DE19962669B4 - Reduction of the sulfur content in gasoline during fluid catalytic cracking - Google Patents

Abstract

A method of reducing the sulfur content of a catalytically cracked petroleum fraction, characterized by the catalytic cracking of an oil feed fraction containing organosulfur compounds at elevated temperature in the presence of a cracking catalyst and a catalyst for reducing the sulfur content in the product comprising a porous molecular sieve, which (i) one first metal component located within the pore structure of the molecular sieve and comprising a metal in an oxidation state greater than zero and (ii) comprising a second metal component located within the pore structure of the molecular sieve and comprising at least one rare earth metal, whereby liquid cracking products with a lower sulfur content are produced.

Description

The invention relates to the reduction of sulfur or the reduction in sulfur content in gasolines and other petroleum products, generated by a catalytic cracking process. The invention provides a catalyst composition for reducing the sulfur content in the product and a process for reducing the sulfur content ready in the product using this composition.

Catalytic cracking is a Petroleum refinery process, especially in the United States on a large scale is applied in which the bulk of the refinery's mixed gasoline pool through catalytic cracking is generated, with almost everything from a catalytic fluidized bed cracking process (FCC procedure) is coming. In the catalytic cracking process high-boiling hydrocarbon fractions by reactions at a higher one Temperature take place in the presence of a catalyst, in low boiling Products converted, with most of the conversion or conversion Cracking takes place in the vapor phase. The feed material is so in gasoline, distillate and other liquid cracked products and also low-boiling gaseous Cracked products with 4 or fewer carbon atoms converted per molecule. The gas consists partly of olefins and partly of saturated Hydrocarbons.

In the crack reactions, a Part of the high-boiling material known as coke deposited the catalyst. This reduces its catalytic activity and regeneration is necessary. After removing the trapped Hydrocarbons from the spent cracking catalyst regeneration by burning the coke, and after that is the activity of the catalyst restored Therefore three characteristic A distinction is made between catalytic cracking steps: a cracking step, in which the hydrocarbons are converted into low-boiling products a step to stripping or separating (hereinafter referred to as stripping ) to the hydrocarbons adsorbed on the catalyst to remove and a regeneration step to remove the coke from the catalyst to burn. The regenerated catalyst is then in the cracking step reused.

Feedstocks for catalytic cracking typically contain sulfur in the form of organic sulfur compounds such as mercaptans, sulfides and thiophenes. Consequently, the cracking process products tend to contain sulfur contaminants, although about half of the sulfur in the cracking process is converted to hydrogen sulfide, primarily by catalytic decomposition of the non-thiophenic sulfur compounds. The distribution of sulfur in the cracking products depends on a number of factors including the feed, the type of catalyst, the additives present, the conversion and other process conditions, but in any case a certain part of the sulfur easily gets into the low boiling or high-boiling gasoline fractions and flows into the product pool. With the increasingly stringent environmental regulations applicable to petroleum products, e.g. B. in the regulations "Reformulated Gasoline (RGF)", the sulfur content of the products has generally been reduced and this is a reaction to the problematic emissions of sulfur oxides and other sulfur compounds into the air due to combustion processes. The reduction in the sulfur content in gasoline is critical not only for SO _x emissions but also for the poisoning of catalytic converters in motor vehicles with sulfur. The poisoning of catalysts causes other emission problems, such as NO _x .

Given the primary position as automotive fuel for automobiles in the United States, environmental concerns are largely directed to the sulfur content of motor gasoline. However, these concerns have also been extended to higher boiling distillate fractions, including light recycle oil (LCO) and heating oil fractions (light heating oil, LFO, and heavy heating oil, HFO), obtained from a catalytic cracking process. Hydrogen desulfurization has long been used in these products to reduce sulfur levels in the product fractions, and this has generally been found to be effective. However, due to the increasing heat-resistant or resistant (hereinafter referred to as heat-resistant) nature of the sulfur compounds, in particular the substituted benzothiophenes with increasing boiling point, the higher-boiling fractions of desulfurization are not as easily accessible as the lower-boiling fractions. In the LCO hydrodesulfurization process, substitution of benzothiophene and dibenzothiophene only methyl and / or alkyl causes a substantial reduction in the desulfurization reactivity of the organic sulfur compounds, and these become "hard sulfur" or "heat-resistant sulfur". An example of a GC (gas chromatogram) of sulfur in LCO is in 1 shown along with the description of the GC for sulfur. A report by Girgis and Gates, Ind. Eng. Chem., 30, 1991, 2021-2058 states that the substitution of a methyl group in the 4-position or in the 4- and 6-positions reduces the desulfurization activity by an order of magnitude. Houalla et al. reports activity loads on the order of 1 to 10, M. Houalla et al., Journal of Catalysis, 61, 1980, 523-527. Lamure-Meille et al. suggest that steric hindrance of the alkyl group causes the low reactivity of methyl substituted dibenzothiophenes, Lamure-Meille et al., Applied Catalysis A: General 131, 1995, 143-157. In view of the utilization of the higher-boiling catalytic cracking products as Be For hydrodesulfurization processes, the incentive to reduce the occurrence of the more heat-resistant organic sulfur compounds in these cracking fractions becomes clear.

One attempt is to remove the sulfur from an FCC feed by hydrotreating or Hydrotreatment (hereinafter referred to as hydrotreating) before starting of cracking. Although this attempt is very effective, it is in the face of it the cost of equipment for as well the implementation the process is expensive because the hydrogen consumption is high. On another attempt is to remove the sulfur from the cracked products through hydrotreating. Although this solution is effective, it has the disadvantage that the valuable octane number of the product can be lost if the high octane Olefins are saturated.

From an economic perspective, it would be desirable that To achieve sulfur removal in the cracking process itself, because thus the main component of the mixed gasoline pool without further Treatment could be desulfurized effectively. There were different ones Catalytic materials to remove sulfur during the FCC process cycle developed, most of the developments aimed however, so far on the removal of sulfur from the exhaust gases of the Regenerator. An earlier one Alumina compound experiment developed by Chevron as additives (hereinafter as additives referred) to the cracking catalyst inventory so that sulfur oxides in the FCC Regenerator adsorbed; the adsorbed sulfur compounds, those that entered the process in the feed were removed during the Crack section of the cycle released as hydrogen sulfide and got to the product extraction section of the plant where it was removed were. See Krishna et al., Additive Improve FCC Process, Hydrocarbon Processing, November 1991, pp. 59-66. The sulfur is removed from the exhaust gases of the regenerator is removed, the sulfur values of the product however, if at all, not significantly affected.

An alternative technology for removing sulfur oxides from the regenerator is based on the use of magnesium-aluminum spinels as additives to the circulating catalyst inventory in the FCCU (system for catalytic fluid bed cracking). This technology has achieved remarkable commercial success under the name DESOX ^® , which is used for the additives in this process. Exemplary patents for this additive type for removing sulfur include US 4,963,520 . 4 957 892 . 4 957 718 . 4,790,982 and other. However, the sulfur values of the product are again not significantly reduced.

A catalyst additive for reduction the sulfur values in liquid Cracked products are described by Wormsbecher and Kim in U.S. Patents 5 376 608 and 5 525 210 are proposed, with a cracking catalyst additive from a Lewis acid supported on aluminum oxide for the production of gasoline with lower sulfur content, this system has however, has not had a clear commercial success. Therefore there is still in need of an effective additive to reduce the Sulfur content of liquid Catalytic cracking products.

In the German patent application No. 199 41 319.3, filed on August 31, 1999, we have catalytic Materials for describes the use in the catalytic cracking process, the the sulfur content of the liquid Products of the cracking process can reduce. These catalysts for Reductions in sulfur content include in addition to a porous molecular sieve component inside the pore structure of this sieve is a metal, its oxidation state larger than Is zero. The molecular sieve is a zeolite in most cases and it can be a zeolite whose properties match those of zeolites with large pores, such as zeolite beta or zeolite USY, or with those of zeolites with medium pore size, such as ZSM-S. to match. Non-zeolitic molecular sieves such as McAPO-5, McAPSO-5, and also mesoporous crystalline materials, such as MCM-41, can be used as the sieve component of the Catalyst can be used. Metals such as vanadium, zinc, iron, Cobalt and Gallium have chosen effective reduction of sulfur in gasoline, with vanadium being the preferred metal. If these materials as a separate, particulate Catalyst additives are used, they are used in combination with the active catalyst for catalytic cracking (usually a faujasite like zeolite Y, especially as zeolite USY) used to feed hydrocarbon materials in a facility for to treat fluid catalytic cracking (FCC), whereby low-sulfur products are manufactured. Because the sieve component of the catalyst for reducing the sulfur content itself is an active cracking catalyst, z. B. zeolite USY, it is also possible to use the catalyst Reduction of the sulfur content in the form of an integrated catalyst system for cracking / reducing to use the sulfur content, the z. B. USY as an active cracking component and the sieve component of the system for reducing the sulfur content with an added matrix material such as silica, clay, and a metal, e.g. B. Vanadium, which includes the functionality for the reduction of the sulfur content.

Another consideration in the manufacture of FCC catalysts is the stability of the catalyst, particularly hydrothermal stability, since crack catalysts are subjected to repeated cycles of reduction (in the cracking step) followed by steam stripping and then oxidative regeneration, by burning coke, a carbon-rich hydrocarbon that is deposited on the catalyst particles during the cracking section of this cycle, large amounts of steam are generated. When developing zeolite cracking catalysts, it was discovered early on that a low sodium content was necessary not only for optimal cracking activity but also for stability, and that rare earth elements, such as cerium and lanthanum, confer greater hydrothermal resistance. See e.g. B. Fluid Catalytic Cracking with Zeolite Catalysts, Venuto et al., Marcel Dekker, New York, 1979, ISBN 0-8247-6870-1.

We now have catalytic materials developed for use in a catalytic cracking process, the reduction in the sulfur content of liquid products of the cracking process, including in particular the gasoline and medium distillate fractions from cracking, can improve. The catalysts of the invention to reduce the sulfur content are those in the US application No. 09 / l44 607 similarly described, because in the pore structure of a molecular sieve component of the catalyst composition there is a metal component whose oxidation state is greater than zero is, again vanadium is preferred. In the present case comprises however, the composition also includes one or more elements of the rare Earth, preferably cerium We have found that through the presence of a rare earth component the stability of the catalyst is improved compared to catalysts that only use vanadium or contain another metal component, and that in certain advantageous cases, especially with cerium as a component of the rare earths, through this existing elements of the rare earth also the activity at the Reduction in sulfur content is improved. Which is surprising since rare earth cations themselves have no activity in the Show reduction in sulfur content.

