SE523251C2 - Process for reducing the sulfur content in a liquid catalytic cracked petroleum fraction, method for catalytic cracking in the floating bed and fluidizable catalyst composition - Google Patents

Abstract

The sulphur content of the liquid products from a catalytic cracking process is reduced by the use of a sulphur reduction catalyst comprising a porous molecular sieve which contains, with the interior pore structure of the sieve, (i) a first metal componet which has an oxidation state grater than zero, and (ii) a second metal component which comprises at least one rare earth metal. The molecular sieve is preferably a large-bore size zeolite such as a faujasite, for example, USY. The primary sulphur reduction component is normally a metal of Period 4 of the Periodic Table, preferably vanadium. The preferred rare earth metal is cerium, although lanthanum may be used alone or in combination with cerium. The sulphur reduction catalyst may be used in the form of separate particle additive or as part of a single combined/integrated cracking/sulphur catalyst.

Description

The catalyst adsorbed hydrocarbons, and a regeneration step for burning coke from the catalyst. The regenerated catalyst is then reused in the cracking step.

Raw materials for catalytic cracking usually contain sulfur in the form of organic sulfur compounds, such as mercaptans, sulphides and thiophenes. The products of the cracking process similarly tend to contain sulfur impurities, even if half of the sulfur is converted to hydrogen sulphide during the cracking process, mainly by catalytic decomposition of non-thiophene sulfur compounds. The distribution of sulfur in the cracking products depends on a number of factors including the raw material, the type of catalyst, the additives present, the turnover and other operating conditions, but in any case a certain part of the sulfur tends to enter the light or heavy petrol fractions and transferred to the product warehouse. Due to the stricter environmental regulations for petroleum products, for example according to the Reformulated Gasoline (RFG) regulations, the sulfur content in the products has generally decreased to take into account emissions of sulfur oxides and other sulfur compounds into the air after combustion procedures. Reduction of sulfur in petrol is not only critical for SOX emissions, but also for sulfur poisoning of catalytic converters in cars. The poisoning of catalytic converters often causes other emission problems, such as NOX.

Environmental considerations have to a greater extent focused on the sulfur content of motor petrol in view of its superior position as motor fuel for passenger cars in the USA. However, these considerations have also extended to high boiling distillate fractions including light cycle oil (LCO) and fuel oil fractions (LFO) (HFOH lytic cracking process). reduction of the levels of sulfur in the product fractions, and in general this has been found to be effective.However, the high-boiling fractions are not as susceptible to desulphurisation as the low-boiling fractions due to the increasingly resistant "The strong nature of the sulfur compounds, in particular substituted benzothiophenes with increasing boiling point. hard sulfur ”or“ resistant sulfur. ”An example of LCO sulfur GC shown in Fig. 1 with GC sulfur specification. In a Review of Girgis and Gates, Ind. Eng. Chem., 30, 1991, 2021-2058, it is reported that substitution of a methyl group at position 4 or positions 4 and 6 reduces the desulfurization activity by an order of magnitude. Houalla et al reported activity decreases of 1-10 orders of magnitude (M. Houalla et al, Journal of Catalysis, 61, 1980, 523-527). Lamure-Meille et al suggested 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). When using the high-boiling catalytic cracking products as raw material flows for hydrogen desulphurisation processes, the motivation to reduce the presence of the more resistant organic sulfur compounds in these cracking fractions becomes increasingly obvious.

One approach has involved the removal of sulfur from the FCC feed stream by hydrotreating before cracking begins. Although this approach is very efficient, it tends to be expensive in terms of the cost of capital for the equipment, as well as operationally, as the hydrogen consumption is high. Another approach has involved the removal of sulfur from the cracked products by hydrogen treatment. Although this approach is also effective, it has the disadvantage that valuable octane product can be lost when the high octanol olefins are saturated. From an economic point of view, it would be desirable to achieve sulfur removal in the actual cracking process, since this would effectively desulfurize the main component of the gasoline blend storage without further treatment. Various catalytic materials have been developed for the removal of sulfur during the FCC process cycle, but so far most developments have focused on the removal of sulfur from the regenerator flue gases. In an early process developed by Chevron, alumina compounds were used as additives to the set of cracking catalyst for adsorption of sulfur oxides in the FCC regenerator, releasing the adsorbed sulfur compounds introduced into the process stream as hydrogen sulfide at the cracking portion of the cycle. product recovery section, where they were removed (see Krishna et al, Additives Improve FCC Process, Hydrocarbon pages 59-66). The sulfur removal product was not significantly affected, if at all.

An alternative technique for removing sulfur oxides from the regenerator is based on the use of magnesium-aluminum spinel compounds as additives to the circulating catalyst set in the FCC.

Under the designation DESOXW, in this process, the technology has achieved a remark used for the additives of considerable commercial success. Examples of patents for this type of sulfur removal additive include U.S. Pat. Nos. 4,957,892, 4,957,718. sulfur levels to some extent.

A catalyst additive for reducing the sulfur content of liquid cracking products has been proposed by Wormsbecher and Kim in U.S. Patents 5,376,608 and 5,525,210, i.e. by using a cracking catalyst additive of alumina supported Lewis acid to produce reduced sulfur gasoline. but this system has not had any significant commercial success. The need for an effective additive to reduce the sulfur content of liquid products from catalytic cracking has therefore remained.

In Swedish patent application No. 9903054-6, corresponding to U.S. patent application 09/144,607, August 1998 (Mobile IP Case 10061), lytic materials for use in the catalytic filing filed on August 31, we have described the cataract cracking process with the ability to reduce the sulfur content of liquid products in the cracking process. These sulfur reduction catalysts include, in addition to a porous molecular sieve component, a metal in an oxidation state in excess of zero within the pore structure of the sieve. The molecular sieve is in most cases a zeolite, and it may be a zeolite having properties similar to those of large pore zeolites, such as beta zeolite or USY zeolite, or with intermediate pore size zeolites, such as ZSM-5. such as MeAPO-5, MeAPSO-5, such as MCM-41, Metals such as vanadium, non-zeolitic molecular sieves, as well as mesoporous crystalline materials, can be used as a sieving component in the catalyst. Zinc, iron, cobalt and gallium were found to be effective in reducing sulfur in gasoline, with vanadium being the preferred metal. When used as a separate particulate catalyst additive, these materials are used in combination with the active catalytic cracking catalyst (usually a faujasite, especially USY zeolite) hydrocarbon feed streams in the (Fcc) sulfur catalytic cracking unit. Since the sieving component in sulfur-reducing, such as Y-zeolite, for processing suspended beds for the production of low catalyst products can itself be an active cracking catalyst, for example USY zeolite, the sulfur-reducing catalyst in the form of an integrated tor, it is also possible to use systems for cracking / sulfur reduction, for example including USY as the active cracking component and the screen component for the sulfur reduction system together with an added eg matrix material such as silica, clay and metal, vanadium, which provides the sulfur reduction functionality.

Another consideration in the production of FCC catalysts has been catalyst stability, especially hydrothermal stability, since the cracking catalysts during use are exposed to repeated reduction cycles (in the cracking step), followed by evaporation with water vapor and then oxidative regeneration which gives large amounts of combustion meadow of coke, a carbon-rich hydrocarbon, which is deposited on the catalyst particles during the cracking part of the cycle. It has been shown early in the development of zeolitic cracking catalysts that not only for optimal cracking and low sodium content, activity, but also for stability, rare earth metals such as cerium and lanthanum gave higher hydrothermal stability (see e.g. Fluid Catalytic Cracking with Zeolite Catalysts, Venuto et al, 1979, ISBN O-8247-6870-1).

We have now developed catalytic materials for use in the catalytic cracking process, which materials have the ability to improve the reduction of the sulfur content of the liquid products from the cracking process, including especially gasoline and the intermediate cracking distillate fractions. . The present sulfur reduction catalyst is similar to those described in U.S. Patent Application No. 09/144,607 in that a metal component in an oxidation state in excess of zero is present in the pore structure of a molecular sieve component in the catalyst composition, preferably vanadium. In the present case, however, the composition comprises one or more rare earth metals, preferably cerium. We have found that the presence of the rare earth metal component increases the stability of the catalyst compared to catalysts containing only vanadium or any other metal component, and that in some favorable cases, especially with cerium as a rare earth metal, the sulfur reduction activity is also increased due to the presence of the 20 25 30 35: S23 251 7 rare earth metals. This is surprising, since the cations of the rare earth metals themselves have no sulfur reduction activity.

In one aspect, the present invention relates to a process for reducing the sulfur content of a liquid catalytically cracked petroleum fraction, which process additionally has the features stated in the characterizing part of claim 1.

In other aspects, the present invention further relates to a process for catalytic cracking in a suspended bed, to a fluidizable catalyst composition and to an integrated fluidizable catalyst composition, which aspects in addition have the features set out in the characterizing part of claims 10, 18 and 27. - dragen.

Preferred embodiments of the various aspects are set forth in the dependent claims.

The present sulfur reduction catalysts can be used in the form of a catalyst additive in combination with the active cracking catalyst in the cracking unit, i.e. in combination with the conventional main component of the circulating set of cracking catalyst, which is usually a matrix-bound zeolite-containing catalyst. , usually Y zeolite. Alternatively, it can be used in the form of an integrated system of cracking / product sulfur reduction catalyst.

According to the present invention, the catalyst composition for removing sulfur comprises a porous molecular sieve containing (i) a metal in an oxidation state exceeding zero within the pore structure of the sieve and (ii) a component in the form of a rare earth metal.

The molecular sieve is in most cases a zeolite, and it may be a zeolite with properties corresponding to the large pore zeolites, such as beta zeolite or USY zeolite, or with intermediate pore size zeolites, such as ZSM-5.

Non-zeolitic molecular sieves, such as man; 12.1; 13:25 »e: '= -_ L2a: .ï <2;: .. * 10 15 20 25 30 35 523 251 8 MeAPO-5, MeAPSO-5, as well as mesoporous crystalline material, such as MCM-41, can used as a screening component for cobalt and gallium are effective. About the selected screen material catalyst. Metals such as vanadium, zinc, iron, have sufficient cracking activity, it can be used as an active catalyst component for catalytic cracking (usually a faujasite, such as Y zeolite) or, alternatively, it can be used in addition to the active cracking component, whether have any cracking activity yourself or not.

