3 5, “yield B, 3,7.7 7, l 6.9,8.1,9.2,5.6,7.1,6.3,7.6 H, i/i um9ewo Ausgan9s=ato 125,120,118,110,102 lll 118,119,109,118 llO t36 lk2 129 1! 3,122,109,105 99 122,109,101,104 96 llO 100 86 84 95 88 96 94 90 96 108 tO0 96 91 93 Gesoltù Val. - D. Output measure of 47.3 54.3 52.0 51.5 54.6 53.5 53.4 56.8 55.2 55.6 51.9 49.3 56.1 6t, 3 50.8 55.4 55.9 54.9 53.1 54.9 50.8 53.5 57.3 51.5 50.9 54.4 52.9 56.3 53.5 53.3 53.0 53.4 54.4 55.5 54.8 55.2 54.7 51.9 52.5 51.0 51.7 table V (continuation) cracking test (1) 1G 1H 2H 3H 4H 5H 11 2I 3I 4I 51 iJ 2J 3J 4J 5J 6J 7J 1K 2K 3K 4K 5K 6K 7K 8K 9K locomotive I] K 12K l1 Z1 3L L 5L 61 IN the 2H Kata2ysator addition in Ge - S” (2) I o 0 0 0 0 0 o 0 0 0 0 0 0 0 o 0 o 0 o 0 0 o o, o5 o, o5 0, o5 0, o5 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 self-service (3) O, ton of 0, I0 0.10 0, I0 0.10 0.25 0.25 0.25 0.25 0.25 0.50 0.50 0.50 0.50 0.50 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0, I0 0.10 8.10 0.10 0.10 0.10 0, I0 0.10 catalyst: Oil weight ratio 7.01 10.04 9.02 8.33 B, 53 7.70 10.06 IL, 0& 9.00 0.50 10.70 0.44 8.50 9.49 7.63 7.72 6.49 8.01 9.53 10.50 7,7! 9,03 7.74 9.98 19.51 8.53 9.37 6.56 19.01 9.86 8.97 7.70 6.54 7.50 10.08 9.10 B, 44 7.05 8.50 5.89 7.71 7.70 transformation VOL. - D. Ausgen9smat. 04,4 89.8 72.0 06.5 59.3 04.3 87.4 70.9 86.3 00.0 74.8 fuel element, 5 66.4 08.7 82.7 81.0 59.2 60.5 65.1 68.5 58.3 62.5 59, t ß5,5 88.6 Bg, 0 75.1 61.9 85.4 69.5 69.8 BO, 9 65.2 60.9 69.5 08.5 68.8 70.7 74.8 ß7,5 70.5 70.9 coke Gew. - % Ausgan9smat, 0.2 7, I 6.2,0.4,5.3,6.4,0.7,7.9,6.6,5.1,6.9,5.8,0.9,6.9,6.1,9.1,5.0,6.8 B, 9,7.4,6.5,7.1 yield H, 1/1 um9ew. Ausgangsmat. 77 74 73 69 00 62 00 00 52 48 61 51 67 87 78 77 77 81 B, 9 plumb bob 8.1 I02 8.9 93 8.0 86 8.3 88 6.5 84 7.9 97 7.9 87 7.5,7.2 88 6.1 77 6.2 76 7.8 04 7.4,5.8 03 6.2 97 7.3 62 6.2 67 7.2 79 7.7 Gasotin VOL. - % D. Ausgangsmat. 52,4 57.2 57.2 58.1 52.7 55.3 56.4 52.6 55.0 53.8 57.2 59.7 55.8 52.9 54.1 51.2 48.2 49.1 49.3 46.9 47.3 50.0 52.9 50.9 52.0 57.0 51.2 54.9 57.2 52.8 58.8 56.0 59.3 02.9 55.9 5ö, 4 62.3 63.6 63, $ 03.0 59.5 58.8 table V (continuation) catalyst cracking addition in Gew. - Test (1) Sn (2) I self-service (3) tN 2N 3 0.10 0,0! 0,10 0.01 0, I0 0.01 0.50 0.50 0.50 0.50 0.50 0.50 Katslysator: Ö1 Gewi: htsverhältnis 7.72 7.70 7.73 transformation VOL. - D. Ausgangsmat. 60,4 65, g 65.4 7.75 7.68 7.74 66.8 63,0 65.5 yield coke Gew. - Ausgangsmat. 7,5,8.3,8.3,5.3,6.0 6, g H=, i/I umgew. Ausgangsmat. g8 101,101 5 “57 Gasolin Vel. - D. Ausgangsmat. 52,8 56.3 55.5 58.2 53.3 56.4 (1) the tests IA to 5a with a catalyst sample were accomplished. Oie test BA to 11A were accomplished with another catalysis gate sample. (2) referred the outer weight of the catalyst before the addition of tin as Oibutylzlnnoxyd and before the addition of Antlmon, if this were used. (3) related to the weight of the catalyst before the addition of Antlmon as Antlmontrls (ü, O-dipropylphnephordithloat) and before the addition of tin, if this were used. As an investigation points to the Fig.1 to 7 represented results, the advantages of the use of tin and antimony in combination vary for example as a function of the concentration of tin and antimony. of the relationship tin to antimony and the relationship catalyst to oil. Fig.l points clearly the unexpectedly good transformation of the raw material within a range of the catalyst to oil of weight ratio from less than 6 to for instance i0, if a catalyst, which contains both tin and antimony, is used. This by the combination antimony and tin caused positive improvement of the conversion is not only more largely than the sum of the positive contribution of antimony and the negative contribution of tin innerI0 half the catalyst: Oil of weight ratio from 6 to 10, but this