The catalysts for reduction according to the invention of the sulfur content can in combination in the cracking system in the form of an additional catalyst with the active cracking catalyst, d. H. in combination with the conventional Main component of the circulating cracking catalyst inventory used become the ordinary one connected to a matrix or embedded in a matrix or bound zeolite (hereinafter referred to as bound) that contains a catalyst which is based on a faujasite zeolite, usually zeolite Y. According to another embodiment can it in the form of an integrated cracking / reducing catalyst system of the sulfur content in the product.

According to the present invention, the catalyst composition comprises to remove sulfur, a porous molecular sieve that (i) inside the pore structure of this sieve there is a metal in an oxidation state of greater than zero and (ii) contains a rare earth component. The molecular sieve is in most cases a zeolite and it can be a zeolite whose properties with those of zeolites with large Pores, such as zeolite beta or zeolite USY, or with those of zeolites only medium pore size, like ZSM-5. Non-zeolitic molecular sieves, such as McAPO-5, McAPSO-5, and also mesoporous crystalline materials, such as MCM-41, can be used as the sieve component of the Catalyst can be used. Metals such as vanadium, zinc, iron, Cobalt and gallium are effective. If the selected sieve material is sufficient cracking activity it can act as an active catalytic component of the cracking catalyst (usually a faujasite such as zeolite Y), or it can be according to another embodiment additionally be used for this active cracking component, regardless of this is whether it has any cracking activity itself.

The compositions of the invention are beneficial to hydrocarbon feedstocks in plants to treat fluid catalytic cracking (FCC), whereby low sulfur gasoline and other low sulfur liquid products, e.g. B, easy Return oil that as Low sulfur mixture component used for diesel or as heating oil can be manufactured. The catalyst materials according to the invention to reduce the sulfur content achieve a very clear Reduction in the sulfur content of the cracked gasoline fraction and can also the sulfur values of light return oil and heating oil products (light heating oil, heavy heating oil) reduce. The reduction in the sulfur content in LCO occurs predominantly in the substituted benzothiophenes and substituted dibenzothiophenes on; the removal of these more heat-resistant species improves the efficiency in reducing the sulfur content in the subsequent hydrodesulfurization process by LCO. The reduction in the sulfur content in HFO can be a quality improvement of the products of the coking plant, from oil to premium coke.

Although the mechanism by which the metal-containing zeolite catalyst compositions containing the sulfur components remove that normally in cracked hydrocarbon products exist, is not exactly known, it involves the conversion organic sulfur compounds in the feed in inorganic Sulfur so this Process is a real catalytic process. It is believed, that in this process the zeolite or other molecular sieve this shape selectivity with different pore sizes, and that the metal seats in the zeolite for the adsorption sites for sulfur species to care.

The drawings are graphical representations, which reduce the performance of the compositions of the invention the sulfur content as described below.

FCC process

Removal catalysts of the invention of sulfur are circulating as a catalyst component Catalyst stock used in a catalytic cracking process, which today almost without exception is a catalytic cracking process (FCC process) is. For convenience the invention will be described using this FCC method, though the additives according to the invention in the older cracking process moving bed type (TCC method) can be used if the particle size suitable is set so that it meets the requirements of this procedure. Except for the addition of the additive according to the invention on the catalyst inventory and some possible changes in the product recovery section, which are explained below the manner in which the procedure is carried out remains unchanged. Consequently can conventional FCC catalysts are used, e.g. B. based on zeolite Catalysts with a faujasite cracking component, as it is in an overview of the Development by Venuto and Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1 and also in numerous other sources, such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Publ. Houston, 1995, ISBN 0-88415-290-1, is described.

• (i) Die Beschickung wird in einer katalytischen Crackzone, normalerweise einer Riser-Crackzone bzw. Steigrohr-Crackzone (nachfolgend als Riser-Crackzone bezeichnet), die bei katalytischen Crackbedingungen arbeitet, durch den Kontakt der Beschickung mit einer Quelle von heißem, regeneriertem Crackkatalysator katalytisch gecrackt, wodurch ein Abfluß erzeugt wird, der Crackprodukte und verbrauchten Katalysator umfaßt, der Koks und abtrennbare Kohlenwasserstoffe enthält,
• (ii) der Abfluß wird abgegeben und, normalerweise in einem oder mehreren Zyklonen, in eine an Crackprodukt reiche Dampfphase und eine feststoffreiche Phase getrennt, die den verbrauchten Katalysator umfaßt,
• (iii) die Dampfphase wird als Produkt abgeleitet und in der FCC-Hauptkolonne und deren zugehörigen Nebenkolonnen fraktioniert, wodurch flüssige Crackprodukte, einschließlich Benzin, erzeugt werden,
• (iv) der verbrauchte Katalysator wird, gewöhnlich nur Dampf, gestrippt, um die eingeschlossenen Kohlenwasserstoffe aus dem Katalysator zu entfernen, danach wird der gestrippte Katalysator oxidativ regeneriert, wodurch heißer, regenerierter Katalysator erzeugt wird, der dann zur Crackzone rezirkuliert bzw. zurückgeleitet wird, um weitere Mengen der Beschickung zu cracken.

To summarize somewhat more briefly, the fluidized bed catalytic cracking process, in which the high-boiling hydrocarbon feed containing organosulfur compounds is cracked into low-boiling products, occurs through the contact of the feed in a cracking process with cyclic circulation of the catalyst and with a circulating inventory of swirlable catalyst for the catalytic cracking , which consists of particles whose size is in the range of 20 to 100 μm (micron). The significant steps in this cyclical process are:

• (i) The feed becomes catalytic in a catalytic cracking zone, usually a riser cracking zone or riser cracking zone (hereinafter referred to as riser cracking zone), which operates under catalytic cracking conditions, by contacting the feed with a source of hot, regenerated cracking catalyst cracked, creating a effluent comprising cracked products and spent catalyst containing coke and separable hydrocarbons,
• (ii) the effluent is discharged and, usually in one or more cyclones, separated into a vapor phase rich in cracked product and a solid phase which comprises the spent catalyst,
• (iii) the vapor phase is derived as a product and fractionated in the main FCC column and its associated secondary columns, thereby producing liquid cracking products, including gasoline,
• (iv) the spent catalyst, usually steam only, is stripped to remove the trapped hydrocarbons from the catalyst, then the stripped catalyst is oxidatively regenerated to produce hot, regenerated catalyst which is then recirculated to the cracking zone, to crack further quantities of the feed.

The feed to the FCC process is typically a high-boiling feed derived from mineral oil, normally with an initial boiling point of at least 290 ° C (550 ° F) and in most cases above 315 ° C (600 ° F). Most separation limits for FCC feeds in the refinery are at least 345 ° C (650 ° F). The end point is dependent the exact nature of the feed or the process features the refinery changeable. The feeds are either a distillate, typically with an end point of 550 ° C (1020 ° F) or above, z. B. 590 ° C (1095 ° F) or 620 ° C (1150 ° F), or alternatively, a (non-distillable) residue material can be used in the feed can be included and this can even include the entire feed or constitute an essential part of it. Distillable feeds include crude oil feeds, like gas oils, z. B. heavy or light atmospheric gas oil, heavy or light vacuum gas oil and also cracked feeds, like light gas oil from a coking device, heavy gas oil a coking device. It can be hydrotreated Feeds, e.g. B. hydrotreated gas oils, in particular heavy gas oil subjected to hydrotreating can be used since the catalysts of the invention however, a significant reduction of the sulfur content can cause can it be possible be to omit the first hydrotreatment, the job of which in There is a reduction in the sulfur content, and still improvements in the Crack assets to reach.

In the process according to the invention, the sulfur content the gasoline part of the liquid Cracking product effectively brought to lower and more acceptable levels, by catalytic cracking in the presence of a catalyst The sulfur content is reduced.

FCC cracking catalyst

The sulfur reduction catalyst compositions of the present invention can be used in the form of a separate particle additive added to the main FCC catalyst for cracking, or, in another embodiment, they can be used as components of the Cracking catalyst are used, which provides an integrated catalyst system for cracking / reducing sulfur content. The cracking component of the catalyst, which is conventionally present to effect the desired cracking reactions and the generation of low-boiling cracking products, is normally based on an active cracking component made from faujasite zeolite, which is conventionally used in one of its forms, such as a calcined, rare earth, zeolite Y. Y-type zeolite (CREY), the production of which is described in US Pat. No. 3,402,996, an ultra-stable Y-type (USY) zeolite as described in US Pat. No. 3,293,192, and also various in part exchanged type Y zeolites as described in U.S. Patent Nos. 3,607,043 and 3,676,368. Cracking catalysts like this are widely available in large quantities from various commercial suppliers. The active cracking component is routinely combined with a matrix material, such as silica or alumina and also clay, to provide the desired mechanical properties (abrasion resistance, etc.) as well as control over the activity of the active zeolite component or components. For effective swirling, the particle size of the cracking catalyst is typically in the range from 10 to 100 μm. When used as a separate particulate additive, the sulfur reduction catalyst (and any other additive) is typically selected to have a particle size and density comparable to that of the cracking catalyst to prevent separation of the components during the cracking cycle.

System for Reduction of the sulfur content of the sieve component

In the present invention, the catalyst comprises to remove sulfur a porous molecular sieve that inside the pore structure of the sieve is a metal in an oxidation state contains greater than zero. The Molecular sieve is in zeolite in most cases and it can be a zeolite, the properties of which match those of zeolites huge Pores, such as zeolite Y, preferably zeolite USY, or zeolite beta, or with those of medium pore size zeolites such as ZSM-5, match, the former class being preferred.

The molecular sieve component of the catalysts according to the invention To reduce the sulfur content can be as stated above a zeolite or a non-zeolitic molecular sieve. If zeolites can be used they also have large zeolites Pores or zeolites with medium pores can be selected (see Shape Selective Catalysis in Industrial Applications, Chen et al., Marcel Dekker Inc., New York 1989, ISBN 0-8247-7856-1, to explain the classifications of zeolites based on the pore size the basic scheme described by Frilette et al. in J. Catalysis 67, 218-222 (1981) is). In addition to their insufficient stability for use in one Catalytic cracking processes are small pore size zeolites such as Zeolite A and erionite, because of their properties, an exclusion due to the molecular size, generally not preferred because they tend to have components of the crack feed and also many components of the crack products excluded. The pore size of the sieve does not appear critical, however, since it was found that both Medium pore size zeolites as well huge Pores as well as the mesoporous crystalline materials such as MCM-41 are effective as shown below is.

Zeolites with properties that match match the existence of a structure of large pores (12-ring), the for the production of the catalysts according to the invention for reduction of the sulfur content can include zeolites Y in their various forms, such as Y, REY, CREY, USY, of which the the latter is preferred, and also other zeolites, such as zeolite L, zeolite Beta, mordenite, including dealuminized mordenite, and zeolite ZSM-18. Zeolites with large pores are generally characterized by a pore structure with a ring opening of marked at least 0.7 nm and medium or intermediate Have pore size a pore opening of less than 0.7 nm but more than 0.56 nm. Suitable zeolites with medium pore size, the can be used include Pentasil zeolites such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-50, ZSM-57, MCM-22, MCM-49, MCM-56, which are all known materials. Zeolites can with of aluminum different lattice metal elements, e.g. B. boron, gallium, iron, Chrome.