The present compositions are useful for processing hydrocarbon feedstocks in catalytic (FCC) and other low sulfur liquid products, such as fluidized bed cracking to produce gasoline light oil from the cycle therefor, which can be used as a low sulfur diesel blend component. or as fuel oil. In addition to achieving a very significant reduction in the sulfur content of the cracked gasoline fraction, the present sulfur reduction catalyst material enables the reduction of the sulfur content of light oil from the cycle thereof and fuel oil products (light fuel oil, heavy fuel oil). The sulfur reduction in LCO is achieved with predominantly substituted benzothiophenes and substituted dibenzothiophenes, the removal of these more resistant substances improving the efficiency of sulfur reduction in the subsequent LCO hydrogen desulphurisation process. The reduction of sulfur in HFO can make it possible to upgrade “coker” products from oil to premium coke.

Although the mechanism by which the metal-containing zeolite catalyst compositions remove sulfur components commonly present in cracked hydrocarbon products has not been precisely investigated, it involves the conversion of organic sulfur compounds in the feed stream to inorganic sulfur, so the process is a real catalytic process. In this process, it is believed that a zeolite or other molecular sieve provides shape selectivity with varying pore sizes, and the metal sites in the zeolite provide adsorption sites for the sulfur substances.

The drawings show curves of the performance of the present sulfur reduction compositions, as described below.

The FCC Process The present sulfur removal catalysts are used as a catalytic component in the circulating set of catalysts in the catalytic cracking process, which today is almost exclusively the process for catalytic cracking in the suspended bed (FCC). For convenience, the invention will be described with reference to the FCC process, although the present additives could be used in the older moving bed (TCC) cracking process with appropriate particle size adjustments to suit the process requirements. In addition to the addition of the present additive to the catalyst set and some possible changes in the product recovery section, which are discussed below, the procedure for operating the process will remain unchanged. Thus, conventional FCC catalysts can be used, such as zeolite-based catalysts with a faujasite cracking component, as described in the comprehensive review of Venuto and Habib in Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247- 6870-l, or, such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Publ. 1995, ISBN O-88415-290-1.

In summary, the catalytic cracking process, as in several other sources, is carried out in the suspended bed, in which the heavy hydrocarbon feed stream containing the organosulfur compounds is cracked into lighter products, by contacting the feed stream in a cyclic cracking process with a catalyst. circulating, fluidizable, catalytic cracking catalyst set consisting of particles ranging in size from 20 to 100 10 15 20 25 30 35 523 251 10 μm. The essential steps in the cyclic process are that: (i) (ii) (iii) the stream is catalytically cracked in a catalytic cracking zone, usually a riser with cracking tube, during operation under catalytic cracking conditions by contact between the raw material flow and a source of hot, regenerative ad cracking catalyst for producing an effluent including cracked products and spent catalyst containing coke and stripping hydrocarbons; the effluent is discharged and separated, usually in one or more cyclones, into a vapor phase rich in cracked products and a phase rich in solids and comprising the spent catalyst; The vapor phase is removed as a product and fractionated in the FCC main column and its associated side columns to produce liquid cracking products including gasoline, the spent catalyst is subjected to evaporation, usually with water vapor, to remove absorbed hydrocarbons from the catalyst, after which it the stripped catalyst is oxidatively regenerated to produce hot, regenerated catalyst, which is then recycled to the cracking zone to crack additional quantities of feedstock.

The raw material flow to the FCC process is often a high-boiling raw material stream of mineral oil origin, usually with an initial boiling point of at least 290 ° C (550 ° F), and in most cases above 315 ° C (600 ° F). The majority of refining limits for FCC feedstocks are at least 345 ° C (650 ° F). The upper limit point varies, depending on the exact nature of the raw material flow or on the operating conditions in the refinery.

Raw material flows can be either distillate, usually with 10 15 20 25 30 35 iszs 251? ll an upper limit of 550 ° C (1020 ° F) or higher, eg 590 ° C (1095 ° F) or 620 ° C (1150 ° F), or alternatively residual material (non-distillable) may be included in the raw material flow and can even make up all or a larger part of the flow of raw materials. Distillable raw material flows include untreated raw material flows, such as gas oils, such as heavy or light atmospheric gas oil, heavy or light vacuum gas oil, as well as cracked raw material flows, such as light and heavy “coker” gas oil. Hydrotreated raw material streams can be used, eg hydrotreated gas oils, especially hydrotreated heavy gas oil, but since the present catalysts are capable of achieving a significant reduction in the sulfur content, it may be possible to dispense with initial hydrotreating when its purpose is to reduce the sulfur content. although improvements in cracking ability are still achieved.

In the process of the present invention, the sulfur content of the gasoline portion of the liquid cracking products is effectively reduced to lower and more acceptable levels by performing the catalytic cracking in the presence of the sulfur reduction catalyst. FCC cracking catalyst. separate particulate additive, which is added to the main cracking catalyst in the FCC, nents in the cracking catalyst to provide one or alternatively they can be used as a compo-integrated cracking / sulfur reduction catalyst system.

The cracking component of the catalyst, which is conventionally present to achieve the desired cracking reactions and the production of low boiling cracking products, is usually based on an active cracking component in the form of faujasite zeolite, which is a conventional Y zeolite in one of its forms, such as a Y-zeolite of the calcined rare earth metal type (CREY) subjected to ion exchange, the preparation of which is described in U.S. Patent No. 3,402,996, Y-zeolite of ultra-stable type 10 5 25 25 12 (UsY), as well as various types of Y zeolites subjected as described in U.S. Patent No. 3,293,192, partial ion exchange, as described in U.S. Patent Nos. 3,607,043 and 3,676,368. Such used cracking- various commercial suppliers. The active cracking component is routinely combined with a matrix material, such as silica or alumina, as well as clay, in order to provide both the desired mechanical properties (abrasion resistance, etc.) and an activity control for the highly active zeolite component or components. The particle size of the cracking catalyst is usually in the range of 10-100 microns for efficient fluidization. If the sulfur reduction catalyst (and any other additive) is used as a separate particle additive, it is usually selected to have a particle size and density comparable to that of the cracking catalyst to prevent component separation during the cracking cycle.

Sulfur Reduction System Sieve Component According to the present invention, the sulfur elimination catalyst comprises a porous molecular sieve containing a metal in an oxidation state in excess of zero in the interior of the pore structure of the screen. The molecular sieve is in most cases a zeolite, and it may be a zeolite with properties similar to those of large pores, preferably USY zeolite, or zeolites, such as Y zeolite, beta zeolite, or with intermediate pore size zeolites, such as ZSM. -5, with the latter group being preferred.

The molecular sieve component of the present sulfur reduction catalysts may, as noted above, be a zeolite or non-zeolitic molecular sieve. , Marcel Dekker Inc., New York 1989, ISBN 0-8247-1105 25 25 25 35 523 251 13 7856-1, with respect to pore size according to the basic scheme prepared by J. Catalysis 67, 218-222 as A zeolite for a discussion of zeolite class divisions with grazing by Frilette et al, (1981)). and erionite, the small pore size zeolites, in addition to having insufficient stability for use in the catalytic cracking process, are generally not preferred due to their molecular size exclusion properties, which tend to exclude the components of the cracking flux, as well as many components. among the cracked products. The pore size of the screen does not appear to be critical, since both medium and large pore size zeolites as shown below have been found to be effective, as well as mesoporous crystalline such as MCM-41.

Zeolites having properties consistent with precursors, the advent of a large pore structure (12-ring) that can be used to prepare the present sulfur reduction catalysts include Y zeolites in its various forms such as Y, REY, CREY and USY, of which the latter forms are preferred, as are other zeolites, such as L-zeolite, free mordenite and ZSM-18 zeolite. The large pore size zeolites are of a beta zeolite pore structure, mordenite including alumina is generally characterized by a ring opening of at least 0.7 nm, and the medium or medium pore size zeolites have a pore opening of less than 0.7 nm, but greater than 0.56 nm. Suitable medium pore size zeolites that can be used include penta- such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-50, MCM-49 and MCM-56, all of which are silzeolites, ZSM-57, MCM-22, known materials. Zeolites can be used with other metal elements in the group than aluminum, such as boron, gallium, iron or chromium.

The use of USY zeolite is particularly desirable, since this zeolite is commonly used as an active cracking component in the cracking catalyst, and it is therefore possible to use the sulfur reduction catalyst in the form of a system with an integrated cracking / sulfur catalyst. 523 251 14 reduction catalyst. The USY zeolite used for the cracking component can also be advantageously used as a screening component for a separate catalyst particle additive, as it continues to contribute to the cracking activity of the entire catalyst present in the unit.

The stability of USY is correlated to small cell unit size (UCS), and for optimal results, UCS should be 2.420 to 2.460 nm, preferably 2.420 to 2.455 nm, with the range 2.420 to 2.445, preferably 2.435 to 2.440 nm, being very suitable. After exposure to repeated evaporation during the FCC cycles, further reductions of UCS occur to a final value which is usually in the range 2.420 - 2.430 nm.

In addition to zeolites, other molecular sieves can be used, although they are not as advantageous, as it has been found that some acidic activity (conventionally measured via the alpha value) is required for optimal performance.

Experimental data indicate that alpha values exceeding 10 (screen without metal content) are suitable for sufficient desulfurization activity, with alpha values in the range 0.2 to 2,000 usually being suitable (the alpha test is a suitable method for measuring total acidity, including both the internal and external acidity, of a solid, such as a molecular sieve, the test is described in U.S. Patent No. 3,354,078, Vol. 4, p. 527 (1965); ° C). Alpha values from 0.2 to 300 represent it in the Journal of Catalysis, p. 278 (1966); The normal range of acid activity in these application texts reported vol 6, and vol 61, s for these additives.

Examples of non-zeolitic screen materials which may constitute suitable support components for the metal component of the present sulfur reduction catalysts include silicates (such as metal silicates and titanium silicates) with varying silica-alumina ratios, metal aluminates (such as germanium aluminates), metal phosphates 251 aluminophosphates, such as silicon and metal aluminophosphates, termed metal-integrated aluminophosphates (MeAPO and ELAPO), metal-integrated silicon aluminophosphates (MeAPSO and ELAPSO), (SAPO), gallogenate silicon aluminophosphates and combinations of these. A discussion of the structural conditions for SAPO, AIPO, MeAPO and MeAPSO can be found in a number of publications, including Stud. Surf.