combination causes a certain reinforcement of the positive contribution of antimony within the range from approximately 6 to approximately 9 for the catalyst: Oil weight ratio, the Fig.1 and 9 is to be taken those surprisingly good yield from Gasolin to, those with a catalyst: Oil weight ratio from approximately 6 to approximately 9.5 in Fig.1 and from approximately 6 to approximately 8.4 in Fig.5 enters, if a catalyst, which contains both tin and antimony, is used. Fig.6 again shows clearly the unexpectedly small accumulation at hydrogen with a catalyst: Oil weight ratio of approximately 7.7, if the catalyst according to invention is used. To the further illustration of the advantage of the presence of tin and antimony in a cracking catalyst are in table VI results of the transformation and the yield with a Katalyt0 sator: Ö1 weight ratio of 7,7: 1 indicated. The values were determined graphically from the associated curves of the Fig.1 to 7, with exception of the Kraektests 13, 14 and 15, their values the average of the appropriate values of the M, N and O-series to correspond, which are indicated in table V. Thus everyone of the cracking attempts indicated in table VI is not an individual attempt, which was actually accomplished, but the attempt was based on a whole set of tests, which were actually accomplished. Nr.374488 1 2 3 4 6 7 8 9 IO ii 12 13 14 Katalysatmr addition in Gew. - % Sn (i) I self-service (2) I 0.01 0, i 0.5,1.0 0 0 0 0 0 0.05 0.01 0.01 0,1O 0.50 0 0 0 O O, O5 0, I 0.25 0.5,1.0 0.05 0.10 0, I0 0.01 0.50 transformation see - % D. Ausgangsmat. 64 62 61.4 62 60.1 84 64.8 63.8 66 61 64.2 69.8 70.7 65.5 55.1 coke Gew. - % Ausgangsmat. 8,0,7.8,7.2,6.6,6.6 yield 6.1,6.0,5.9,6.3,6.8,6.9,6.6,7.5,8.3,6.4 H2, I/l umgew. Ausgan8smat. IL 114,114 i03 94 94 73 57 53 09 69 79 iO1 57 Gasolln VOL. - % D. Ausgengsmat. i 53.3 52.7 54.1 54.6 53.9 52.5 55.0 55.1 56.1 50.0 56.8 61.1 59.1 56.5 56.0 (I) referred euf the weight of the Katelyseters before the addition of tin as Dibutylzinnoxyd, (2) related to the weight of the catalyst before the addition the antimonies as the Antlmontris (O, O-dibutylphosphordlthloat) and before the addition of tin, if such an addition took place. As the table VI shows, is the transformation of the raw material and the yield at Gasolin with the cracking tests 1 to 15, with which the catalysts according to invention were used, surprisingly highly in the comparison with transformations and Gasolinausbeuten with the cracking tests 1 to 10, which were accomplished with catalysts, which did not lie in the context of the invention. So is for example transformation raw material and Gaselinausbeute in attempts 12 and 13 far high, when one based on the basis of the change of the characteristics, on the Rcsultaten of the comparison attempt i, where neither antimony nor tin are present, the attempt 2, where only tin could accept and the attempt 7, where only Antimen is present, if eat these changes additive are. SE one became on the basis of the attempts 1, 2 and 7 the raw material transformation in the attempts 12 and 13 predicts with 64 + (62 - 64) + (64.8 - - 64) = 62.8 VOL. - %. One would predict the Gasolinausbeute in the attempts 12 and 13 with 53,3 + (52.7 - 53.3) + (55.0 - 53.3} = 54.4 VOL. - % of the raw material. Everyone of these predicted values lies substantially lower than the values for the appropriate characteristics, as they are indicated in the attempts 12 and 14. On similar basis the Umwandlnng of the raw material and the yield at Gasolin are surprisingly high in the attempt 14, if they are compared with the Oharakteristiken of the catalyst in the attempts i, 3 and 6. An interpolation made for the estimation of the value for a catalyst, which exhibits the antimony content of the