The use of USY zeolite is particularly desirable since this zeolite is typically used as the active cracking component of a cracking catalyst, and it is therefore possible to use the sulfur reduction catalyst in the form of an integrated cracking / sulfur reduction catalyst system. The USY zeolite used as the cracking component can also advantageously be used as a sieve component for a separate particulate additional catalyst, since it also contributes to the cracking activity of the entire catalyst present in the plant. At USY, the stability is related to the small size of the lattice unit, and for optimal results the UCS (size of the lattice unit) for the zeolite USY in the finished catalyst should be 2.420 to 2.460 nm, preferably 2.420 to 2.455 nm, with a range of 2.420 to 2.445 nm, preferably 2.435 to 2.440 nm is very suitable. After the influence of the repeated steam treatment of the FCC cycles, further ver the UCS is reduced to a final value, which is normally in the range from 2.420 to 2.430 nm.

In addition to the zeolites, others can Molecular sieves are used, although these are not so beneficial could be, for this optimal performance apparently requires some acidic activity is (which is conventional only the α value is measured). Test values show that α values of more than 10 (sieve without Metal content) for adequate desulfurization activity is appropriate, while α values in Range of 0.2 to 2000 are usually suitable. (The α test is a suitable method for measuring total acidity, including both internal as well as external acidity, a solid material such as of a molecular sieve. This test is described in U.S. Patent No. 3,354,978, in the Journal of Catalysis, vol. 4, p. 527 (1965), vol. 6, p. 278 (1966) and Vol. 61, p. 395 (1980). The ones in this description listed α values measured at a constant temperature of 538 ° C.) α values of 0.2 to 300 represent the normal range of acidic activity for this Materials when used as additives.

Exemplary non-zeolitic sieve materials which can provide suitable carrier components for the metal component of the catalysts according to the invention for reducing the sulfur content include silicates (such as metallosilicates and titanosilicates) with different silicon dioxide / aluminum oxide ratios, metalloaluminates (such as germanium aluminates), metallophosphates, aluminophosphates such as silica - And metalloaluminophosphates, which are referred to as aluminophosphates with integrated metal (MeAPO and ELAPO), silicoaluminophosphates with integrated metal (MeAPSO and ELAPSO), silicoaluminophosphates (SAPO), gallogermanates and combinations thereof. An explanation of the structural relationships between SAPO, AIPO, MeAPO and MeAPSO can be found in a number of sources, including Stud. Surf. Catal. 37 13-27 (1987). The AIPO contain aluminum and phosphorus, while in the SAPO some of the phosphorus and / or both some of the phosphorus and aluminum are replaced by silicon. In addition to aluminum and phosphorus, the MeAPO contains various metals such as Li, B, Be, Mg, Ti, Mn, Fe, Co, An, Ga, Ge, and As, while the MeAPSO also contains silicon. The negative charge of the Me _a Al _b P _c Si _d O _e lattice is compensated for by cations, where Me is magnesium, manganese, cobalt, iron and / or zinc. Me _x APSO are described in U.S. Patent No. 4,793,984. SAPO type screen materials are described in U.S. Patent No. 4,440,871, MeAPO type catalysts are described in U.S. Patent Nos. 4,544,143 and 4,567,029, ELAPO catalysts are described in U.S. Patent No. 4,500 651 and ELAPSO catalysts are described in European patent application 159 624. Certain molecular sieves are e.g. For example, described in the following patents: MgAPSO or MAPSO - U.S. Patent No. 4,758,419, MnAPSO - U.S. Patent No. 4,686,092, CoAPSO - U.S. Patent No. 4,744,970, FeAPSO - U.S. Patent No. 4 683,217 and ZnAPSO - U.S. Patent No. 4,935,216. Certain silicoaluminophosphates that may be used include SAPO-11, SAPO-17, SAPO-34, SAPO-37, other certain screen materials include MeAPO-5, MeAPSO-5.

Another class of crystalline support materials that can be used is the group of mesoporous, crystalline materials, e.g. B. the materials MCM-41 and MCM-48. These mesoporous crystalline materials are described in U.S. Patent Nos. 5,098,684, 5,102,643 and 5,198,203. MCM-41, which in US 5,098,684 is characterized by a microstructure with a uniform hexagonal arrangement of pores with diameters of at least 1.3 nm, after calcining it shows an X-ray diffraction pattern with at least ad spacing of more than 1.8 nm and a hexagonal electron diffraction pattern, the can be indexed with ad ₁₀₀ value of more than 1.8 nm, which corresponds to the d distance of the peak in the X-ray diffraction diagram. The preferred catalytic form of this material is an aluminosilicate, although other metallosilicates can be used. MCM-48 has a cubic structure and can be made by a similar manufacturing process.

metal components

Two metal components are introduced into the molecular sieve support material to produce the catalyst compositions of the invention. A component is a rare earth element, such as lanthanum, or a mixture of rare earth elements, such as cerium and lanthanum. The other metal component can be considered the primary sulfur reduction component, although the manner in which it performs the sulfur reduction is not clear, as explained in the application, Serial No. 09/144607, whereupon for the description of sulfur reduction catalyst compositions containing vanadium and other metal components that are effective for this purpose. For the sake of simplicity, this component of the composition is referred to in this application as the primary component for reducing the sulfur content. For the metal (or metals) to be effective, it (s) should be present within the pore structure of the sieve component. Metallic zeolites and other molecular sieves can be made by: (1) adding metals to the sieve or a catalyst containing the sieve (s) subsequently, (2) synthesizing the sieve (s) containing the metal atom (s) in the Lattice structure contains (included) and (3) synthesis of the sieve (s) with voluminous metal ions enclosed in the zeolite pores. After the addition of the metal components, the washing should to remove unbound ionic species, and that Drying and calcining can be done. These methods are generally known per se. The subsequent addition of metal ions is preferred for the sake of simplicity and for economic reasons, it allows available sieve materials to be converted to be used for the additives according to the invention. A wide variety of methods for the subsequent addition of metals can be used to produce the catalyst according to the invention, e.g. B. an aqueous exchange of metal ions, a solid exchange with metal halide salt (s), the impregnation with a metal salt solution and the evaporation of metals. In any case, it is important to add the metal (s) so that the metal component gets into the pore structure of the sieve component.

If the metal is the primary component to reduce the sulfur content as exchanged cationic Species present in the pores of the sieve component has been found that the Hydrogen transfer activity of the metal component is reduced so far that the Hydrogen transfer reactions, the while of the cracking process take place with preferred metal components normally be kept at an acceptable low level. So the coke and light gas production increases somewhat during cracking, however, it remains within tolerable limits. Because the unsaturated lead can be used in any case as an alkylation feed and recirculated to the gasoline pool in this way, there is none significant loss of hydrocarbons in the gasoline sector, the is caused by the use of the additives according to the invention.

Due to concerns about excessive coke and hydrogen production in the cracking process should the metals for the introduction in the additives not a distinct one hydrogenation demonstrate. For this reason, precious metals such as platinum and palladium are which have strong hydrogenation / dehydrogenation functionality, not wanted. Base metals and combinations of base metals with strong hydrogenation functionality like nickel, molybdenum, Nickel tungsten, cobalt molybdenum and nickel-molybdenum, are not wanted for the same reason. The preferred base metals are metals of period 4, groups 5, 8, 9, 12, 13 (IUPAC classification, previously groups VB, VIII, IIB and IIIA) of the periodic table. Vanadium, zinc, iron, cobalt and gallium are effective, with vanadium represents the preferred metal component. It’s surprising that vanadium used in this way in an FCC catalyst composition can, since it is normally assumed that vanadium a very harmful one Influence on Has zeolite cracking catalysts and there have been many efforts undertook to develop vanadium suppressors. See e.g. B. Worm cup et al., Vanadium Poisoning of Cracking Catalysts: Mechanism of Poisoning and Design of Vanadium Tolerant Catalyst System, J. Catalysis 100, 130-137 (1986). The arrangement of vanadium immobilized within the pore structure of the vanadium sieve and prevents vanadic acid species to become who is in harmful Can connect way with the sieve component, and the invention Zeolite-based catalysts for reducing the sulfur content, containing vanadium as the metal component was repeated Cycles of reducing and oxidative conditions / steam treatment conditions subjected to for representative of the FCC cycle are, each with a different environment for the metal appearance the characteristic zeolite structure was preserved in every case.

Vanadium is particularly suitable for reducing the sulfur content in gasoline when carried on USY zeolite. The resulting structure of the V / USY catalyst to reduce the sulfur content is particularly interesting. Although other zeolites show a reduction in the sulfur content in gasoline after the addition of metals, they tend to convert gasoline to C ₃ and C ₄ gas. Although much of the converted C ₃ = and C ₄ = can be alkylated and re-mixed into the gasoline pool, the high C ₄ ^- wet gas yield can be a problem since many refineries are limited by the capacity of their wet gas compressor. The structure of the metal-containing USY is similar to that of today's FCC catalysts; this advantage would make it possible to adjust the V / USY zeolite content in a catalyst mixture to the desulfurization value to be achieved without any mandatory restrictions due to the FCC system. The catalyst made from vanadium on zeolite Y, the zeolite typically being USY, is therefore a particularly advantageous combination for reducing the sulfur content in gasoline in the FCC process. The USY, in which particularly good results were found, is a USY with a size of the grating unit in the range from 2.420 to 2.460 nm, preferably in the range from 2.420 to 2.450 nm, e.g. B. 2.435 to 2.450 nm (after treatment). Combinations of non-noble metals, such as vanadium / zinc, as the primary component for reducing the sulfur content can also be advantageous for the overall reduction in the sulfur content.

The amount of the primary sulfur reduction metal component in the sulfur reduction catalyst is typically 0.2 to 5 weight percent, typically 0.5 to 5 weight percent (as metal based on the weight of the sieve component) Quantities outside this range, e.g. B. 0.10 to 10 wt .-%, however, a certain effect can be found when removing sulfur. When the screen is incorporated into a matrix, the amount of primary metal component for reducing the sulfur content, in relation to the total weight of the catalyst composition, typically ranges from 0.1 to 5, more typically from 0.2 to 2, for practical purposes of this formulation % By weight of the total catalyst.