Catal. 37 13 - 27 (1987). phosphorus, while in SAPO part of the phosphorus and / or part of the AIPO contains aluminum and of both the phosphorus and the aluminum is replaced by silicon. In MeAPO, in addition to aluminum and phosphorus, various metals are present- B, Be, Mg, Ti, Mn, Fe, Co, An, Ga, Ge being, such as Li, and As, while MeAPSO also contains silicon. The negative charge for the MeaAlbPcSidOe network is offset by cations, cobalt, and / or zinc. MeXAPSO is described in U.S. Pat. are described in U.S. Pat. No. 4,758,419, MnAPSO in U.S. Patent No. 4,686,092, CoAPSO in U.S. Patent No. 4,744,970, FeAPSO in U.S. Patent No. 4,683,217 and ZnAPSO in U.S. Patent No. 4,935,216. Specific silicon aluminophosphates such as are useful include SAPO-11, SAPO-17, SAPO-34 and SAPO-37, sieve materials include MeAPO-5 and MeAPSO-5. while other specific Another class of crystalline support materials that may be used is the group of mesoporous crystalline materials exemplified by MCM-41 and MCM-48 materials. These mesoporous crystalline materials are described in U.S. Patent Nos. 5,998,684, 5,102,643 and 5,198,203. 523 251 16 arrangement of pores with diameters of at least 1.3 nm, and after calcination it has an X-ray diffraction pattern with at least a d-distance of more than 1.8 nm and a hexagonal electron diffraction pattern which can be indexed with a dl0O value exceeding 1.8 nm corresponding to the d-distance of the peak in the X-ray diffraction pattern. The preferred catalytic form of this material is the aluminosilicate, although other metal silicates may also be used. MCM-48 has a cubic structure and can be produced using a similar manufacturing method.

Metal Components Two metal components are incorporated into the molecular sieve support material in order to provide the present catalytic compositions. One component is a rare earth metal, such as lanthanum, or a mixture of rare earth metals, such as cerium and lanthanum. The second metal component can be considered as the primary sulfur reduction component, although the manner in which it exerts its sulfur reduction effect is not clear, as discussed in patent application 09/144 607, to which reference is made for a description of sulfur reduction catalyst compositions containing other vanadium pine components that are effective for this purpose. For the sake of simplicity, this component of the composition will be referred to in the present patent application as the primary sulfur reduction component. To be effective, this metal (or metals) should be present within the pore structure of the screen component. Metal-containing zeolites and other molecular sieves can be prepared by (1) subsequent addition of metals to the sieve or to a catalyst containing the sieve or sieves, (2) synthesizing the sieve or sieves containing metal atoms in the framework structure, and by (3) synthesis of the screen or screens with entrapped, bulky metal ions in the zeolite pores. After addition of the metal component, washing to remove unbound ionic substances as well as drying and calcination should be performed. These techniques are all known per se. Subsequent addition of metal ions is preferred for simplification and economic reasons, enabling available screen materials to be converted for use in the present additives. A variety of methods for the post-addition of metals can be used to prepare a catalyst according to the invention, for example, exchange of metal ions in aqueous medium, exchange in the solid state using one or more metal halide salts, impregnation with a metal salt solution and vapor deposition. of metals. In each case, however, it is important to carry out the addition of metal (s) so that the metal component penetrates into the pore structure of the screen component.

It has been found that when the metal in the primary sulfur reduction component is present as a cation material subjected to ion exchange in the pores of the screen component, the hydrogen transfer activity of the metal component is reduced to the point where the hydrogen transfer reactions occurring during the cracking process are usually maintained at acceptable levels. - nenterna. The formation of coke and light gas may increase slightly during cracking, but thus remains within tolerable limits. Since the unsaturated lightweight end products can be used in any case as alkylation feedstock and thus recycled to the gasoline depot, there is no significant loss of hydrocarbons in the gasoline range due to the use of the present additives.

Due to the consideration of excess coke and hydrogen formation during the cracking process, the metals for incorporation into the additives should not exhibit hydrogenation activity to any great extent. For this reason, noble metals, such as platinum and palladium, which have strong hydrogenation-dehydration functionality, are not desirable. Base metals and combinations of strong metal molybdenum base metals, nickel ringing functionality such as nickel, tungsten, cobalt molybdenum and nickel molybdenum, are not desirable for the same reason. The preferred base metals are metals from period 4, groups 5, 8, 9, 12 and 13 (IUPAC classification, former groups VB, VIII, IIB and IIIA) in the periodic table. Vanadium, zinc, iron, cobalt and gallium are effective, with vanadium being the preferred metal component. It is surprising that vanadium can be used in this way in an FCC catalyst composition, since vanadium is usually believed to have a very serious effect on zeolite cracking catalysts, and great efforts have been made to develop vanadium vaporizers (see, e.g., Wormsbecher et al., Vanadium Poisoning of Cracking Catalysts: Mechanism of Poisoning and Design of Vanadium Tolerant Catalyst System, J.

Catalysis 100, 130-137 (l986)). The position of the din within the sieve pore structure immobilizes It is believed to be vanadata and prevents it from being converted to vanadic acid material, which can be harmfully combined with the sieve component, but in any case the present zeolite-based sulfur reduction catalysts containing vanadium as a metal component scratched cycles between reducing and oxidative conditions / evaporation conditions that are representative of the FCC cycle while maintaining the characteristic zeolite structure, indicating a different environment for the metal.

Vanadium is particularly suitable for the reduction of gasoline sulfur when it is supported on USY zeolite. The resulting structure of the V / USY sulfur reduction catalyst is particularly interesting. While other zeolites after metal addition show gasoline sulfur reduction, however, they tend to convert gasoline to C3 and C4 gas. Although much of the converted C3 = and C4 = can be alkylated and remixed back into the gas storage, the wet exchange of C4 gas can be a problem, as many refineries are limited in their hydrogen compressor capacity.

Metal-containing USY has a similar structure obtained as current FCC catalysts, this advantage would allow adjustment of the V / USY zeolite content in a catalyst mixture to a limitless desulfurization melt level due to FCC unit constraints. The vanadium on the Y zeolite catalyst, where the zeolite is represented by USY, is therefore particularly favorable for gasoline sulfur reduction in the FCC. The USY which has been found to give particularly satisfactory results has a small cell unit size in the range from 2.420 to 2.460 nm, 2.420 to 2.450, e.g. 2.435 to 2.450 nm, preferably in the range (after treatment). Combinations of base metals, such as vanadium / zinc as the primary sulfur reduction component, can also be beneficial in terms of overall sulfur reduction.

The amount of primary sulfur reduction metal component in the sulfur reduction catalyst additive is usually from 0.2 to 5% by weight, usually 0.5 to 5% by weight (such as metal relative to the weight of the sieving component), but amounts outside this range, for example from 0.10 to 10% by weight. %, may still prove to have some sulfur-eliminating effect. When the screen is matrix bound, the amount of metals present usually ranges from 0.1 to 5, more preferably from 0.2 to 2% by weight of the entire catalyst.

The second metal component of the sulfur reduction catalyst composition comprises one or more rare earth metals which are present within the pore structure of the molecular sieve and which are believed to be in the form of cations which have undergone ion exchange on exchangeable sites on the sieve component. The rare earth metal (RE) component significantly improves the stability of the catalyst in the presence of vanadium. Higher cracking activity can be achieved, for example, by means of a RE + V / USY catalyst compared to a V / USY catalyst, while a comparable petrol sulfur reduction is obtained. Rare earth metals in the lanthanide series from atomic numbers 57 to 71, such as lanthanum, cerium, dysprosium, praseodymium, samarium, europium, gadolinium, ytterbium and lutetium, can be used in this way, but in terms of commercial availability are 10 15 20 25 30 35 523 Usually lanthanum and mixtures of cerium and lanthanum are preferred. Cerium has been shown to be the most effective component in the form of rare earth metal in terms of both sulfur reduction and catalyst stability, and its use is therefore preferred, although satisfactory results can also be obtained with other rare earth metals, as shown below.

The amount of rare earth metal is usually from 1 to 10% by weight of the catalyst composition, usually 2-5% by weight. In relation to the weight of the screen, the amount of rare earth metal is usually from 2 to 20% by weight, usually 4-10% by weight based on the screen, depending on the ratio between screen and matrix. Cerium can be used in amounts from 0.1 to 10, usually from 0.25 to 5, wt%, based on the catalyst composition, and usually from 0.2 to 20, usually from 0.5 to 10, wt%, based on sight.

The rare earth metal component can be conveniently incorporated into the molecular sieve component by ion exchange on the screen, either in the form of the non-matrix bound crystal or the matrix bound catalyst. When the composition is formulated with the preferred USY zeolite screen, a very effective incorporation method is the addition of the rare earth metal ions to the USY screen (usually 2.445 - 2.465 nm in cell unit size), followed by further steam calcination to reduce the cell unit size. for USY to a value usually in the range of 2.420 to 2.460 nm, after which the primary metal component can be added if not already (mainly sodium) with respect to both stability and present. USY should have a low alkali metal content satisfactory cracking activity, and this is usually ensured by means of ammonium ion exchange during the ultrastabilization process to a desirable low sodium content of at most 1% by weight, preferably at most 0.5% by weight, on the screen. 10 15 20 25 30 35: S23 251 21 The metal components are incorporated into the catalyst composition in a manner that ensures that they penetrate into the inner pore structure of the screen. The metals can be incorporated directly into the crystal or the matrix-bound catalyst.

When using the preferred USY zeolite as a sieve component, this can be conveniently accomplished as described above by recalcining a USY cracking catalyst containing the rare earth metal component to ensure a small cell unit size and then incorporating the metal, eg vanadium, by ion exchange or by impregnation under conditions that allow cation exchange to take place, so that the metal ion is immobilized in the pore structure of the zeolite. Alternatively, the primary sulfur reduction component and the rare earth metal component may be incorporated into the screen component, eg USY zeolite or ZSM-5 crystal, after any necessary calcination to remove organic matter from the synthesis, after which the metal-containing component may be formulated. to the final catalyst composition by adding the cracking and matrix components, and the formulation is spray dried to form the final catalyst.

When the catalyst is formulated as an integrated catalyst system, the active cracking component of the catalyst is preferably used as a screening component for the sulfur reduction system, preferably in the form of a faujasite, eg USY zeolite, both for simplification of production and for preserving controlled cracking properties. However, it is possible to incorporate another active crack into an integrated screen material, such as ZSM-5 zeolite, catalyst systems, and such systems may be useful when the properties of the other active screen material are desired, such as the properties of ZSM-5. The impregnation / ion exchange process should in both cases be carried out with a controlled amount of metal, so that the required number of seats is left on the screen for catalysis of the cracking reactions, which may be desirable for the active cracking. 251 22 component or any secondary cracking components present, eg ZSM-5.