catalyst in attempt 14, but no tin has. On similar basis the conversion of the raw material and the yield at Gasolin are higher in the attempt ii, than one would predict I, 2, 3 and 6 with the help of an interpolation with view of the values of the attempts. Likewise the conversion of the raw material to attempt 15 is more highly than one with attention of the values of the attempts i, 4 and 9 predicting could. Furthermore the conversion of the raw material and the yield at Gasolin, which will receive Ii on use of the catalyst in the attempt, are more highly than the average of the values for the appropriate characteristics in the attempts 3 and 7, in which the catalyst contains antimony or tin in absence of the other component. The concentration of these components is equal the sum of the concentrations of antimony and tin in the catalyst with attempt IITH actual is however the Gasolinausbsute with attempt 11 more highly than with everyone of the attempts 3 or 7. in similar way is the conversion of the raw material and the Gasolinausbeute, which will receive 15 with attempt, more highly as the average of the values for the appropriate characteristics in the attempts 5 and I0 and indeed higher than each of the values for the appropriate characteristics, as they are shown for the attempts 5 and 10. Also with the catalysts in the attempts 12, 13 and 14 received values for the conversion of the raw material and the yield at Gasolin are more highly as each value and also higher than the average of these values for the appropriate Charaktsristika that antimony industrial union or tin containing catalysts, in absence the other component, with a concentration, those equal are in each case the sum of the concentrations of Antlmon and tin with the catalysts the one of the attempts 12, 13 and 14. The values for the antimony or tin, in each case in absence of the other component, containing catalysts were received by interpolation 8 values indicated for the attempts 3 and of the 4 and/or 7 and. A comparison of the attempt 12, in which the catalyst of an aging was submitted by longer storing with attempt 13, in which a similar catalyst was used, which after the production 34 days it was stored, before he was used in the KrackversuGh, shows that although the used catalyst is very good with both attempts, which is unfavorable general effect of a long-continuing Altorung by storage. Although the conversion of the raw material to attempt is better 13 than in attempt 12, Koksund hydrogen portion is smaller gröi it as in attempt 12 and the Gasolinausbeute in attempt 13. Example 4: A commercial cracking catalyst from amorphous silicon dioxide and alumina, nationalized with neolithischem material, which in a usual cracking plant one used and afterwards in the laboratory one regenerated, was used for the production of Kraekkatalysatoren with different quantities of antimony, tin or antimony and tin. The source for antimony was antimony trichloroethylene (O, O-dipropylphosphordithioat) and the source for tin was Dibutylzlnnbis (isocctylmercaptoacetat}. This connection has the formula (numerical control H9) 2 Sn (SCH2 CO2 C8 H - ISO) z. The characteristics of the used cracking catalyst before the recovery in the laboratory are indicated in table VII. Table VII surface 89.2 m2/g Poronvolumen 0.30 ml/g composition silicon 2ö, 5 thread - % aluminum 19.7 Gew. - % calcium O, 037 Gew. - % sodium 0.49 Gew. - % potassium 0.076 Gew. - % lithium 0.005 Gew. - % phosphorus 0.09 Gew. - % cerium O, 60 Gew. - % nickel 0.038 Gew. - % vanadium 0, II Gew, - % iron 0.62 Gew. - % titanium 0.77 Gew. - % carbon 0.17 Gew. - % of this used, trade [lbliche cracking catalyst with the characteristics indicated in table VII, in the laboratory by heating up in the fluid