The second metal component of the catalyst composition to reduce the sulfur content comprises a metal or metals the rare earths found in the pore structure of the molecular sieve are present and are believed to be in the form of cations that have been exchanged for the interchangeable places that are present on the sieve component. The component of the rare Earth (RE) improves the stability of the catalyst in the presence of vanadium clearly. With a catalyst from RE + V / USY z. B. in comparison with a V / USY catalyst better cracking activity be achieved while a comparable reduction in the sulfur content in gasoline is achieved. Rare earth elements from the lanthanide series, from atomic number 57 to 71, such as lanthanum, cerium, dysprosium, praseodymium, Samarium, Europium, Gadolinium, Ytterbium and Lutetium, can be given commercial availability are used in this way, usually are lanthanum and Mixtures of cerium and lanthanum preferred. It was determined, that cer given the reduction in sulfur content and also the stability of the catalyst the most effective component of rare earths is, and its use is therefore preferred, although also with other rare elements Good results can be achieved as listed below.

The amount of rare metal Earth is typically 1 to 10% by weight of the catalyst composition, in most cases 2 to 5% by weight. Based on the weight of the sieve, the amount of Rare earth metals normally 2 to 20% by weight and in most cases 4 to 10% by weight of the sieve, depending on the sieve: matrix ratio. cerium can be present in amounts of 0.1 to 10% by weight, normally 0.25 to 5% by weight the catalyst composition, and based on the amount of sieve is usually 0.2 to 20% by weight, in most cases at 0.5 to 10% by weight.

The rare earth component can by exchanging on the sieve, either in the form of not in a matrix-bound crystal or the matrix-bound crystal Catalyst, appropriately introduced into the molecular sieve component. When the composition is made with the preferred zeolite USY formulated, a very effective way of getting started is Rare earth ions in the USY sieve (typically with one Size of the grid unit from 2.445 to 2.465 nm), followed by an additional one Calcine with steam so the size of the grid unit of the USY is reduced to a value typically in the range of 2.420 to 2.460 nm, after which the primary metal component is added can, if it does not already exist. The USY should because of the stability as also because of a satisfactory cracking activity Alkali metal (mainly Sodium); this is usually done by one during the Ultrastabilization process made ammonium exchange up to a desired one low sodium value of not more than 1% by weight, preferably not more than 0.5% by weight secured on the sieve.

The metal components are so in introduced the catalyst composition that is certain that it is in reach the inner pore structure of the sieve. The metals can directly in the crystal or in the catalyst embedded in a matrix introduced become. If the preferred zeolite USY is used as the sieve component this can be done appropriately as described above by the cracking catalyst USY, which is a component of the rare earths contains is calcined again so that a small size of the grid unit is ensured and then a metal, e.g. B. vanadium, by ion exchange or by impregnating under Conditions introduced that will allow a Cation exchange takes place so that the metal ion in the pore structure of the zeolite is immobilized. According to another embodiment can the primary Component for reducing the sulfur content and the component from a rare earth metal into the sieve component, e.g. B. Zeolite USY, or a crystal of ZSM-5, will be introduced after the necessary Calcination was made to organic materials from the Remove synthesis, after which the metal-containing component to the finished catalyst composition can be formulated by added the cracking and matrix components and the formulation spray dried which will produce the finished catalyst.

If the catalyst is integrated Catalyst system is formulated, it is both because of the simplicity the manufacture as well for preferred to maintain the controlled cracking properties, the active cracking component of the catalyst as a sieve component of the system for reduction the sulfur content, preferably in the form of a faujasite, e.g. B. Zeolite USY to use. However, it is possible to use another one when cracking active screen material, such as zeolite ZSM-5, in the integrated catalyst system introduce, and such systems can be advantageous if the properties of the second active screen material, z. B. the properties of ZSM-5, are desirable. In both cases an impregnation / exchange process be made with a regulated amount of metal so that the required Number of seats remains on the sieve to catalyze the cracking reactions, that of the active cracking component or any existing secondary Cracking components, e.g. B. ZSM-5, are desired.

use the catalyst composition to reduce the sulfur content

The most convenient way of use the sulfur reduction catalyst normally exists in a separate particle addition to the catalyst inventory. In its preferred form, with zeolite USY as sieve component, leads the Add the catalyst additive to the entire catalyst inventory Plant not to that total cracking evident due to the cracking activity of the USY zeolite decreases. The same applies if another sieve component active cracking material is used. If the composition in used in this way, it can be used in the form of pure sieve crystal be up to the exact size for use was granulated at the FCC (without matrix, but with added metal components). However, the metal-containing sieve is usually embedded in a matrix, to achieve adequate abrasion resistance of the particles and maintain a satisfactory swirl. conventional Matrix materials for Cracking catalysts, such as aluminum oxide or silicon dioxide-aluminum oxide, usually with a sound addition, are for suitable for this purpose. The amount of the matrix in relation to the Sieve is usually 20: 80 to 80: 20 by weight. It can be conventional Methods of connecting to a matrix are applied.

Use as a separate particulate catalyst additive allows that relationship the component for reducing the sulfur content and the cracking catalyst component according to the amount of sulfur in the feed and the desired Desulfurization level is optimized; if he used this way it is typically used in an amount of 1 to 50% by weight of the entire catalyst inventory used in the FCCU, in the most cases is the amount 5 to 25% by weight, e.g. B. 5 to 15 wt .-%. About 10% are the norm for most practical purposes. The addition can be carried out in a conventional manner, with catalyst replenishment, the regenerator, or by any other suitable method can be added. The addition remains long time for the removal of sulfur is active, although feeds with very high sulfur content in shorter Times of loss of activity for sulfur removal to lead can.

An alternative to using a separate particle addition is the use of the catalyst to reduce the sulfur content in the cracking catalyst introduced which is an integrated catalyst for FCC cracking / sulfur reduction is made in gasoline. When reducing the metal components the sulfur content can be used in combination with a sieve, which is different from the active cracking component, e.g. B. on ZSM-5 or zeolite beta if the main active component for cracking Is USY the amount of the component to reduce the sulfur content (sieve plus metals) typically up to 25% by weight of the total catalyst or less, which corresponds to the amounts in which they are considered separate Particle addition can be used as described above is.

In addition to the cracking catalyst and the sulfur removal additive, other catalytically active components may be present in the circulating inventory of the catalytic material. Examples of such other materials include the octane enhancing catalysts based on zeolite ZSM-5 are based, promoters for the combustion of CO, which are based on a supported noble metal such as platinum, additives for desulfurizing the exhaust gas, such as DESOX ^® (Magnesium-aluminum Spinel), vanadium scavengers and residues cracking additives, as already cited in Krishna, Sadeghbeigi, and Scherzer, Octane Enhancing Zeolitic FCC Catalysts, Marcel Dekker, New York, 1990, ISBN 0-8247-8399-9. These other components can be used in their conventional amounts.

The effect of the additives according to the invention is in reducing the sulfur content of the liquid cracking products, in particular the low-boiling and high-boiling gasoline fractions, although these reductions even in the higher boiling Distillate products, including light return oil and light and heavy fuel oil fractions, can be achieved, making this the hydrodesulfurization reactions more accessible because the more heat resistant Sulfur compounds are removed. The distillate fractions can then with less strict, more economical Conditions are desulfurized, creating distillate products generated that are suitable as a diesel or mixture component for heating oil are.

The cracking process itself takes place in the normal way with the addition of the catalyst for reduction the sulfur content, either in the form of an additive or as an integrated one Catalyst for catalytic cracking / reduction of sulfur content (individual Catalyst particles). The cracking conditions are more conventional Art.

The one by using this catalyst Sulfur removed during the cracking process is converted into an inorganic one Form converted and released as hydrogen sulfide, which in the FCCU product extraction section in the same way as the conventional hydrogen sulfide released during the cracking process to normal Way can be won. The higher exposure to hydrogen sulfide can additional Make requirements for the treatment of acid gas / water the significant reductions in the sulfur content in However, gasoline is unlikely to be considered restrictive.

If the preferred form of the above described catalyst can be used with the catalysts of the invention very significant reductions in the sulfur content in the cracked product be achieved in some cases up to 50%, based on the basic case with a conventional one Cracking catalyst, with constant conversion. A decrease in Sulfur content in gasoline of 25% can be according to the present Invention with many additives easy to achieve, as shown in the examples below. For medium Distillate fractions, including the LCO Group, can reductions of up to 25% can also be achieved as follows listed in the examples is, with a decrease in the value of the heat-resistant sulfur compounds, including with alkyl substituted benzothiophenes and dibenzothiophenes. The extent of Reduction in the sulfur content can be from the original content of the crack feed depend on organic sulfur, the most significant reductions in feeds with higher sulfur content be achieved. The metal content of the equilibrium catalyst in the plant can also influence the degree of desulfurization achieved, with a lower content of metals, especially the vanadium content, favors greater desulfurization on the equilibrium catalyst. The desulfurization is at a vanadium content of the e-catalyst (Equilibrium catalyst) of less than 1000 ppm very effective, although the catalysts of the invention themselves at a much higher one Vanadium levels remain effective. The reduction in the sulfur content can not only improve the quality of the product but also an increase the yield of the product in cases where the End point of the refinery cracked gasoline due to the sulfur content the high-boiling gasoline fraction is restricted; by providing an effective and economical one Way of reducing the sulfur content of a high-boiling gasoline fraction can the end point of the gasoline can be extended without referring to that expensive hydrotreating resorted to must become, with which the economy the refinery is advantageously influenced. Removing various Thiophene derivatives, the opposite removal by hydrotreating in less severe conditions resistant is also desirable if afterwards hydrotreatment is contemplated.

example 1

Production of the catalyst series 1

All samples in Catalyst Series 1 are made from a single source of spray dried material consisting of 50% USY, 21% silica sol and 29% clay. USY initially had a lattice unit size of 2.454 nm, an SiO ₂ / Al ₂ O ₃ molar ratio of 5.46 and a total surface area of 810 m ² / g.

A V / USY catalyst, Catalyst A, was prepared by suspending the above spray-dried catalyst at pH = 6 with NH ₄ OH, followed by filtering, exchange with ammonium sulfate, and washing with water. The catalyst was calcined at 704 ° C (1300 ° F) in the presence of steam for 2 hours and impregnated with vanadyl oxalate. Steam calcination reduced the size of the zeolite lattice unit and improved its stability in the presence of vanadium.

A V / USY catalyst, the catalyst B, was prepared in the same way as Catalyst A, except that this first suspend the catalyst at a pH between 3.2 and 3.5 was done.

Two RE + V / USY catalysts, Catalysts C and D, were prepared in the same manner as Catalyst B, except that after replacement with ammonium sulfate, the catalysts were subjected to exchange with solutions of a rare earth chloride, which resulted in the Catalyst 2 or 4% by weight of RE ₂ O _{3 were} added. In the rare earth solution used, part of the Ce ^{3+ had been} extracted or removed (hereinafter referred to as extracted), so it contained only a few Ce ions.