Use of the Catalyst Sulfur Reduction Catalyst The most convenient way to use the sulfur reduction catalyst is usually as a separate particulate additive to the catalyst set. the lysator set in the unit did not result in any significant reduction in the total cracking due to the cracking activity of the USY zeolite. The same applies when another active cracking material is used as a screening component. When used in this way, the composition can be used in the form of a pure screen crystal, pelletized (without matrix but with added metal components) to the correct size for FCC use. Usually, however, the metal-containing screen is matrix-bound in order to achieve sufficient particle abrasion resistance and to maintain satisfactory fluidization. Conventional cracking catalyst matrix materials, such as alumina or silica-alumina, usually with added clay, are suitable for this purpose. The amount of matrix in relation to visibility is usually from 20:80 to 80:20 with respect to weight. Conventional matrix bonding techniques can be used.

Use as a separate particulate catalyst additive enables the ratio of the sulfur reduction and cracking catalyst components to be optimized with respect to the amount of sulfur in the feed stream and the desired amount of desulfurization, and when used in this manner it is usually used in an amount of 1 to 50% by weight. based on the entire catalyst set in the FCC unit, in most cases the amount is from 5 to 25% by weight, eg from 5 to 15% by weight. About 10% represents a standard for most practical purposes. The additive can be added in a conventional manner, such as together with the catalyst provided to the regenerator, or by any other suitable method. The additive remains active with respect to sulfur removal for long periods of time, although raw material flows containing very high sulfur contents may result in loss of sulfur removal activity for shorter periods of time.

The alternative to using the separate particulate additive is to use the sulfur reduction catalyst incorporated into the cracking catalyst to provide an integrated FCC cracking / gasoline sulfur reduction catalyst. If the sulfur reduction metal components are used in combination with a screen other than the active cracking component, eg on ZSM-5 or beta zeolite when the main active cracking component is USY, the amount of sulfur reduction component (screen and metals) is usually up to 25% by weight or less , based on the entire catalyst, which corresponds to the amounts in which it can be used as a separate particulate additive, as described above.

Other catalytically active components may be present in the circulating set of catalytic material in addition to the cracking catalyst and the sulfur removal additive. Examples of such other materials include the octane-promoting catalysts based on ZSM-5 zeolite, CO combustion promoters based on a supported noble metal, such as platinum, desulfurization additives for flue gas, such as DESOXTM (magnesium-aluminum spinel), vanadium traps and bottom cracking additives. Krishna, Sadeghbeigi, op cit and Scherzer, Octane Enhancing Zeolitic FCC Catalysts, Marcel Dekker, 1990, ISBN 0-8247-8399-9. components can be used in their conventional amounts.

New York, These other The effect of the present additives is to reduce the sulfur content of liquid cracking products, especially the light and heavy gasoline fractions, although reduction is also achieved in high boiling distillate products including light cycle oil and light and heavy 10 15 20 25 30 35 523 2s1 24 fuel oil fractions, making this more suitable for hydrogen desulfurization techniques by removing the more resistant sulfur compounds.

The distillate fractions can then be desulphurised under less stringent, more economical conditions for the production of distillate products suitable for use as a blend component for diesel or domestic heating oil.

The cracking process itself is normally carried out by adding the sulfur reduction catalyst, either as an additive or as an integrated catalytic cracking / sulfur reduction catalyst (a single particulate catalyst). The cracking conditions are conventional.

The sulfur removed using the catalyst is converted to inorganic form and released as hydrogen sulfide, which can be recovered normally in the product recovery section of the FCC in the same manner as the hydrogen sulfide is conventionally released in the cracking process. The increased hydrogen sulphide load may give rise to additional requirements for treatment with acid gas / water, but with the significant reductions in sulfur achieved in petrol, these can probably not be judged to be limiting.

Significant reduction of sulfur in gasoline can be achieved by using the present catalysts, in some cases up to 50% relative to the base case using a conventional cracking catalyst, with constant reaction using the preferred form of catalyst described above. A reduction of sulfur in gasoline of 25% can be easily achieved with many of the additives according to the invention, as shown by the examples below. For the intermediate distillate fractions including the LCO fraction, reductions of up to 25% can also be achieved, as shown below in the examples, coupled with a reduction in the content of resistant sulfur compounds including alkyl-substituted benzothiophenes and dibenzothiophenes. The extent of sulfur reduction can be due to the content of original organic sulfur in the cracking raw material flow, whereby the greatest reductions are achieved with raw material flows with higher sulfur contents.

The metal content of the equilibrium catalyst in the unit can also affect the degree of desulfurization achieved, whereby a low metal content, the lysator promotes increased desulfurization. Desulfurization is particularly effective in the case of vanadium, in equilibrium cat- very effective with vanadium contents in the E-catalyst of less than 1,000 ppm, although the present catalysts remain effective at even much higher vanadium contents.

The sulfur reduction can be effective not only in improving product quality, but also in increasing product yield in cases where the refinery's upper limit for cracked petrol has been limited by the sulfur content of the heavy petrol fraction, and by providing an efficient and economical way to reduce sulfur. the content of the heavy petrol fraction, the upper limit for petrol can be extended without the need for the use of expensive hydrogen treatment, which has a concomitant beneficial effect on the refinery economy. Removal of the various thiophene derivatives that are resistant to removal due to hydrogen treatment under less severe conditions is also desirable if subsequent hydrogen treatment is relevant.

Example 1 Preparation of Catalyst Series 1 All samples in Catalyst Series 1 were prepared from a single source of spray dried material consisting of 50% USY, 21% silica sol and 29% clay. USY had an initial cell unit size of 2.454 nm, a molar ratio of SiO2 to Al2O3 of 5.46 and a total surface area of 810 m 2 / g.

A V / USY catalyst, Catalyst A, was prepared by slurrying the above spray dried catalyst with NH 4 OH at a pH of 6, followed by filtration, ammonium sulfate ion exchange and washing with water. The catalyst was calcined in the presence of water vapor at 133 ° F for 2 hours and impregnated with vanadyl oxalate. The steam calcination reduced the cell unit size of the zeolite and improved its stability in the presence of vanadium.

A V / USY catalyst, similar to Catalyst A, except that Catalyst B, was prepared on the initial slurry of the catalyst was carried out at a pH of between 3.2 and 3.5.

Two RE + V / USY catalysts, Catalysts C and D, were prepared in the same manner as Catalyst B except that after the ammonium sulfate ion exchange, the catalysts were subjected to ion exchange with solutions of rare earth chlorides to give 2 and 4% by weight of REZO3, respectively. on the catalyst. In the rare earth metal solution used, some of its Ce3 + ions had been extracted, the solution containing only a few cerium ions.

A C

These catalysts were then deactivated with water vapor to simulate catalyst deactivation in an FCC unit in a suspended bed meadow heater at 770 ° C (1420 ° F) for 20 hours using 50% steam. The physical properties of the calcined and vapor-deactivated catalyst are summarized in Table 1. 10 l5 20 -523 251 27 Table 1 Physical properties of type V, RE + V and Ce + V catalysts with USY / silica sol (series 1 ) V / USY V / USY RE + v / Usy RE + v / USY Ce + V / UsY Cat A Cat B Cat C Cat D Cat E Calcined catalyst V additive, weight% 0.36 0.37 0.39 0 .38 0.39 REZO3 additive, weight% NA N.A. 2.0 4.1 5.1 Ce 2 O 3, wt% N.A. N.A. 0.49 0.95 4.95 La 2 O 3, wt% N.A. N.A. 0.96 1.83 0.03 Nazo, fold% 0.30 0.24 0.42 0.21 0.19 Cell unit size, nm 2.433 2.433 2.442 2.443 2.442 Deactivated catalyst (cPs 77 ° C, 20 h) Surface area, m2 Cell Unit Size, nm 2.425 2.424 2.426 2.428 2.428 Example Gel 2 Preparation of Catalyst Series 2 A V / USY catalyst, Catalyst F, was prepared using a USY zeolite having a silica to alumina ratio of 5 , 4 and a cell unit size of 2.435 nm. A liquid catalyst was prepared by spray drying an aqueous slurry containing 50% by weight of the USY crystals in a matrix of silica sol and clay. The matrix contained 22% by weight of silica sol and 28% by weight of kaolin clay. The spray dried catalyst was subjected to ion exchange with NH 4 + with a solution of ammonium sulphate and then dried.

Then the USY catalyst was impregnated with a solution of vanadium oxalate to the target 0.5% by weight of V.

A RE + V / USY catalyst, using a USY zeolite having a catalyst G ratio, was prepared between silica and alumina of 5.5 and a cell unit size of 2.454 nm. USY was subjected to ion exchange with NH 4 + in a solution of ammonium sulfate. USY subjected to ion exchange with NH4 + was then subjected to ion exchange with cations of rare earth metals (eg La3 +, Ce3 + etc) in a solution of mixed chlorides of rare earth metals. In the solution of rare earth metals used, most of its Ce3 + ions had been extracted, containing very little Ce. USY subjected to RE ion exchange was further washed, dried and calcined in the presence of water vapor in a rotary calciner at 760 ° C (1400 ° F). The steam calcination reduced the cell unit size of the zeolite to 24.40 Å and improved its stability in the presence of vanadium. A liquid catalyst was prepared by spray drying an aqueous slurry containing 50% by weight of the RE-USY crystals in a matrix of silica and clay.

The matrix contained 22% by weight of silica sol and 28% by weight of kaolin clay. The spray-dried catalyst was subjected to ion exchange with NH 4 + in a solution of ammonium sulphate and tor- (100 ° F) for 2 hours. After calcination, the RE / USY catalyst was then impregnated and calcined at 540 ° C with VOSO4 solution.

Catalyst H was prepared using procedures similar to Catalyst G, except that a mixed REC13 solution containing predominantly CeCl 3 was used for the ion exchange for USY. Catalyst H was prepared using a commercial USY zeolite having a silica to alumina ratio of 5.5 and a cell unit size of 2.454 nm. USY was subjected to ion exchange with NH 4 + in a solution of ammonium sulphate. USY subjected to ion exchange with NH 4 + was then subjected to ion exchange with a solution of CeCl 3 containing a certain amount of lanthanum. USY subjected to ion exchange was further washed, dried and calcined in the presence of water vapor in a rotary calciner at 760 ° C (1400 ° F). size to 2.440 nm. A Liquid Catalyst Prepared The steam calcination reduced the cell units of the zeolite by spray drying an aqueous slurry containing 50% USY crystals containing rare earth metal in a matrix of silica sol and clay.