bed with air on 649°C and by maintaining this temperature over 1 h one regenerated. The catalyst was cooled then in the fluid bed with nitrogen on ambient temperature, about 25°C. The received catalyst was called catalyst Y and used as follows. A part of the catalyst Y was used for the production of a catalyst composition, with which on i00 Gew. - Parts catalyst Y 0.01 Gew. - Parts antimony and 0.001 Gew. - Telle tin and/or 0.02 Gew. - Parts antimony and 0.002 Gew. - Parts tin came. The composition with the lower Ant [rnonund tin content was manufactured by addition by two Cycl “hexane solutions under agitating to catalyst Y, whereby the one of these solutions the computed quantity of Dibutylzinnbis (isooctylmercapteacetat} and the other one the computed mixes a mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordithioat) with 10,9 Gew. - % antimony contained. Afterwards the received mixture on a hot plate was dried. The composition with higher Antimonund le tin content was manufactured by mixing the catalyst Y with a cyclohexane solution, which contained the computed quantity of Dibutylzinnbis (isooctylmercaptoaeetat). The mixture was dried on a hot plate. The received dry mixture was mixed with cyclohexane solution, those the computed quantity of a mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordithioat], the 10.9 Gew. - % Antlmon contained, agitated. The received mixture was dried on a hot plate. Another portion of catalyst Y became for the production of a catalyst composition with 0,002 and 0,011 Gew. - Parts tin on 100 Gew. - Parts of the catalyst Y uses. With both of these compositions a solution of the computed quantity of Dibutylzinnbis (isooctylmercaptoacetat) was mixed in cyclohexane or toluol with the catalyst Y. The received mixture was getroeknet on a hot plate. Finally still another some of the catalyst became Y for the production of a catalyst composition with 0,011 and 0,02 Gew. - Parts antimony ever 100 Gew. - Parts catalyst Y uses. With each these two compositions became the computed quantity of a mineral oil solution of Antimentris (O, O-dipropylphosphordithioat) with 10,9 Gew. - % antimony in Cyelohexan with catalyst y mixes. The received mixture was dried on a hot plate. Each of these 0 catalyst compositions was further-treated as follows. The catalyst became in a quartz reactor of Laboratoriumsgr6Be in the fluid bed with nitrogen of ambient temperature (about 25°C) heated up on 48Z°C. Subsequently, it was heated up in the Wirbelhett with hydrogen on 649sC. At this temperature the catalyst 5 min was held with nitrogen in the Wirhelbett and treated afterwards with air in the same way 15 min long. In a case the catalyst was held again for 5 min with 049 " C with nitrogen in the Wirbelhett. The catalyst was then aged I0 of cycles long, whereby each cycle was accomplished as follows. The catalyst was cooled for about 0.5 to i min in the Wirbelhett with air on for instance 482°C. Then a treatment with nitrogen followed about 1 min at the same temperature long. Subsequently, the catalyst 2 min in the Wirhelbett with nitrogen and hydrogen was heated up 649°C and held at this temperature a further minute with nitrogen in the fluid bed. Subsequently, with 649°C the catalyst 10 min was treated with air in the Wirhelbett. After i0 of such ageing cycles the catalyst on ambient temperature (about 25°C) in the fluid bed with nitrogen became cooled. ùDiese 6 aged catalysts and catalyst Y were used in seven series of a cracking RH of generation cycle. The cracking stage became over a range the catalyst: ÖI relationship using approximately 35 to 37 g of the catalyst accomplished in the fluid bed in a quartz reactor. As raw material for the cracking stage became a mixture consisting of ß8,12 Gew. - Parts