A Ce + V / USY catalyst, Catalyst E, was prepared in the same manner as Catalyst B, except that after replacement with ammonium sulfate, the catalyst was exchanged with a cerium chloride solution, whereby 5% cerium (as CeO ₂ ) were added.

To deactivate the catalyst in a FCC plant to simulate these catalysts 20 hours at 770 ° C (1420 ° F) deactivated in a fluidized bed steam treatment device, 50% Steam was used. The physical properties of the calcined and the steam deactivated catalysts are in Table 1 summarized.

Table 1 Physical properties of the catalysts V, RE + V and Ce + V USY / silicon dioxide sol (series 1)

Example 2

Production of the catalyst series 2

A V / USY catalyst, Catalyst F, was made with a USY zeolite with a silica / alumina ratio of 5.4 and a lattice unit size of 2.435 nm. A fluid catalyst was prepared by spray drying an aqueous suspension containing 50% by weight of USY crystals in a silica sol / clay matrix. The matrix contained 22% by weight silica sol and 28% by weight kaolin clay. The spray dried catalyst was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution and then dried. The USY catalyst was then impregnated with a solution of vanadium oxalate to a target value of 0.5% by weight V.

A RE + V / USY catalyst, Catalyst G, was made with a USY zeolite with a silica / alumina ratio of 5.5 and a lattice unit size of 2.454 nm. The USY was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution. The USY exchanged with NH ₄ ⁺ was then subjected to an exchange with rare earth cations (e.g., La ³⁺ , Ce ³⁺ , etc.) by exchanging with a solution of mixed rare earth chlorides. Most of the Ce ^{3+ was} extracted from the rare earth solution used, which contained very little Ce. The RE exchanged USY was also washed, dried and calcined at 760 ° C (1400 ° F) in a rotating calciner in the presence of steam. The calcining with steam reduced the size of the lattice unit of the zeolite to 2.44 nm (24.40 Å) and improved its stability in the presence of vanadium. A fluid catalyst was prepared by spray drying an aqueous suspension containing 50% by weight RE / USY crystals in a silica sol / clay matrix. The matrix contained 22% by weight silica sol and 28% by weight kaolin clay. The spray dried catalyst was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution, and was then dried and calcined at 540 ° C (1000 ° F) for 2 hours. After the calcination, the RE / USY catalyst was treated with a VOSO ₄ solution impregnated.

The catalyst H was prepared by methods similar to the catalyst G was used except that a solution of mixed ReCl ₃ for the exchange of USY mainly containing CeCl. ₃ The catalyst H was produced using a commercially available zeolite USY with a silicon dioxide / aluminum oxide ratio of 5.5 and a size of the lattice unit of 2.454 nm. The USY was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution. The USY exchanged with NH ₄ ⁺ was then exchanged with a solution of CeCl ₃ containing some lanthanum. The exchanged USY was also washed, dried, and calcined at 760 ° C (1400 ° F) in a rotating calciner in the presence of steam. by calcining with steam, the size of the lattice unit of the zeolite was reduced to 2.440 nm. A fluid catalyst was prepared by spray drying an aqueous suspension containing 50% by weight of the USY crystals containing rare earths in a silica sol / clay matrix. The matrix contained 22% by weight silica sol and 28% by weight kaolin clay. The spray dried catalyst was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution, and was then dried and calcined at 540 ° C (1000 ° F) for 2 hours. After the calcination, the catalyst was impregnated with a VOSO ₄ solution. The physical properties of the calcined catalysts are summarized in Table 2.

Table 2 Physical properties of the catalysts V / USY, RE + V / USY / silicon dioxide sol (series 2)

Example 3

Production of the catalyst series 3

A V / USY catalyst, the catalyst I was using a commercially available USY in the H form (crystal) with a ratio of Silicon dioxide / aluminum oxide of 5.4 and size of the lattice unit of 2.435 manufactured. A fluid catalyst was made by a aqueous suspension, the 40% by weight USY crystals, 25% by weight silicon dioxide, 5% by weight Contained alumina and 30 wt .-% kaolin clay, spray dried has been. The spray-dried Catalyst was calcined at 540 ° C (1000 ° F) for 3 hours. The resulting one H form of the USY catalyst was obtained by an impregnation process up to incipient wetness up to a target value of 0.4% by weight V impregnated with a vanadium oxalate solution. The impregnated V / USY catalyst was also used 3 hours at 540 ° C (1000 ° F) calcined in air. The finished catalyst contains 0.39% V.

A Ce + V / USY catalyst, Catalyst J, was made from the same spray dried H form of the USY intermediate catalyst as Catalyst I. The H-form of the USY catalyst was after an impregnation process until the beginning of moisture up to a target value of 1.5 wt .-% Ce-Be charge impregnated with a solution of Ce (NO ₃ ) ₃ . The resulting Ce / USY catalyst was calcined in air at 540 ° C (1000 ° F) for 3 hours, followed by steaming at 540 ° C (1000 ° F) for 3 hours. The catalyst was then impregnated with a vanadium oxalate solution to a target value of 0.4% by weight V using an impregnation process. The impregnated Ce + V / USY catalyst was also calcined in air at 540 ° C (1000 ° F) for 3 hours. The finished catalyst contains 1.4% Ce and 0.43% V

Table 3 Physical properties of catalysts V and Ce + V USY silica alumina clay (series 3)

Example 4

Production of the catalyst series 4

All samples in Catalyst Series 4 were made from a single source of spray dried material consisting of 50% USY, 21% silica sol and 29% clay. The underlying USY had a silica / alumina ratio of 5.4 and a lattice unit size of 2.435 nm. The spray-dried catalyst was suspended at pH = 6 with a solution of (NH ₄ ) ₂ SO ₄ and NH ₄ OH to give Na ⁺ , then washed with water and calcined in air at 650 ° C (1200 ° F) for 2 hours.

A V / USY catalyst, the catalyst K, was made with the above H form of the USY catalyst. The H form of the USY catalyst was made using an impregnation process up to the beginning of moisture up to a target value of 0.5% by weight V with a vanadium oxalate solution impregnated. The impregnated V / USY catalyst also became 2 hours at 650 ° C (1200%) calcined in air. The finished catalyst contains 0.53% V.

A Ce + V / USY catalyst, Catalyst L, was made from the above H form of the USY catalyst. The H-form of the USY catalyst was subjected to an exchange with a solution of CeCl ₃ up to a target value of 0.75% by weight Ce loading. The resulting Ce / USY catalyst was calcined in air and impregnated with a vanadium oxalate solution to a target value of 0.5% by weight V using an impregnation process to the onset of moisture. The impregnated Ce + V / USY catalyst was also calcined in air. The finished catalyst contains 0.72% Ce and 0.52% V.

A Ce + V / USY catalyst, Catalyst M, was made from the above-mentioned H form of the USY catalyst by exchanging it with a solution of CeCl ₃ up to a target value of 3% by weight of Ce loading has been. The resulting Ce / USY catalyst was calcined in air and impregnated with a vanadium oxalate solution to a target value of 0.5% by weight V using an impregnation process to the onset of moisture. The impregnated Ce + V / USY catalyst was also calcined in air. The finished catalyst contains 1.5% Ce and 0.53% V.

A Ce + V / USY catalyst, the catalyst N, was prepared from the above-mentioned H form of the USY catalyst by an impregnation process until the beginning of moisture with a solution of CeCl ₃ up to a target value of 1.5% by weight. -% Ce loading was made. The resulting Ce / USY catalyst was calcined in air and impregnated with a vanadium oxalate solution to a target value of 0.5% by weight V using an impregnation process to the onset of moisture. The impregnated Ce + V / USY catalyst was also calcined in air. The finished catalyst contains 1.5% Ce and 0.53% V.

To simulate the deactivation of a catalyst in an FCC system, the catalysts were deactivated for 20 hours at 770 ° C (1420 ° F) in a fluidized bed steam treatment device, 50% Steam and 50% gas were used. The gas flow was changed from air, N ₂ , propylene and an N ₂ mixture to N ₂ every 10 minutes and then the air cycle was used again to simulate the coking / regeneration cycle of an FCC (cyclic steam treatment) , Two sets of deactivated catalyst samples were generated: the cycle of deactivation with steam ended with the combustion of air (completion with oxidation) for one batch of the catalysts and the other ended with propylene (completion with reduction only). The coke content of the catalyst from the "termination with reduction" is less than 0.05% C. The physical properties of the calcined and of the steam-treated (termination with oxidation) catalysts are summarized in Table 4.

Table 4 Physical properties of the catalysts V and Ce + V USY / silicon dioxide sol (series 4)

Example 5

Production of the catalyst series 5

All samples in the catalyst series 5 were made from a single source of spray dried material, which consisted of 40% USY, 30% silica sol and 30% clay. The underlying H-form of USY had a ratio of Silicon dioxide / aluminum oxide of 5.4 and a lattice unit size of 2.435 nm. The spray dried Catalyst was calcined in air at 540 ° C (1000 ° F) for 3 hours.

A Ce / USY catalyst, catalyst O, was made with the above-mentioned H form of the USY catalyst. The H-form of the USY catalyst was impregnated with a solution of Ce (NO ₃ ) ₃ by means of an impregnation process to the onset of moisture up to a target of 1.5% by weight Ce loading. The resulting Ce / USY catalyst was calcined in air at 540 ° C (1000 ° F), followed by a 3 hour steam treatment at 540 ° C (1000 ° F).

A Ce + V / USY catalyst, the catalyst P, was made from catalyst 0. The Ce / USY catalyst was made after an impregnation process up to the beginning of moisture up to a target value of 0.5% by weight V with a vanadium oxalate solution impregnated. The impregnated Ce + V / USY catalyst was dried and in air at 540 ° C (1000 ° F) for 3 hours calcined. The finished catalyst contains 1.4% Ce and 0.49% V.

A Ce + V / USY catalyst, catalyst Q, was made from catalyst O by exchange with a solution of VOSO ₄ at pH ~ 3 to a target V loading of 0.5 wt%. The resulting Ce + V / USY catalyst was dried and calcined in air at 540 ° C (1000 ° F) for 3 hours. The finished catalyst contains 0.9% Ce and 0.47% V. The physical properties of the calcined catalysts are summarized in Table 5.