The matrix contained 22% by weight of silica sol and 28% by weight of kaolin clay. The spray-dried catalyst was subjected to ion exchange with NH 4 + in a solution of ammonium sulphate and then dried and calcined at 540 ° C (10 ° F) for 2 hours. After 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 V / USY and RE + V / USY silica catalysts (series 2) V / USY RE + V / USY RE + V / USY Cat F Cat G Cat H Calcined catalyst V additive, Weight% 0, 0.43 0.44 REZO3 additive, weight% NA 1.93 2.66 ce2o3, wt% N.A. 0.21 2.42 Na 2 O, wt% 0.13 0.16 0.20 Surface area, m2-g'1 327 345 345 Cell unit size, nm 2,435 - - Example 3 Preparation of catalyst series 3 A V / USY catalyst, catalyst I , was prepared using a commercial H-form of USY (crystal) with a bulk ratio of silica to alumina of 5.4 and a cell unit size of 2.435 nm. A liquid catalyst was prepared by spray drying an aqueous slurry containing 40% by weight of the USY crystals, 25% by weight of silica, 5% by weight of alumina and 30% by weight of kaolin clay. The spray-dried catalytic (100 ° F) resulting H-form of the USY catalyst was impregnated, the satin was calcined at 540 ° C for 3 hours. to incipient wetness impregnation. The impregnated V / USY catalyst was further calcined in air at 540 ° C (100 ° F) for 3 hours.

The final catalyst contains 0.39% V.

A C 5% by weight of Ce additive using a method of impregnation to incipient wetness. The resulting Ce / USY catalyst was calcined in air at 540 ° C (100 ° F) for 3 hours, followed by steam heating at 540 ° C (100 ° F) for 3 hours.

Thereafter, the catalyst was impregnated with a vanadium oxalate solution to the target 0.4% by weight V by impregnation to incipient wetness. The impregnated Ce + V / USY catalyst was further calcined in air at 540 ° C (100 ° F) for 3 hours. The final catalyst contains 1.4% Ce and 0.43% V.

Table 3 Physical properties of V and Ce + V / USY catalysts of silica-alumina clay (series 3) V / USY ce + v / USY Cat I Cat J Calcined catalyst v addition, wt% 0.39 0, 43 Ce additive, weight% NA 1.4 Surface area, m2-g'1 302 250 Alpha 130 12 Ucs, nm 2,436 2,437 Example 4 Preparation of catalyst series 4 All samples in catalyst series 4 were prepared on the basis of a single source of spray-dried material consisting of 50% USY, 21 % silica sol and 29% clay. The USY starting material had a bulk ratio between silica and alumina of 5.4 and a cell unit size of 2.435 nm. The spray dried catalyst was slurried with a solution of (NH 4) 2 SO 4 and NH 4 OH at a pH of 6 to remove Na +, followed by washing with water and calcination in air at 650 ° C (1200 ° F) for 2 hours.

A V / USY catalyst, Catalyst K, was prepared using the above H-form of the USY catalyst. The H-form of the USY catalyst was impregnated with vanadium oxalate solution to the target 0.5% by weight of V by impregnation to incipient wetness. The impregnated V / USY catalyst was further calcined in air at 650 ° C (1200 ° F) for 2 hours. The final catalyst contains 0.53% V.

A Ce + V / USY catalyst, Catalyst L, was prepared from the above-mentioned H-form of USY catalyst. The H-form of the USY catalyst was subjected to ion exchange with a CeCl 3 solution to give 0.75% by weight of Ce. The resulting Ce / USY catalyst was calcined in air and impregnated with a vanadium oxalate solution to the target 0.5% by weight V by impregnation to incipient wetness. The impregnated Ce + V / USY catalyst was further calcined in air. The final catalyst contains 0.72% Ce and 0.52% V.

A Ce + V / USY catalyst, Catalyst M, was prepared starting from the above H-form of USY catalyst by ion exchange with a CeCl 3 solution to the target 3% by weight of Ce. The resulting Ce / USY catalyst was calcined in air and impregnated with a vanadium oxalate solution to the target 0.5% by weight V by impregnation to incipient wetness. further in air. The final catalyst contains 1.5% Ce and 0.53% V.

A Ce + V / USY catalyst, Catalyst N, was prepared. The impregnated Ce + V / USY catalyst was calcined from the above H-form of USY catalyst by impregnation to incipient wetness with a solution of CeCl % Ce. The resulting Ce / USY catalyst was calcined in air and impregnated with a vanadium oxalate solution to the target 0.5% by weight V by impregnation to incipient wetness. The impregnated Ce + V / USY catalyst was further calcined in air. The final catalyst contains 1.5% Ce and 0.53% V.

These catalysts were then deactivated with water vapor to simulate catalyst deactivation in an FCC unit in a fluidized bed steam heater at 770 ° C (1420 ° F) for 20 hours using 50% water vapor and 50% gas. The gas flow was changed from air, N2, propylene and N2 mixture and to N2 every ten minutes, after which air was circulated back to simulate the coking / regeneration cycle in an FCC unit (cyclic meadow heating).

Two sets of deactivated catalyst samples were formed, the vapor deactivation cycle ending with one for one batch of combustion in air (final oxidation) catalysts, and the other ending with propylene (final reduction). The coke content of the catalyst produced by "final reduction" is less than 0,05% C. The physical properties of the calcined catalysts and vapor-treated (final oxidation) are summarized in Table 4.

Table 4 Physical properties of V and Ce + V / USY catalysts with silica sol (series 4) V / USY Ce + V / USY Ce + V / USY Ce + V / USY Cat K Cat L Cat M Cat N Calcined catalyst V additive, Weight 0.53 0.52 0.53 0.53 Ce additive, weight% NA 0.72 1.5 1.5 Na, ppm 890 1190 1190 l260 Deactivated catalyst (CPS 770 ° C, 20 h) Surface area, m2-g'1 237 216 zos 204 Cell unit size, nm 2.425 2.423 2.425 2.425 10 15 20 25 30 Example 5 Preparation of Catalyst Series 5 All samples in Catalyst Series 5 were prepared starting from a single source of spray dried material consisting of 40% USY, 30% colloidal silica sol and 30% clay. The USY starting material in H-shape had a bulk ratio of silica to alumina of 5.4 and a cell 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 prepared using the above H-form of USY catalyst.

The H-form of USY catalyst was impregnated with a solution of Ce (NO 3) 3 to the target of 1.5% by weight of Ce by using a method of impregnation to incipient wetness. The resulting Ce / USY catalyst was calcined in air at 540 ° C (1000 ° F), followed by steam heating at 540 ° C (1000 ° F) for 3 hours.

A Ce + V / USY catalyst, Catalyst P, was prepared starting from Catalyst O. The Ce / USY catalyst was impregnated with vanadium oxalate solution to the target 0.5% by weight V by impregnation to incipient wetness. The impregnated Ce + V / USY catalyst was dried and calcined in air at 54 ° C (100 ° F). The catalyst contains 1.4% Ce and 0.49% V.

A Ce + V / USY catalyst, Catalyst Q, for 3 hours. The final was prepared starting from Catalyst O by ion exchange with a solution of VOSO4 at a pH of about 3 to the target 0.5% by weight of V. The Ce + V / USY catalyst was dried and calcined in air at 540 ° C (1000 ° F). The final catalyst contained 0.9% Ce and 0.47% V. for 3 hours.

The physical properties of the calcined catalysts are summarized in Table 5. Table 5 Physical properties of Ce and Ce + V / USY catalysts with silica and clay (series 5) Ce / USY Ce + V / USY Ce + V / USY Cat O Cat P Cat Q Calcined catalyst V additive, Weight: NA 0.49 0.47 Ce addition, weight% 1.6 1.4 0.9 Na, ppm - - 940 Yrarea, m2-g'1 284 281 272 Alpha - 10 14 Cell unit size, nm 2.435 2.436 2.436 Example 6 Preparation of RE + V / USY catalyst with silica sol An RE + V / USY catalyst, catalyst R, was prepared using a NaY zeolite having a silica to alumina ratio of 5.5 and a cell unit size of 2.465 nm. Zeolite Y was subjected to ion exchange with NH 4 + with an ammonium sulfate solution. Y which underwent ion exchange with NH 4 + was then subjected to ion exchange with cations of rare earth metals (eg La3 +, Ce3 + etc) by ion exchange with a solution of mixed chlorides of rare earth metals, from which most of Ce3 + was removed by extraction, so that the solution contained very little cerium. Y subjected to ion exchange with RE was further washed, dried and calcined in the presence of water vapor at 705 ° C (1300 ° F) for 2 hours. The steam calcination reduced the cell unit size of the zeolite and improved its stability in the presence of vanadium. A liquid catalyst was prepared by spray drying an aqueous slurry containing 50% by weight of the RE-USY crystals in a matrix of silica and clay. The matrix contained 22% by weight of silica sol and 28% by weight of kaolin clay. The spray-dried catalyst was subjected to ion exchange with NH 4 + 10 15 20 25 i523 251 u | v n o. 35 with an ammonium sulfate solution and dried and then calcined at 540 ° C (10 0 ° F) for 1 hour. The physical properties of the calcined catalyst are summarized in Table 6.

Table 6 Physical properties of RE + V / USY catalyst with silica sol RE + V / USY Cat R Calcined catalyst V additive, weight% 0.43 RE2O3 additive, weight% 1.93 CeO2 additive, weight% 0.21 Nazo, wt% 0.16 Surface area, m2 / g 345 Cell unit size, Å 24.58 Example 7 Preparation of Ce + V / USY catalyst with silica sol A Ce + V / USY catalyst, catalyst S, was prepared using a NaUSY zeolite with a silica-aluminum ratio of 5.5 and a cell unit size of 2,454 nm. USY was subjected to ion exchange with NH 4 + with a solution of ammonium sulfate. USY which underwent ion exchange with NH4 + was subjected to a new ion exchange with Ce3 + cations with a solution of cerium chloride containing a small amount of other ions of alkaline earth metals (eg La3 +, Pr, Nd, Gd, etc). USY undergoing ion exchange with Ce was further washed, dried and calcined in the presence of water vapor at 750 ° C (1300 ° F) for 2 hours. The steam calcination reduced the cell unit size of USY and improved its stability in the presence of vanadium. A liquid catalyst was prepared by spray drying an aqueous slurry containing 50% by weight of Ce / USY crypts 251. ~ | v n v f a ø o n n n »36 stables in a matrix of silica sol and clay. The matrix contained 22% by weight of silica sol and 28% by weight of kaolin clay.