gas oil, 11.98 G8w. - Parts heavy rotating oil and 19.87 Gew. - Uses parts Sehlammöl. With each cycle the cracking stage was long accomplished with for instance 510°C and with atmospheric pressure 0.5 min. The regeneration was made with for instance 6490C and with atmospheric pressure approximately 30 min long in the fluid bed with air. The reactor was rinsed before and after each Kraekstufe for cleaning with nitrogen, the mixture of the raw materials, which was used in the cracking stage, had a API - density with lB*C 25.4 ven, as this is indicated also in table II. The value for the API density with 160C, according to the same method was intended for the gas oil component 27.3, for which heavy rotating oil intends 17.5 and for the mud oil with 2,2. An analysis of the Gas61s resulted in that it 0.99 Gew. - % sulfur and 0.133 Gew. - % nitrogen contained. The results of the cracking attempts, those with different catalyst: L-conditions were accomplished, are summarized in table VIII. All cracking attempts, which were accomplished with a given catalyst, were taken up to the table, with exception of those, which resulted in obviously wrong results, are it due to a failure of the device or due to one mensohlioheu mistake. In particular attempts, beß those the material remainder been ruled out outside of the range from 100 + 5% lay. The attempts with a given catalyst were accomplished in the order, as they are indicated in the table. With catalysts, which were treated with tin, any more than 6 days between the production and the first accomplished test or between two following each other tests did not elapse. Among them also tests are included, which were incorrect for the reasons stated above. The Fig.8 le and 9 of the designs shows a diagram of a comparison of selected attempts of the table VIII. a series of at least five attempts with a given catalyst with different Kata] more ysater: Ö1-Verhältnissen was laid on on a curve and resulted in the flat represented curves. A pair of attempts with a given catalyst and approximately constant catalyst: Oil relationship is represented as individual point. Each of these points represents the average of the values, on which it is based. Catalyst Krack2ugabe in Gew. - - Test Sn (1) I I IA 0 2A 0 3A 0 4A 0 5a 0 APPROX. 0 1B 0.002 28 0.002 IC 0.011 0.011 3C 0.011 4C 0.011 5C 0.011 BC 0.011 0.011 0.011 9C 0.011 IOC 0.011 ID 0 0 0 0 5D 0 0 0 0 90 0 I00 0 eyelid 0 table VIII self-service (2) 0 7.01 0 6.07 0 4.98 0 9.02 0 5.07 0 4.55 0 5.40 0 5.51 0 5.50 0 5.50 0 4.50 0 5.00 0 6.24 0 5.00 0 6, g7 0 7.98 0 8.98 0 4.51 0.011 5.50 0.011 8.03 O, Olt 7.01 0.011 6.24 O, Olt 5.00 0.011 4.50 0.011 5.00 0.011 8,99 0,011 7.00 0.011 5.49 0.011 6.22 catalyst: Oil weight ratio transformation VOL. - D. Out anosmat. 54,0 52.7 47.8 57.6 51.7 48.2 48.7 50.4 48.4 47.1 44.7 51.6 52.0 48.9 56.1 61.0 6), I 47.4 coke Gew. - Ausgan9smat. 5,5,4.7,5.0,7.0,4.8,4.4,6.2,6.0,5.1,5.3,5.2,4.0,5.5,5.9,0.5,7.8,7.0,4.5 51.2 56.6 52.8 55.3 45.8 45.7 48.6 5g, 8 54.8 40.5 55.4 yield 5.0,6.4,5.8,5.1,4.9,4.4,5.3,7.1,6.0,5.3,5.5 H=, 1/1 um9e Ausgan9smat. 2g 28 28 19 18 22 18 22 26 24 24 21 23 22 17 14 14 17 14 Gasolin VoI. - D. Ausgan smat. 44,9 45.0 42.0 4@, g 44.4 41.7 42.9 46.6 43.4 43.0 39.4 44.6 47.0 43.5 47.4 46.1 50.3 41.6 45.6 50.3 45.3 46.9 41.8 39.6 44.1 50.0 44.1 B6,0 47.6 table VIZI (continuation) catalyst cracking addition in Gew. - Z - Test Sn (1) (2) IE 0 2E 0 IF 0.001 2F 0.001 3F 0.001 4F 0.001 5F 0.001 5F 0.001 7F 0.001 BP 0.001 9F 0.001 IOF 0.001 11F 0.001 0.002 0.002 0.002 0.002 5@ 0.002 I self-service 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.02 0.02 0.02 catalyst: Oil weight ratio 5,5B 5.46 5.53 5,4B B, 02 7.02 8.98 ß, 24 5.00 5.00 5.49 6,0! 