Table 5 Physical properties of the catalysts Ce and Ce + V USY / silicon dioxide clay (series 5)

Example 6

Preparation of the catalyst RE + V / USY / silica sol

A RE + V / USY catalyst, the catalyst R, was made with the NaY zeolite with a silica / alumina ratio of 5.5 and a lattice unit size of 2.465 nm. Zeolite Y was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution. The Y exchanged with NH ₄ ⁺ was then subjected to an exchange with rare earth cations (e.g. La ³⁺ , Ce ³⁺ , etc.) by exchanging with a solution of mixed rare earth chlorides from which the most of the Ce ³⁺ had been removed by extraction so that the solution contained very little cerium. The Y exchanged with RE was also washed, dried and calcined at 705 ° C (1300 ° F) in the presence of steam for 2 hours. Steam calcination reduced the size of the zeolite lattice unit and improved its stability in the presence of vanadium. A fluid catalyst was prepared by spray drying an aqueous suspension containing 50% by weight of RE-USY crystals in a silica target / clay matrix. The matrix contained 22% by weight silica sol and 28% by weight kaolin clay. The spray dried catalyst was replaced with NH ₄ ⁺ by changing only one ammonium sulfate solution and then dried and calcined at 540 ° C (1000 ° F) for 1 hour. After the calcination, the RE / USY catalyst was impregnated with a vanadium oxalate solution. The physical properties of the calcined catalyst are summarized in Table 6.

Table 6 Physical properties of the catalyst RE + V USY / silica sol

Example 7

Preparation of the catalyst Ce + V / USY / silica sol

A Ce + V / USY catalyst, catalyst S, was made with the NaUSY zeolite with a silica / alumina ratio of 5.5 and a lattice unit size of 2.454 nm. The USY was exchanged with NH ₄ ⁺ by exchanging with an ammonium sulfate solution. The USY exchanged with NH ₄ ⁺ was then exchanged with Ce ³⁺ cations by exchanging with a cerium chloride solution containing a small amount of other rare earth ions (e.g. La ³⁺ , Pr, Nd, Gd, etc .) contained. The CeY-exchanged USY was also washed, dried, and calcined in the presence of steam at 705 ° C (1300 ° F) for 2 hours. Steam calcination reduced the size of the USY lattice unit and improved its stability in the presence of vanadium. A fluid catalyst was prepared by spray drying an aqueous suspension containing 50% by weight Ce / USY crystals in a silica sol / clay matrix. The matrix contained 22% by weight silica sol and 28% by weight kaolin clay. The spray dried catalyst was replaced with NH ₄ ⁺ by exchanging with an ammonium sulfate solution, and then dried and calcined at 540 ° C (1000 ° F) for 1 hour. After the calcination, the Ce / USY catalyst was impregnated with a vanadium sulfate solution. The physical properties of the calcined catalyst are summarized in Table 7. Table 7 Physical properties of the Ce + V / USY / silica sol catalyst

Test procedure: evaluation the cracking performance

The catalysts of Example 1 through 7 were evaluated at the FCC, and the results are in the examples 8 to 15 listed. Mixed catalysts (one test compound plus equilibrium catalyst) were the cracking activity for gas oil and selectivity with the ASTM microactivity test (MAT test), reviewed a modified form of ASTM method D-3907, where a feed from vacuum gas oil (VGO) was used. Some of the additional catalysts were in of a circulating pilot riser system, using a vacuum gas oil or a the hydrotreated feed was used. The compositions of the three VGO feeds and one with the catalyst feed strict hydrotreating feed (cat feed hydroteated feed) (CFHT) used in these examples are shown in Table 8.

Table 8 Properties of the crack feeds

A range of cracking conversions was obtained by changing the catalyst / oil ratios in the reactions carried out at 527 ° C (980 ° F). The ranges of the separation limits for the cracking products were:
Gasoline: C ₅ ⁺ to 220 ° (125-30 ° F)
Light LCO: 220 to 310 ° C (430-590 ° F)
Heavy LCO: 310 to 370 ° C (590-700 ° F)
Light heating oil: (LFO) 220 to 370 ° C (430-700 ° F)
Heavy fuel oil (HFO) 370 ° C + (700 ° F +)

From each material balance, the gasoline product was analyzed by GC of Sulfur (AED) to determine the sulfur concentration in the gasoline. In order to reduce experimental errors in the sulfur concentration associated with fluctuations in the cut-off point in the distillation of gasoline, the sulfur species in the range from thiophene to C ₄ -thiophenes in synthetic crude oil (except benzothiophene and higher-boiling S-species) were quantified, and these The sum was defined as "cut gasoline S" or "gasoline fraction S" (hereinafter referred to as "cut gasoline S") (cut-gasoline S).

For the determination of the sulfur content of distillate fractions, the it boiled above the gasoline range (Examples 14 and 15) synthetic crude oil the atmospheric Subjected to distillation to separate the gasoline. Then the residual fraction subjected to another vacuum distillation, creating two LFO / LCO fractions (light LCO and heavy LCO) and HFO were generated. The sulfur species in the LCO sample were quantified with a GC (gas chromatograph), the was equipped with a "J&W 100 m DB-Petro" column and a "Sievers 355B" sulfur detector. The concentration of the sulfur species of each LCO was based on the percentage of sulfur species from gas chromatography and the total sulfur content calculated using an XPS method had been measured.

Example 8

Evaluation of the catalytic Fluid bed cracking of series 1 catalysts

The catalysts of Example 1 were 20 hours at 770 ° C (1420 ° F) deactivated in a fluidized bed steam treatment device, wherein 50% steam and 50% gas were used as described above in Example 4, which ended with combustion in air (completion with oxidation). 25% by weight of the steam-treated additional catalysts were using an equilibrium catalyst with a very low Metal value (120 ppm V and 60 ppm Ni) mixed from an FCC system.

The performance of these catalysts In catalytic cracking, VGO No. 1 was used as the cracking feed in the microactivity test evaluated. The performance of the catalysts are in Table 9 summarized, being the product selectivity up to a constant conversion, 65% by weight conversion of the feed only 220 ° C in one material (430 ° F) or below, was intrapolated.

Table 9 Performance of Series 1 Catalysts in Catalytic Cracking, VGO No. 1

The catalyst / oil ratios in Table 9 show that blends of deactivated V / USY and E-Cat. in higher catalyst / oil ratio than the base case with 100% equilibrium catalyst require one Achieve 65% conversion (catalyst / oil 3.3 vs. 3.0, i.e. 10% reduction of activity). This is due to the lower cracking activity of the V / USY catalysts in the relationship to the equilibrium catalyst. In comparison, the Addition of RE + V / USY catalysts does not affect the catalyst / oil ratio, to achieve 65% conversion. This catalyst / oil results show that the RE + V / USY catalysts are more stable and maintain their cracking activity better than V / USY catalysts.

Compared to the basic case with the equilibrium catalyst, the addition of the catalysts V / USY and RE + V / USY caused minor changes in the overall product structure achieved. There was little increase in hydrogen and coke yield. There were also minor changes in the yields of C ₄ ^- gas, gasoline, light return oil and heavy heating oil. The addition of the catalysts V / USY and RE + V / USY significantly changed the S concentration in gasoline. When 25% by weight of each catalyst A or B (V / USY reference catalysts) was mixed with the FCC equilibrium catalyst, a 39.0% and 40.8% reduction in the sulfur concentration in gasoline was achieved. When 25% by weight of the RF / USY catalyst (Catalysts C and D) was added to the equilibrium catalyst, the activities in reducing the sulfur content in gasoline were comparable to that of the reference catalysts (38-40%). The catalyst RE + V / USY, which mainly contains cerium as a rare earth metal (catalyst E), resulted in a 43.1% reduction in the S content in gasoline, which additionally reduced the S content in gasoline by 4% , ie a 10% improvement over the V / USY and mixed RE / USY catalysts. All catalysts have a comparable loading with vanadium (0.36-0.39%).

These results show that the addition of rare earth elements the cracking activity of a V / USY catalyst improved. The changes the yields of the cracked products are negligible. Among the rare earth ions Earthen Cer shows the unique ability that the Ce + V / USY catalyst not under the conditions of fluid catalytic cracking just a higher one cracking activity but also greater activity when reducing of the sulfur content in gasoline shows. The rare catalyst Earth RE / USY with no significant amounts of cerium in reducing the S content in gasoline has no further advantage over V / USY, whereas the presence of cerium in the V / USY catalysts or RE / USY (without essential values of cerium) the sulfur value in Gasoline further decreased.

Example 9

Comparison of the cracking activity of the catalysts series 2

Catalysts V and RE + V / USY of Example 2 (Series 2 catalysts, F, G, H catalysts) were deactivated with steam for different lengths of time at 770 ° C (1420 ° F) to compare the stability of the catalysts. The catalysts were steamed for 2.3, 5.3, 10, 20 and 30 hours in a fluid bed steam processor using 50% steam and 50% gas (cyclical steaming, completion with reduction as in the previous example 4 is described). The preservation of the surface of the deactivated catalysts is in 2 represented graphically.

The cracked activity for gas oil was tested on the steam deactivated catalysts using the ASTM microactivity test (ASTM, Method D-3907) with the vacuum gas oil No. 2 (more than 2.6 wt% S). With a second 30 second contact time and a reaction temperature of 545 ° C (980 ° F) with a constant catalyst / oil ratio of 4: 1, the conversion to 220 ° - (430 ° F-) in% by weight was measured , In 3 the conversions are plotted as a function of steam deactivation time.

The in 2 Preservation of the surface shown indicates that the catalysts V / USY and E + V / USY show comparable preservation of the surface under different conditions of hydrothermal deactivation, which suggests that all three catalysts have a comparable stability of the lattice structure. In the 3 However, the graphical representation of the conversion shown clearly reflects that RE + V / USY has a much better preservation of the cracking activity if the severity or hardness (hereinafter referred to as severity) of the hydrothermal deactivation increases. With hydrothermal deactivation, the improvement in cracking activity from version V / USY to version RE + V was 15% conversion. No clear differences were observed between the RE versions with different amounts of cerium. These results are consistent with those of Example 8, in which RE + V / USY achieved the conversion to be achieved with a lower catalyst / oil ratio than V / USY. These conversion results show that the RE + V / USY catalysts are more stable and retain their cracking activity better than the V / USY catalysts. The addition of rare earth ions to the USY followed by steam calcination to reduce the size of the zeolite lattice unit improved the stability of the catalyst in the presence of vanadium.

Example 10

Evaluation of the catalysts series 3 for fluid catalytic cracking

Catalysts V and Ce + V / USY of Example 3 (Catalysts I, J) were deactivated for 20 hours at 770 ° C (1420 ° F) in a fluid bed steam processor using 50% steam and 50% gas, such as is described in Example 4 above, and with the combustion of air was heard (conclusion with oxidation). 25% by weight of the steamed auxiliary catalysts were mixed with the FCC equilibrium catalyst with low metal content (120 ppm V and 60 ppm Ni). The mixed catalysts were then evaluated using the MAT test as described above, using VGO # 1 as the feed.

The performance of the catalysts Series 3 for feed VGO No. 1 are summarized in Table 10, where the product selectivity up to a constant conversion, 70% conversion of the feed into a material at 220 ° C- (430 ° F-), intrapolated has been.