The spray dried catalyst was subjected to ion exchange with NH 4 + with a solution of ammonium sulphate and then dried and calcined at 540 ° C (1000 ° F) for 1 hour.

After 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 Ce + V / USY catalyst with silica sol Ce + V / USY Cat S Calcined catalyst V additive, weight% 0.44 RE2O3 additive, weight% 2.66 CeO2, additive, weight% 2, 42 Na 2 O, weight% 0.20 Surface area, m2-g'1 345 Cell unit size, nm 2,446 Experimental procedure: Evaluation of cracking properties Catalysts from Examples 1-7 were evaluated with respect to FCC, and the results are reported in Examples 8-15.

The mixed catalysts (one sample and equilibrium catalyst) were tested for gas oil cracking activity and selectivity using the ASTM microactivity (MAT) test, D-3907, using a vacuum gas oil feedstock ( VGO). a circulating pilot riser unit using one modified from the ASTM process Some of the catalyst additives are evaluated in vacuum gas oil or a hydrotreated feed stream. The combinations of the three VGO flows and one (“severely 10 'S23 251 37 cat feed hydrotreated feed”) (CFHT) used in these examples are shown in Table 8.

Table 8 Properties for cracking flows Additive properties VGO No. VGO No. VGO No. CFHT l 2 3 API Weight 26.6 22.5 24.2 23.6 Aniline point, C 83 73 187 164 CCR, weight% 0.23 0.25 0, 6 0.09 Sulfur, weight% 1.05 2.59 1.37 0.071 Nitrogen, ppm 600 860 900 1200 Basic nitrogen, ppm 310 340 290 380 Ni, ppm 0.32 - 0.2 0.2 V, ppm 0, 68 - 0.1 0.2 Fe, ppm 9.15 - o 0.3 Cu, ppm 0.05 - 0 O Na, ppm 2.93 - 0.6 1.2 Similar distillates, ° C IBP 181 217 192 172 50 wt% 380 402 430 373 99.5 wt% 610 553 556 547 A range of cracking reactions was obtained by varying the catalyst to oil ratios for reactions carried out at 527 ° C (90 ° F).

The ranges of the limit points for the cracked products were: c5 + to 22o ° C (125-43o ° F) Petrol Light LCO Heavy LCO Light fuel oil (LFO) Heavy fuel oil (HFO) 220-310 ° C 310-370 ° C (430 -59 ° F) (590-70 ° F) 220-370 ° C (430-700 ° F) (700 ° F +) 370 ° C + 10 15 20 25 30 35 V52: 251. - n | .f a u u o a o v now 38 The products in the gasoline range from each material balance were analyzed using a sulfur GC (AED) to determine the gasoline sulfur concentration. To reduce experimental errors in the sulfur concentration associated with fluctuations in the distillation limit for gasoline, the sulfur substances ranging from thiophene to C4 thiophenes were quantified in synthetically produced raw material ("syncrude") (with the exception of the benzothiophene with higher sulfur and sulfur boiling point), and the sum was defined as “cut-gasoline S”.

To determine the sulfur content of the distillate fractions boiling in an area over the gasoline range (Examples 14 and 15), the synthetically prepared feedstock was subjected to atmospheric distillation to separate the gasoline. The bottom fractions were then further vacuum distilled to give two LFO / LCO fractions (light LCO and heavy LCO) and HFO. The sulfur compounds in the LCO sample were quantified using GC equipped with a column of type J&W 100 m DB-Petro and a sulfur detector of type Sievers 355B. The concentration of each LCO sulfur compound was calculated on the basis of the percentage of sulfur compounds from the gas chromatograph and the total sulfur content measured using the XPS method.

Example 8 Evaluation of Catalyst Series 1 in Catalytic Floating Catalyst Cracking The catalysts of Example 1 were deactivated by water vapor in a suspended bed steam heater at 770 ° C (1420 ° F) for 20 hours using 50% water vapor and 50% gas. as described in Example 4 above, which was terminated by combustion in air (final oxidation). 25% by weight of the unheated catalyst additives were mixed with a very low metal equilibrium catalyst (120 ppm V and 60 ppm Ni) from an FCC unit.

The catalytic cracking performance of the catalysts was evaluated using VGO No. 1 as 523 251: u c u u »39 cracking raw material effluent in the microactivity test. The performance of the catalysts is summarized in Table 9, where product selectivity has been interpolated to a constant turnover, ie to 65% by weight conversion of flow to a material with a limit point not exceeding 220 ° C (430 ° F). 10 523 251 |.-..- «0 40 Table 9 Catalytic cracking properties of Catalyst Series 1, VGO No. 1.

ECat + 25% + 25% + 25% + 25% + 25% V / USY V / USY RE + RE + RE + V / USY V / USY V / USY Base case Cat A Cat B Cat C Cat D Cat E FOOD product exchange Turnover, weight% 65 65 65 65 65 65 Cat./Oil 3.0 3.3 3.3 2.9 3.0 2.9 Incremental yield H2 yield, weight% 0.03 +0.05 +0.05 + 0.04 +0.02 +0.04 C1 + C2 gas, weight% 1.1 +0.1 +0.1 + O +0.1 +0 C3 gas total, 4.3 +0.1 +0.1 -0.1 +0 -0.2 wt% C3 = yield, wt% 3.7 +0.1 +0.1 +0 +0 -0.1 C4 gas total, 9.3 +0.1 +0.2 -0.1 +0 -0.3 wt% C4 = yield, wt% 4.7 +0.3 +0.4 +0.4 +0.1 +0 cs * -Gasoline, wt% 47.6 -0.6 -0.4 + o, 4 + o + o, s LFO, wt% 29.6 +0 +0.2 + O +0.1 +0 HFO, Weight fb 5.4 +0 -0.2 + 0 -0.1 +0 Coke, weight% 2.4 +0.3 +0.0 -0.2 -0.1 -0.1 Sulfur limit value in 618 377 366 369 382 352 petrol, ppm% reduction of Base 39.0 40.8 40.4 38.3 43.1 sulfur limit value in petrol The ratio of catalyst to oil in Table 9 shows that the mixtures of deactivated V / USY and ECat require a higher ratio between catalyst and oil than the base case with 100% equilibrium catalyst to achieve 65% turnover (3.3 for catalyst per 3.0 for oil, i.e. a reduction of the activity of 10%). This is due to lower cracking activity of the V / USY catalysts relative to the equilibrium catalyst. The addition of the RE + V / USY catalysts did not comparatively increase the catalyst-oil ratio to achieve 65% conversion. These results regarding the catalyst to oil ratio indicate that the RE + V / USY catalysts are more stable and maintain their cracking activity better than the V / USY catalysts.

Compared to the base case with equilibrium catalyst, the addition of V / USY and RE + V / USY catalyst gave small changes in the overall product yield structure. There was a certain increase in hydrogen and coke yields. In addition, a small change was observed regarding the exchanges of C4 gas, petrol, light oil from the cycle for this and heavy fuel oil. Addition of the V / USY and RE + V / USY catalysts significantly changed the sulfur concentration in gasoline. When 25% by weight of each of Catalyst A or B (V / USY) was mixed with equilibrium FCC catalyst, 39.0 and 40.8% reduction of sulfur con- the catalysts (catalysts C and D) were added to the equilibrium catalyst reference catalysts, the concentration in gasoline. lysis, the sulfur reduction activities in gasoline are comparable to those for the reference catalysts (38-40%).

The RE + V / USY catalyst containing mainly cerium as a rare earth metal (catalyst E) gave a reduction of 43.1% of sulfur in gasoline to reduce the sulfur content of gasoline by a further 4%, i.e. an improvement of 10% compared to V / USY and mixed RE / USY catalysts. All catalysts have a comparable (0.36-0.39%).

These results show that the addition of rare vanadium additive to earth metals improves the cracking activity of a V / USY catalyst. Only small changes in the yields of cracked product are obtained. Among the ions of rare earth metals, cerium exhibits a unique property in that the Ce + V / USY catalyst not only exhibits higher cracking activity, but also exhibits increased sulfur reduction. ø u: u 525 251 42 activity in petrol under catalytic cracking conditions in a suspended bed. The RE / USY rare earth metal catalyst without large amounts of cerium provides no further advantage over V / USY in terms of sulfur reduction in gasoline, while the presence of cerium further reduced the sulfur content of gasoline for V / USY or RE / USY (without higher cerium levels) catalysts.

Example 9 Comparison of the cracking activity of catalyst series 2 The V and RE + V / USY catalysts from Example 2 (catalyst series 2; catalyst F, G, H) were deactivated with water vapor at 770 ° C (1420 ° F) for different time periods for comparison of catalyst stability. The catalysts were treated with water vapor in a 5.3 vapor heater of 50% water vapor and 50% gas (cyclic vapor heating, suspended bed for 2.3, 10, 20 and 30 hours using final reduction, as described in Example 4 above). .

The surface retentions of the deactivated catalysts are plotted in Figure 2.

The vapor deactivated catalysts were tested for gas oil cracking activity using the ASTM microactivity test (ASTM Procedure D-3907) with vacuum gas oil No. 2 (above about 2.6% by weight S). At a contact time of 30 seconds and a reaction temperature of 545 ° C (980 ° F), a weight% -conversion to materials with a maximum limit of 220 ° C (430 ° F) was measured at a constant ratio of catalyst to oil of 4: 1. The conversions as a function of the water vapor deactivation time are plotted in Fig. 3.

The surface retentions shown in Figure 2 indicate that the V / USY and RE + V / USY catalysts exhibit comparable surface retention at different hydrothermal deactivation conditions, indicating that all three catalysts have comparable framework structure stability. However, the turnover plot shown in Fig. 3 clearly indicates that RE + V / USY has much improved cracking activity in 1 Ir; u n 1. nu ~ = u co: ~ u | n n> ~ v 1 -n 0 1 in c nu u n | v n | v 1; ; ø o =, n 0 v.; un nu x; a a; un ».mun c I x x 0 eu ~ sv Q a v 1 o n I I I o 4 vu vn: Q wuu en 43 retention when the intensity of hydrothermal deactivation increases. In hydrothermal deactivation, the improvement in cracking activity between the V / USY and RE + V versions was a turnover of 15%. No obvious differences were observed between the RE versions with different amounts of cerium. These results are consistent with those of Example 8, where RE + V / USY achieved the desired conversion at a lower catalyst to oil ratio than V / USY. These sales results indicate that the RE + V / USY catalysts are more stable and maintain their cracking activity in a better way than the V / USY catalysts. The addition of rare earth ions to USY, followed by calcination with water vapor to reduce the cell unit size of the zeolite, improved catalyst stability in the presence of vanadium.