4,48 ß, 99 5.49 6.23 8.03 9.02 transformation Voi. - % D. Ausgen9smet. 52,2 54.4 54.3 47.9 5b, 4 58.7 5b, 6 5ö, 7 47.7 49.5 50.9 52.2 4B, 0 53.6 4B, 2 50.5 57.1 59.4 5.0,4.6 yield 5.2,4.0,7.3,5.3,7.7,5.7 5! 4, g 5.2,5.9,5.2,4.9,4.7,5.4,7.2 ö, 5 H, llt umgew. Ausgangemat. i i 13 23 eat 14 industrial union eat 13 17 ii II 14 22 16 19 2B Basolln VOL. - D. Auegangsmat. 43,2 45.1 4B, 8 43.8 51.2 51, B 49.5 4B, 0 44.6 45.6 43, t 46.2 39.3 43.8 44.6 40.6 47.7 50.0 (I) related to the weight of the catalyst before the additive of Oibutylz [nnb [o (isooctylmereaptoecetot) and taken place before the additive of the antimony, case such. (2) related to the weight the catalyst before the addition of Antlmon as the Antlmon ris (O, O-dlpropylphosphordlthloat) and before admit from tin, if such takes place. Due to the same proof as in the example 3 Fig, B shows that the catalyst 0.002 Gew. - Parts tin and 0.02 Gew. - Parts antimony ever 100 Gew. - Parts of the catalyst before the treatment with Zinnund antimony connections, one fibre-rapid-end low accumulation at coke with a low catalyst: ÖI weight ratio, e.g. 5,5: I, causes. Still many more remarkably Fig.9 shows that a Katalysater with 0,801 Gew. - Parts tin and 0.01 Gew. - Parts of Antimen ever 100 Gew. - Parts catalyst before the treatment a surprisingly with Zinnund Antimenverbindungen, high yield at Gaselin with catalyst: ÖI Gewiehtsverhältnissen from approximately 5 to approximately 9 furnishes and an unexpectedly high transformation of the outer one sgangsmateria] s with middle catalyst: Ö118-Gewichtsverhältnissen and a surprisingly low accumulation of hydrogen with catalyst: Ol - Gewiehtsverhältn ssen within the range of 6 to 9 furnish. Example 5: This calculated example is to show that this preferential execution of the invention can be accomplished also in industrial yardstick. In a usual cracking plant become with 181 t of the Kraokkatalysators 3.863.700 1 daily an oil with spec. Weight 16e/18°0, 0.929 gekrankt. Around a Krackkata] ysator with 0,15 Gew. - % antimony and 0.015 Gew. - % tin, related to the untreated catalyst, too received, to the raw material of antimony trichloroethylene (O, O-dipropylphosphordithioat) in 17 days are long added quantities, which correspond to 6 ppm antimony, and Dibutylzinnbis (isooctylmercaptoacetat) in quantities, which correspond to 0.6 ppm tin. With one only I0 days continuing addition to the raw material is attached antimony trichloroethylene (O, G-dipropylpbospherdithioat) in an amount, the 9 ppm antimony, and Dibutylzinnbis (isooctylmercapotoaoetat) in an amount, which corresponds to 0.9 ppm tin. Around the antimony content with 0,15 Gew, - % and the tin content with 0,015 Gew. - % to hold, the addition of Antimonund Z must [it nnverbindungen to the raw material to take place in such a way that in the raw material a content will receive tin from 3 ppm antimony and 0.3 ppm, if daily 7.2 t catalyst are inferred from the cracking reactor system and replaced by untreated catalyst. If only 5.4 t catalyst are daily replaced, the addition is sufficient, over Antimonund Zlnngehalt of the catalyst system with 0,195 and/or with 0,0135 Gew. - to hold %. This means that 208.63 kg of a Mineral611ösung von Antimontris (O, O-dipropylphosphordithioat) with an antimony content of 11 Gew. - % and 17.84 kg commercial Dibutylzlnnbis (isooctylmercaptaacetat) with a tin content of 18,1 Gew. - % the Ausgangsmatsrial i0 days to be long daily added must (at 17 days 135.75 and/or Ii, 80 kg], in order to reach indicated Antimonund tin content on the catalyst. In order the angegebeI0 nen values to maintain, must the raw material daily 07, BB kg of this mineral oil solution of antimony trichloroethylene (O, O-dipropylphosphordithloat) and 5.07 kg commercial Dibutylzinnbis (isoootylmercaptoacetat) to be added,