Table 10 Performance of Series 3 Catalysts in Catalytic Cracking

Table 10 compares the FCC performances of the catalysts V / USY and Ce + V / USY / silica-alumina clay, which are each mixed with an equilibrium catalyst from the FCC (E-Cat.), After the cyclic deactivation only steam (completion with Oxidation). Compared to the basic case with the E-Cat. the addition of V / USY and Ce + V / USY catalyst changes the entire product structure achieved only slightly. The changes in the yield of C _4– gas, gasoline, light return oil and heavy heating oil are each small. Slight increases in hydrogen and coke yields were observed. Although the changes in product yields were small, the V / USY and Ce + V / USY catalysts significantly changed the concentration of S in gasoline. When 25% Catalyst I (V / USY Reference Catalyst) was mixed with an equilibrium catalyst from the FCC, a 29% reduction in sulfur concentration in gasoline was achieved. In comparison, the Ce + V / USY catalyst (catalyst 7) resulted in a 56% reduction in the S content in gasoline. The addition of Ce to the V / USY catalyst reduced the S content in gasoline by a further 27%, ie an improvement over the V / USY reference catalyst of 93%. Both catalysts have comparable vanadium loads (0.39% compared to 0.43% V). In view of the fact that Ce itself shows no activity in reducing the sulfur content in gasoline (see Example 11 below), these results are quite unexpected and clearly show the advantages of adding cerium.

Example 11

Evaluation of the catalysts series 4 after cyclical steam treatment in catalytic Fluid cracking

In this example, the performance of the catalysts V and Ce + V from example 4 are summarized. The Series 4 catalysts were deactivated by a cyclic steam treatment (completion with reduction) as described above in Example 4, then mixed in a weight ratio of 25:75 with the equilibrium catalyst from the FCC with low metal content (120 ppm V and 60 ppm Ni) and tested with the feed VGO No. 1. The results are summarized in Table 11. Table 11 Performance of the catalysts V and Ce + V / USY / silica sol in catalytic cracking

Table 11 compares the FCC performances of the additional catalysts V / USY and Ce + V / USY / silicon dioxide sol after the cyclic deactivation with steam (termination with reduction). Compared to the basic case with the E-Cat. the addition of the V / USY and Ce + V / USY catalysts caused very little changes in the overall product structure achieved. The yields of C _4– gas, gasoline, light return oil, heavy heating oil and coke were each changed by less than 0.2% by weight. The addition of the V / USY and Ce + V / USY catalysts changed the concentration of S in gasoline to different degrees. When 25% by weight of Catalyst K (V / USY Reference Catalyst) was mixed with the FCC equilibrium catalyst, a 5.2% reduction in sulfur concentration in gasoline was achieved. For comparison, the Ce + V / USY catalysts (catalysts M and N) resulted in a 17.4% reduction in the S content in gasoline. The addition of Ce to the V / USY catalyst reduced the S content in gasoline by a further 12.3%, ie an improvement over the V / USY reference catalyst of 237%.

Example 12

Evaluation of the catalysts series 4 after cyclical steam treatment in catalytic Fluid cracking

In this example are the benefits the V and Ce + V / USY catalysts of Example 4 after a cyclic Deactivation combined with steam. The catalysts of example 4 were made by cyclic steaming as in the previous example 4 described, deactivated (completion with oxidation) and were then in a weight ratio from 25:75 with an equilibrium catalyst from the FCC with low Mixed metal content (120 ppm V and 60 ppm Ni). The one with the feed Evaluation results obtained from VGO No. 1 are summarized in Table 12.

Table 12 Performance of the catalysts V and Ce + V / USY silica sol in catalytic cracking

Table 12 compares the FCC performances of the additional catalysts V / USY and Ce + V / USY / silicon dioxide sol after cyclical deactivation with steam (completion with oxidation). In comparison with the basic case with the E-Cat. the addition of the V / USY and Ce + V / USY catalyst caused minor changes in the overall product structure achieved. There was only a moderate increase in hydrogen and coke yields. Small changes in the yield of C ₄ gas, gasoline, light return oil and heavy heating oil were also observed. The addition of the V / USY and Ce + V / USY catalysts significantly changed the concentration of S in gasoline. If 25 wt .-% of the catalyst K (V / USY reference catalyst) with an equilibrium weight catalyst mixed by the FCC, the sulfur concentration in gasoline was reduced by 51.1%. In comparison, the Ce + V / USY catalysts (catalysts L and M) resulted in a 58.1% and 61.3% reduction in S content in gasoline, respectively. The addition of Ce to the V / USY catalyst reduced the S content in gasoline by a further 7.0 to 10.2%, ie an improvement over the V / USY reference catalyst of up to 20%.

The values of the product yields of the V / USY and Ce + V / USY catalysts show that the changes in yield from E-Cat. are based on the addition of vanadium to the USY catalyst. The product yields of the V / USY catalyst are that of the Ce + V / USY catalysts comparable, apart from the S value in petrol. Lay these results suggests that Ce the activity of the V / USY additional catalyst in reducing the sulfur content in gasoline with little impact on product yields improved.

Example 13

Evaluation of the catalysts series 5 in fluid catalytic cracking, investigation the sponsoring effects

In this example are the benefits of the catalysts Ce and Ce + V from Example 5 according to that described above Deactivation through cyclic steam treatment (completion with reduction) summarized. The deactivated catalysts were in a weight ratio of 25: 75 with an equilibrium catalyst from the FCC with low Mixed metal content (120 ppm V and 60 ppm Ni). The only VGO loading Results obtained in No. 1 are summarized in Table 13.

Table 13 Performance of the catalysts Ce and Ce + V / USY / silica clay in catalytic cracking

Table 13 compares the FCC performances of the additional catalysts Ce / USY and Ce + V / USY / silicon dioxide clay after the cyclic deactivation with steam (termination with reduction). Compared to the basic case with the E-Cat. the addition of the Ce / USY catalyst caused almost no change in overall product yields. The addition of the Ce + V / USY catalyst led to slight changes in the overall product structure achieved. There were only moderate increases in hydrogen and coke yield and slight changes in yields of C _4– gas, gasoline, light return oil and heavy fuel oil. The addition of the Ce / USY catalysts did not change the S concentration in gasoline. In contrast, surrendered the Ce + V / USY catalysts (catalysts P and Q according to the invention) reduced the S content in gasoline by 29.8% and 27.7%, respectively. These results show that cerium itself has no activity in reducing the sulfur content in gasoline. Cer appears to have a promotional effect on vanadium, which improves the activity of the V / USY additive catalyst in reducing the sulfur content in gasoline.

Example 14

The catalyst R was in a Circulating pilot riser system ("Davison Circulating Riser") in combination only a typical FCC equilibrium catalyst with the feed VGO No. 3 (Table 8) evaluated. Before the evaluation, the RE + V / USY catalyst deactivated with steam at 770 ° C (1420 ° F) for 20 hours, whereby 50% steam and 50% gas were used. 25% by weight of the steam treatment Additional catalyst underwent an equilibrium catalyst (530 ppm vanadium and 330 ppm Ni) mixed by an FCC system.

Table 14 shows the FCC performances summarized the catalysts, being the product selectivity until constant conversion, 75% by weight conversion of the feed into a material at 220 ° C- (430 ° F-), intrapolated has been.

Table 14 Performance of the catalyst RE + V / USY / silica sol in catalytic cracking

Compared to the base case, the addition of 25% by weight of the RE + V / USY catalyst only did the trick minor changes in the overall product structure achieved. There were negligible increases in H ₂ and coke yield. Slight changes in the yields of C _4– gas, gasoline, light return oil and heavy heating oil were also observed. The addition of the RE + V / USY catalyst significantly changed the sulfur concentration in gasoline; a reduction in the sulfur concentration in gasoline of 20% was achieved. In addition to the reduction in the sulfur content in gasoline, a significant reduction in the sulfur content in LCO has been observed, it is equivalent to a total reduction in sulfur content in LCO of 9%.

In Table 15 and 4 the sulfur species are shown in LCO. LCO contains wide ranges of sulfur species from benzothiophene and dibenzothiophene. The reductions in sulfur content were more pronounced with substituted benzothiophenes and substituted dibenzothiophenes, such as C ₃₊ benzothiophenes and C ₁ - to C ₄₊ dibenzothiophenes. The results are quite unexpected, as substituted dibenzothiophenes are bulkier and are expected to be more difficult to crack and desulphurize at the FCC.

Table 15 Sulfur speciation of the LCO from feed VGO No. 3

Example 15

Evaluation of the catalysts Ce + V / USY / silicon dioxide sol in fluidized-bed catalytic cracking The Ce + V / USY catalyst from Example 7 (catalyst S) was evaluated for 40 days in combination with a typical FCC catalyst in circulating fluidized-bed cracking, which was strict Hydrotreated FCC feed from Table 8 (CFHT feed) was used. The FCC equilibrium catalyst of the base case has very low metal values (200 ppm V and 130 ppm Ni). During the first 15 days a mixture with 50/50 of fresh FCC catalyst and the Ce + V / USY catalyst from Example 7 was added to the FCC regenerator only 1.4% of the catalyst inventory per day. From the 15th to the 40th day, a mixture with 85/15 of fresh FCC catalyst and the Ce + V / USY catalyst with 1.4% of the catalyst inventory per day was added to the FCC regenerator. The temperature of the regenerator was maintained at approximately 705 ° C (1300 ° F) during the evaluation. Two samples of the equilibrium catalyst (E-Cat.) Were collected: the first was taken before the addition of Ce + V / USY (base case) men and the second on the 40th day. Based on the analysis of Ce and V, the loading of the Ce + V / USY catalyst is estimated at 12%.

Table 16 shows the FCC performances summarized the catalysts, being the product selectivity to constant conversion, 70% by weight conversion of the feed into a material at 220 ° C- (430 ° F-), intrapolated has been.

Table 16 Performance of the Ce + V / USY / silica sol catalyst in catalytic cracking

Compared to the basic case with the E-Cat. the addition of the Ce + V / USY catalyst only caused minor changes in the overall product structure achieved. There were negligible increases in H ₂ and coke yields. Small changes in the yield of C _4– gas, gasoline, light return oil, and heavy heating oil were also observed. The addition of the Ce + V / USY catalyst significantly changed the concentration of S in gasoline. When 12 wt% Ce + V / USY catalyst was mixed in the FCC equilibrium catalyst, a 21% reduction in sulfur concentration in gasoline was achieved. In addition to the reduction in the sulfur content in gasoline, significant reductions in the sulfur content in LCO and HFO have been observed.

The sulfur species in the light LCO fraction were analyzed by GC of sulfur. The concentration of each organosulfur class was as in Table 17 and 5 shown for light LCO.