Example 10 Evaluation of Catalyst Series 3 in Catalytic Cracking in Fluid Bed The V and Ce + V / USY catalysts of Example 3 (Catalysts I and J) were deactivated with water vapor in a fluidized bed steam heater at 770 ° C (1420 ° F). for 20 hours using 50% water vapor and 50% gas, as described in Example 4 above, which was terminated by combustion in air (final oxidation). 25% by weight of unheated catalyst additives were mixed with a low metal FCC equilibrium catalyst (120 ppm V and 60 ppm Ni). The mixed catalysts were then evaluated using the MAT test described above using raw material flow VGO No. 1. V The properties of the catalysts in series 3 using raw material flow VGO No. 1 are summarized in Table 10, where product selectivity is interpolated to a constant turnover, ie 70% by weight conversion of flux to materials with a limit of not more than 220 ° C (43o ° F>. nav-no 10. u. n. uun x. | z Yes. _ - .uv | nu v.> . v. _ ._ -. ß. - ø...... u. ". _. _.... u n. 0 .. i .. .z '_.. uun .. l» u I 1: "... product yield Turnover, weight% 70 70 70 Ka: / oil 3.3 3.8 3.7 Incremental yield H2 yield, weight% 0.03 +0.04 +0.13 C1 + C2 gas, weight% 1 , 4 + 0, 1 + 0, 1 C3 gas in total, 5.4 + 0, 1 -0.1 wt% C3 = yield, weight% 4.5 + 0, 1 -0.1 C4 gas in total , 10.9 +0.2 -0.2 wt% C4 = yield, wt% 5.2 +0.4 +0.2 iC4 yield, wt% 4.8 -0.2 -0.4 C5 + petrol, wt% 48.9 -0.3 -0.3 LFO, wt% 24.6 +0.5 + 0.3 HFO, Weight: 4.7 -0.2 -0.1 Coke, weight% 2.7 +0 +0.5 Sulfur limit value in 529 378 235 petrol, ppm% reduction of Base 29 56 sulfur limit value in petrol In table The FCC properties of V / USY and Ce + V / USY catalysts of silica-alumina clay each mixed with an FCC equilibrium catalyst (ECat) oxidation are compared. after cyclic deactivation in water vapor (concluding In comparison with the ECat base case, a till- .nu-co - 10 15 20 25 30 4523 251 ...

I I l | I J i 'v ~ ~' '-. ». »- 45 placement of V / USY and Ce + V / USY catalyst only small changes in the overall product yield structure. The changes in yield with respect to C4 gas, petrol, light oil from the cycle for this and heavy fuel oil are all small. Moderate increases in hydrogen and coke yields were observed. Although the changes in product yield were small, the V / USY and Ce + V / USY catalysts significantly changed the sulfur concentration in gasoline. When 25% by weight of Catalyst I (V / USY reference catalysts) was mixed with an FCC equilibrium catalyst, a 29% reduction in the sulfur concentration in gasoline was achieved. The Ce + V / USY catalyst (catalyst J) gave a comparatively 56% reduction in sulfur in gasoline. Addition of Ce to the V / USY catalyst reduced the sulfur content of gasoline by a further 27%, ie an improvement of 93% compared to the V / USY reference catalyst. Both catalysts have comparable vanadium additives (0.39% and 0.43% V, respectively). Given the fact that Ce itself has no sulfur-reducing activity in petrol (see example ll below), these results are quite unexpected and clearly show the benefits of cerium addition.

Example 11 Evaluation of series 4 catalyst in catalytic cracking in the suspended bed after cyclic vapor heating.

The properties of the V and Ce + V catalysts of Example 4 are summarized in this example. The Series 4 catalysts were deactivated with water vapor, as described above in Example 4 by cyclic vapor heating (final reduction), followed by mixing with FCC equilibrium catalyst containing low metal contents (120 ppm V and 60 ppm Ni) in a weight ratio of 25:75 and was tested using a raw material flow of type VGO No. 1. The results are summarized in Table 11. 46 Table 11 Properties in catalytic cracking of V- and Ce + V / USY catalysts of silica sol ECat + 25% + 25% + 25% Base case V / USY cat Ce + V / USY Ce + V / USY (Cat K) (Cat M) (Cat N) FOOD product yield Sales, weight% 65 65 65 65 Cat./Oil 3 .0 3.4 3.2 3.3 Incremental yield H2 yield, weight% 0.03 +0.02 +0.02 +0.02 C1 + C2 gas, weight% 1.1 +0 +0 + 0.1 C3 gas total, 4.4 -0.1 -0.1 +0 wt% C3 = yield, wt% 3.7 +0 -0.1 +0 C4 gas total, 9.5 - 0.1 -0.2 -0.1 wt% C4 = yield, wt% 4.8 +0.1 + 0.1 + 0.1 C4 yield, wt% 4.1 -0.2 -0 .3 -0.1 C5 + gasoline, weight% 47.4 +0.1 +0.5 +0.1 LFO, weight% 29.7 -0.2 + O -0.1 HFO, fold t% 5.3 +0.2 + 0 +0.1 Coke, weight% 2.3 + 0.1 + 0.1 +0 Sulfur limit value in petrol, ppm 516 489 426 426% reduction of sulfur limit value Base 5.2 17 .4 17.4 in petrol Table 11 compares the FCC properties of V / USY and Ce + V / USY catalysts with silica sol after cyclic deactivation in water vapor (final reduction). Compared to the ECat base case, addition of the V / USY and Ce + V / USY catalysts gave very small changes in the overall product yield structure. The yields of hydrogen gas, C4 gas, petrol, light oil from the cycle thereof, heavy fuel oil and coke were changed by less than 0.2% by weight each. Additions of the V / USY and Ce + V / USY catalysts altered the sulfur concentration in gasoline to varying degrees. When 25% by weight of catalyst K (V / USY reference catalyst) was mixed with FCC equilibrium catalyst, a 5.2% reduction in the sulfur concentration in gasoline was achieved. Ce + V / USY catalysts (Catalysts M and N) gave a comparatively 17.4% reduction in the sulfur concentration in gasoline. Addition of Ce to the V / USY catalyst reduced the sulfur concentration in gasoline by a further 12.3%, ie an improvement of 237% compared to the V / USY reference catalyst.

Example 12 Evaluation of Series 4 Catalyst in Catalytic Floating Catalytic Cracking After Cyclic Vapor Heating The properties of the V and Ce + V catalysts of Example 4 after cyclic deactivation with water vapor are summarized in this example. The catalysts of Example 4 were deactivated by cyclic vapor heating as described above in Example 4 (final oxidation) and then mixed with the low metal FCC equilibrium catalyst (120 ppm V and 60 ppm Ni) in a weight ratio of 25:75. The obtained evaluation results for the flow of raw materials of type VGO No. 1 are summarized in Table 12. 523 251:, ïwf :; : ¥ = ~ Û %%? Å 48 Table 12 Properties of V- and Ce + V / USY catalyst with silica sol in catalytic cracking ECat + 25% + 25% + 25% V / USY-cat Ce + V / USY Ce + V / USY Base case (Cat K) (Cat L) (Cat M) MAT product yield Turnover, weight% 70 70 70 70 Cat / Oil 2.8 3.7 3.6 3.4 Incremental yield H2 yield , weight% 0.03 +0.12 +0.13 +0.12 C1 + C2 gas, weight% 1.5 +0.2 +0.2 + 0.1 C3 gas in total, 5.5 + 0.1 +0 -0.1 wt% C3 = yield, wt% 4.7 + O +0 -0.1 C4 gas total, 11.1 +0 +0 -0.2 wt% C4 = - yield, weight% 5.8 +0.1 +0.1 +0 iC4 yield, Weight% 4.6 -0.1 -0.2 -0.2 c5 + petrol, weight% 49.4 -1, o -0.9 -0.5 LFO, weight% 25.6 -0.1 +0 +0.2 HFO, weight% 4.4 + 0.1 +0 -0.2 Coke, weight% 2.3 +0.6 + 0.5 +0.5 Sulfur limit value in 579 283 243 224 petrol, ppm% reduction of Bas 51.1 58.1 61.3 sulfur limit value in petrol 10 15 20 25 30 35 523 251, au. .u - u | I @ Y ° '' o a | o now 49 Table 12 compares the FCC properties of V / USY and Ce + V / USY catalyst additives with silica after cyclic deactivation with water vapor (final oxidation). Compared to the ECat base case, the addition of V / USY and Ce + V / UST catalyst gave small changes in the overall product yield structure. There were moderate increases in hydrogen and coke yields. In addition, small changes were observed in the yield of C4 gas, petrol, light cycle oil and heavy fuel oil. Addition of V / USY and Ce + V / USY catalysts significantly changed the sulfur concentration in gasoline. When 25% by weight of Catalyst K (V / USY Reference Catalyst) was mixed with an FCC equilibrium catalyst, a reduction of 5.1% of the sulfur concentration in gasoline was obtained. In comparison, the Ce + V / USY catalysts (catalysts L and M) gave 58.1 and 6.1% reduction of the sulfur content of gasoline, respectively. Addition of Ce to the V / USY catalyst reduced the sulfur content of the gasoline by a further 7.0-10.0%, ie up to 20% improvement over the V / USY reference catalyst.

The product yield values for the V / USY and Ce + V / USY catalysts indicate that the yield changes from ECat are due to the addition of vanadium to the USY catalyst. The product yields for the V / USY catalyst are comparable to those for the Ce + V / USY catalysts, but not in terms of the sulfur content of petrol. These results indicate that Ce increases the sulfur reduction activity in gasoline for the V / USY catalyst additive with little effect on product yields.

Example 13 Evaluation of catalyst series 5 in catalytic cracking in the suspended bed, study of improving effects.