Table 17 Sulfur speciation of the light LCO from a CFHT feed

As in 5 shown, light LCO contains mainly benzothiophene sulfur species. The reductions in sulfur content, which are equivalent to a total decrease in sulfur content in light LCO of 27%, were more pronounced with substituted benzothiophenes such as C ₁ - to C ₃₊ benzothiophenes. The results are quite unexpected, as substituted benzothiophenes are more voluminous and are expected to be more difficult to crack and desulphurize at the FCC.

The sulfur species in the heavy LCO fraction were as in Table 18 and 6 shown. The heavy LCO mainly contains dibenzothiophene sulfur species. The reductions in sulfur (14% overall for heavy LCO) were more pronounced for substituted dibenzothiophenes, such as C ₁ - to C ₄₊ -dibenzothiophenes. The results are quite unexpected, as substituted dibenzothiophenes are more voluminous and are expected to be more difficult to crack and desulfurize at the FCC.

Table 18 Sulfur speciation of the heavy LCO from a CFHT feed

The catalyst for reduction of the sulfur content is in the reduction of benzothiophene and Dibenzothiophene sulfur species as well as thiophene sulfur species active. The reduction in the sulfur content mainly takes place at substituted benzothiophenes and substituted dibenzothiophenes instead of. These results suggest that the C-S bonds in the alkyl-substituted thiophenes more reactive and cracking better accessible are.

The rapid reduction in the sulfur content with substituted thiophenes, substituted benzothiophenes and substituted dibenzothiophenes was quite unexpected and improved the effectiveness the subsequent LCO hydrodesulphurisation process. With the LCO hydrodesulfurization process it is generally known that a Methyl and / or alkyl substitution of benzothiophene and dibenzothiophene the desulfurization reactivity of organic sulfur compounds significantly reduced and that "hard sulfur" or "heat-resistant sulfur" is formed. In this Invention produces LCO which contains a smaller amount of substituted benzo and contains dibenzothiophenes, with a diesel fuel using the hydrodesulfurization process lower sulfur content than the comparable LCO with a usual FCC catalyst was made.

Claims (35)

Process for reducing sulfur content a catalytically cracked petroleum fraction, characterized by the catalytic cracking of an oil feed fraction, which contains organosulfur compounds at elevated temperature in the presence a cracking catalyst and a reduction catalyst the sulfur content in the product comprising a porous molecular sieve which (i) a first metal component located inside the pore structure of the molecular sieve and a metal in an oxidation state of greater than zero comprises and (ii) has a second metal component located inside the pore structure of the molecular sieve and at least one Includes rare earth metal, which makes liquid Cracked products with a lower sulfur content are produced. A method according to claim 1, characterized in that the catalyst for reducing the sulfur content in the product is a zeolite with large pores or medium pore size as molecular sieve components te and as the first metal components comprises vanadium, zinc, iron, cobalt and / or gallium. A method according to claim 1 or 2, characterized in that that the Zeolite with large Pores a faujasite zeolite includes. Method according to one of the preceding claims, characterized characterized that the comprises first metal component vanadium. A method according to claim 2, characterized in that the second metal component lanthanum alone or in combination with cerium includes. A method according to claim 2, characterized in that the includes second metal component cerium. Method according to one of the preceding claims, characterized characterized that the second metal component in an amount of 1 to 10 wt .-% of the catalyst composition is available. Method according to one of the preceding claims, characterized characterized in that the Catalyst to reduce the sulfur content in the product Zeolite USY with the size of the lattice unit (UCS) from 2.420 to 2.460 nm and a ratio of Silicon dioxide / aluminum oxide of at least 5.0 as a molecular sieve component and zinc and / or vanadium in an oxidation state as the first metal component of greater than zero and as the second metal component cerium alone or in combination with Lanthanum covers. Method according to one of the preceding claims, characterized characterized in that the Catalyst to reduce the sulfur content a separate, particulate Additional catalyst is. Method according to one of the preceding claims, characterized characterized that the liquid cracking products with a lower sulfur content a gasoline fraction, a return oil fraction and a heating oil fraction include, the return oil and the heating oil boil above the gasoline fraction. Catalytic fluidized bed cracking process, thereby characterized that a high-boiling hydrocarbon feed, the organosulfur compounds contains through contact with a circulating inventory of a catalyst for the fluid catalytic cracking of particles with a size in the range from 20 to 100 μm consists in a cracking process with cyclically recirculating catalyst is catalytically cracked into low-boiling products; by doing: (I) the feed is catalytically cracked in a catalytic cracking zone which works in catalytic cracking conditions by the Feed with a source of a regenerated cracking catalyst is brought into contact, thereby producing a drainage of the cracking zone, which comprises cracked products and spent catalyst which Contains coke and separable hydrocarbons, (ii) the mixed Drain discharged and into a vapor phase rich in crack product and one rich in solids Phase comprising the spent catalyst is separated, (Iii) the vapor phase is released as a product and the vapor is fractionated becomes what makes liquid Crack products are produced that include gasoline, (Iv) the solid phase of the spent catalyst separated to the trapped hydrocarbons from the catalyst to remove, (v) the separated catalyst from the stripper to a regenerator for the catalyst is directed (vi) the separated catalyst is regenerated by contact with an oxygen-containing gas, producing regenerated catalyst, and (vii) the Regenerated catalyst is recirculated to the cracking zone, so that it with additional amounts of high-boiling hydrocarbon feed in Contact comes the sulfur product of the liquid cracking products is reduced by catalytic cracking in the presence of a Catalyst for reducing the sulfur content in the product is carried out, which is a porous Molecular sieve with (i) a first component located inside the pore structure of the molecular sieve and a metal in an oxidation state greater than zero comprises and (ii) a second metal component located inside the Pore structure of the molecular sieve is located and at least one element which includes rare earths, includes. A method according to claim 11, characterized in that the Crack catalyst a faujasite zeolite embedded in a matrix includes. Method according to one of claims 11 or 12, characterized in that the catalyst for Reducing the sulfur content in the product comprises a zeolite with only large pores or medium pore size as the molecular sieve component, vanadium as the first metal component and cerium alone or in combination with at least one other rare earth metal as the second metal component. Method according to one of claims 11 to 13, characterized in that that the Large pore zeolite of the catalyst to reduce the sulfur content in the product comprises a faujasite zeolite. Method according to one of claims 11 to 14, characterized in that that the comprises first metal component vanadium. Method according to one of claims 1 to 15, characterized in that that the second metal component lanthanum alone or in combination with cerium includes. A method according to claim 11, characterized in that the includes second metal component cerium. Method according to one of claims 11 to 17, characterized in that that the second metal component in an amount of 1 to 10 wt .-% of the catalyst composition is available. Method according to one of claims 11 to 18, characterized in that that the liquid Cracked products are a gasoline fraction with a lower sulfur content and a return oil fraction with lower sulfur content, which boils above the gasoline fraction, include. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking, the sulfur content of a catalytically cracked gasoline fraction to reduce in the catalytic cracking process, characterized in that that she fluidizable particles with a size in the range from 20 to 100 μm from (i) a porous Molecular sieve component (ii) of a first metal component, the comprises a metal in an oxidation state greater than zero, the inside the pore structure of the porous molecular sieve component is arranged, and (iii) a second metal component which a Includes rare earth metal, those inside the pore structure of the porous molecular sieve component is arranged includes. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to claim 20, characterized in that the porous molecular sieve component a porous Screen component for includes hydrocarbon cracking. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to claim 20 or 21, characterized in that the porous molecular sieve component a USY zeolite with the size of the lattice unit from 2.420 to 2.460 nm and a quantitative ratio of silicon dioxide / aluminum oxide of at least 5.0. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to one of the claims 20 to 22, characterized in that the porous molecular sieve component a USY zeolite with the size of the lattice unit from 2.420 to 2.435 nm and a quantitative ratio of silicon dioxide / aluminum oxide of at least 5.0. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to one of the claims 20 to 23, characterized in that it is the first metal component 0.1 to 5% by weight of vanadium, based on the weight of the zeolite, contains the first metal component. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to one of the claims 20 to 24, characterized in that they act as a second metal component a combination of cerium and at least one other metal Includes rare earths. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to claim 20, characterized in that it cerium as a second metal component includes. Catalyst composition for reducing the sulfur content in a product from the catalytic Fluid bed cracking according to one of Claims 20 to 26, characterized in that the metal components are introduced into the zeolite as exchanged canonical species within the zeolite pores. Catalyst for reducing the sulfur content in the product of fluidized catalytic cracking according to one of the Expectations 20 to 27, characterized in that it has a matrix component as a catalyst additive for fluid bed cracking is formulated. Catalyst for reducing the sulfur content in a fluid catalytic cracking product according to claim 20, characterized in that he as an integrated catalyst for Fluid catalytic cracking / reduction of sulfur content is formulated in the product to be a high-boiling hydrocarbon feed to crack, causing liquid Cracking products are produced, including gasoline, and the sulfur content of the catalytically cracked gasoline fraction while of the catalytic cracking process to reduce the swirlable Particles with a size in the range from 20 to 100 μm one Hydrocarbon cracking component comprising includes a zeolite molecular sieve located inside the pore structure of the zeolite arranged (i) a first metal component, the vanadium, Comprises zinc, iron, cobalt and / or gallium and (ii) a second metal component, which comprises at least one rare earth metal. Integrated catalytic fluidized bed cracking / reduction catalyst the sulfur content in the product according to claim 29, characterized in that that he 0.1 to 5% by weight of vanadium as the first metal component, based on the weight of the zeolite. Integrated catalytic fluidized bed cracking / reduction catalyst the sulfur content in the product according to one of claims 29 or 30, characterized in that the second metal component a combination of cerium and at least another rare earth metal in an amount of 1 to 5 % By weight of the catalyst. Integrated catalytic fluidized bed cracking / reduction catalyst the sulfur content in the product according to any one of claims 29 to 30, characterized in that the second metal component a combination of cerium in an amount from 1 to 5% by weight of the catalyst. Integrated catalytic fluidized bed cracking / reduction catalyst the sulfur content in the product according to any one of claims 29 to 32, characterized in that the Zeolite molecular sieve a zeolite USY with the size of the lattice unit from 2.420 to 2.460 nm and a quantitative ratio of silicon dioxide / aluminum oxide of at least 5.0. Catalyst composition for reducing the Sulfur content in a product from fluid catalytic cracking according to one of the claims 29 to 30, characterized in that the porous molecular sieve component a USY zeolite with the size of the lattice unit from 2.420 to 2.435 nm and a quantitative ratio of silicon dioxide / aluminum oxide of at least 5.0. Catalyst for reducing the sulfur content in a fluid catalytic cracking product according to claim 29, characterized in that he as an integrated catalyst for Fluid bed cracking / reduction of the sulfur content with a Matrix component and a faujasite zeolite as a crack component is formulated.