The properties of the Ce and Ce + V catalysts of Example 5 after cyclic deactivation with water vapor (final reduction) as described above are summarized in this example. The deactivated catalysts were mixed with low metal FCC equilibrium catalyst (120 ppm V and 60 ppm Ni) in a weight ratio of 25:75. 10 15 .. ..

'' "'“'. "..".. ". C - - ~ '' '' Å 'v nu. u v. . I H. . . ,,. , _, _,,,,. . . U. ; - ;; -; ; . ... . . . .. .-,. . . . .. ... The results obtained with the VGO No. 1 commodity flow are summarized in Table 13.

Table 13 Properties of Ce- and Ce + V / USY catalysts with 'silica clay in catalytic cracking ECat + 25% + 25% + 25% Bas- Ce / USY Ce + V / USY Ce + V / USY case (Cat O) (Cat P) (Cat Q) FOOD product yields Turnover, weight% 70 70 70 70 Cat / oil 3.2 3.4 3.7 3.9 Incremental yield H2 yield, weight% 0.04 +0 + 0.07 +0.07 C1 + C2 gas, weight% 1,5 + 0,1 + 0,1 + 0,1 C3 gas in total, weight% 5,7 + 0,1 -0,1 +0 C3 = yield, weight% 4.8 +0 + 0 + 0 C4 gas total, weight% 11.5 +0 -0.3 -0.1 C4 = yield, weight% 5.7 +0 + O .1 + 0.1C4 yield, weight% 4.9 +0 -0.3 -0.2 C5 + petrol, weight% 48.8 -0.2 -0.2 -0.7 LFO, Weight% 25.5 +0 + 0.1 + 0.1 HFO, Weight 4.5 +0 -O, 1 -0.1 Coke, weight% 2.4 +0 +0.3 +0.6 Sulfur granular value in 486 487 341 351 petrol, ppm% reduction of sulfur- Base 0 29.8 27.7 limit value in petrol Table 13 compares the FCC properties of Ce / USY and Ce + V / USY catalyst additives with silica clay after cyclic deactivation with water vapor (final reduction). In comparison with the ECat base case, the addition of the Ce / USY catalyst hardly produced any changes in total product yields. Addition of the Ce + V / USY catalyst gave small changes to the total product yield structure. There were moderate increases in hydrogen and coke yields, as well as small changes in yields with respect to C4 gas, petrol, light cycle oil and heavy fuel oil. Addition of Ce / USY catalysts did not change the sulfur content of gasoline. On the other hand, Ce + V / USY catalysts (catalysts P and Q according to the invention) gave a 29.8% and 27.7% reduction in the sulfur content of petrol, respectively. These results indicate that cerium itself has no sulfur reduction activity in gasoline. Cerium appears to have a promoting effect on vanadium to increase the activity of a V / USY catalyst additive for sulfur reduction in gasoline.

Example 14 Catalyst R was evaluated in a Davison Circulating Riser in combination with a typical FCC equilibrium catalyst using a VGO No. 3 feedstock flow (Table 8). Prior to evaluation, the RE + V / USY catalyst was deactivated with water vapor at 770 ° C (1420 ° F) for 20 hours using 50% water vapor and 50% gas. 25% by weight of the water vapor treated catalyst additive was mixed with an equilibrium catalyst (530 ppm vanadium and 330 ppm Ni) from an FCC unit.

The FCC properties of the catalyst are summarized in Table 14, where product selectivity is interpolated to a constant turnover, ie 75% by weight conversion of the raw material flow to a material with a maximum limit of 220 ° C (430 ° F). 52 Table 14 Properties of a RE + V / USY ~ catalyst with silica sol in catalytic cracking ECat +2 5% RE + V / USY Base case (Cat R) Product yields in the riser unit Turnover, weight% 75 75 Catalyst / oil 7.0 6, 7 Incremental yield H2 yield, weight% 0.03 +0.01 C3 total, weight% 6.5 -0.1 c4 total, weight% 12.1 -0.1 C5 + petrol, weight% 49.4 - 0.1 LFO, weight% 18.3 -0.1 HFO, weight% 6.7 +0.1 Coke, weight% 4.1 +0.3 Sulfur limit value in petrol, ppm V 735 589 LCO sulfur, weight% 2.36 2.16% reduction of sulfur granule value in Bas 20 petrol% reduction of LCO sulfur Bas 9 In comparison with the base case, the addition of 25% by weight of RE + V / USY catalyst gave small changes in the overall product yield structure. There were negligible increases in H2 and coke yields. In addition, small changes in the yields were observed with respect to C4 gas, petrol, light oil from the cycle on this and heavy fuel oil. Addition of the RE + V / USY catalyst significantly changed the sulfur concentration in gasoline, resulting in a 20% reduction in the sulfur concentration in gasoline. In addition to a reduction in the sulfur content of petrol, a significant reduction in sulfur in LCO was observed, which is equivalent to a total reduction of 9% LCO sulfur. . ooooou 10 15 20 25 _, ... u n: n 1 | .I ',.' \ X i ',,; oo u v - 'ii I' '. . . ». . - - - I '' 'n i v I::: | v. I: z * z; ”',', I n a - g g - ',,, _ ... u .. .. -. 53 Sulfur compounds in LCO are shown in Table 15 and Fig. 4.

LCO contains a variety of benzothiophene and dibenzothiophene sulfur compounds. The sulfur reductions were more prominent for substituted benzothiophenes and substituted dibenzothiophenes, such as C3 + benzothiophenes and C1-C4 + dibenzothiophenes. The results are quite unexpected, as substituted dibenzothiophenes are bulkier and are expected to be more difficult to crack and desulfurize in the FCC.

Table 15 Sulfur specification in LCO from a raw material flow of type VGO no. 3 (Weight% sulfur in LCO) ECat + 25% RE + V / USY Base case (Cat I) Benzothiophene 0.04 0.04 Cl-benzothiophenes 0.22 0.24 C2-benzothiophenes 0.39 0.38 C3 + -benzothiophenes 0.47 0.38 Dibenzothiophenes 0.10 0.09 C1-dibenzothiophenes 0.36 0.32 C2-dibenzothiophenes 0.39 0.35 C3-dibenzothiophenes 0.24 0 .22 C

The C -flow). The FCC equilibrium base catalyst had very low metal contents (200 ppm V and 130 ppm Ni). During the first 15 days, a 50/50 mixture of fresh FCC catalyst and Ce + V / USY catalyst was added. »N - now the lysator from Example 7 to the FCC regenerator at 1.4% of the catalyst set per day. From the 15th to the 40th day, a mixture of 85/15 fresh FCC catalyst and Ce + V / USY catalyst was added to the FCC regenerator at 1.4% of the catalyst set per day. Re- (1300 ° F) during the evaluation. Two equilibrium catalyst (ECat) samples, the generator temperature maintained at about 705 ° C were collected, the first being taken before the Ce + V / USY addition (base case) and the second on the 40th day. Based on Ce and V analysis, the addition of the Ce + V / USY catalyst was estimated at 12%.

The FCC properties of the catalysts are summarized in Table 16, where the product selectivity is interpolated to a constant turnover, ie a conversion of 70% by weight of raw material flow to a material with a maximum limit of 200 ° C (430 ° F). 10 523 251 55 Table 16 o w Properties of Ce + V / USY catalyst with silica sol in catalytic cracking n u o a | | eu ECat + 12% Ce + V / USY Base case (Cat S) Product exchange in the riser unit Sales, weight% 70 70 Catalyst / oil 6.5 6.4 Incremental yield H2 yield, weight% 0.02 +0.0 C3 total , weight% 4.8 +0.0 C4 total, weight% 9.3 + 0.1 cs * gasoline, vicre 51.9 -0.2 LFO, Weight% 24.0 -0.2 HFO, weight% 6.1 + 0.1 Coke, weight% 2.6 +0.1 Sulfur limit value in petrol, ppm 100 79 Sulfur in light LCO, ppm 815 599 Sulfur in heavy LCO, ppm 1957 1687 HFO sulfur, ppm 2700 1700% reduction of sulfur granule value in Bas 21 petrol% reduction of sulfur in light LCO Bas 27% reduction of sulfur in heavy LCO% reduction of HFO sulfur BaS 14 wt% sulfur Bas 37 Weight% sulfur in spent catalyst <0.06 <0.06 I comparison with the ECat base case, addition of the Ce + V / USY catalyst gave small changes in the overall product yield structure. There were negligible increases in H2 and coke yields. In addition, small changes were observed with respect to C4 gas, petrol, light oil from the bike on it and heavy fuel oil. Addition of the Ce + V / USY catalyst significantly altered the sulfur content of gasoline. When 12% by weight of the Ce + V / USY catalyst was mixed in the FCC equilibrium catalyst, a reduction of 21% of the sulfur concentration in gasoline was obtained. In addition to the sulfur reduction in gasoline, significant sulfur reductions were observed in LCO and HFO.

The sulfur compounds in the light LCO fraction were analyzed using sulfur GC. The concentration of each class of organic sulfur was as shown in Table 17 and Fig. 5 for light LCO.

Table 17 Sulfur specification in light LCO from CFHT flow (ppm sulfur in light LCO) ECat + 12% RE + V / USY Base case (Cat J) C3 + thiophenes 4 1 Benzothiophene 20 14 Cl benzothiophenes 141 106 C2 benzothiophenes 237 174 C3 + -benzothiophenes 295 215 Dibenzothiophenes 17 14 C1-dibenzothiophenes 47 34 C2-dibenzothiophenes 32 25 C3-dibenzothiophenes 20 13 C4 + -dibenzothiophenes 3 1 Total 815 599 As shown in Fig. 5, light LCO mainly contains benzothiophene sulfur compounds. The sulfur reduction, which is equivalent to a total reduction of 27% of sulfur in light LCO, was more prominent for substituted benzothiophenes, such as C1-C3 + benzothiophenes. The results are quite unexpected, as substituted benzothiophenes are more bulky, and they are expected to be more difficult to crack and desulfurize in the FCC. 10 15 20 25 523 251. ->. . iv - nvuo nu 57 The sulfur compounds in the heavy LCO fraction were as shown in Table 18 and Fig. 6. Heavy LCO contains mainly dibenzothiophene sulfur compounds. dibenzothiophenes. The results are quite unexpected, as substituted dibenzothiophenes are bulkier and are expected to be more difficult to crack and desulfurize in the FCC.

Table 18 Specification of heavy LCO sulfur from CFHT flow (ppm heavy LCO sulfur) ECat + 12% RE + V / USY Base case (Cat J) Benzothiophene O C1 benzothiophenes 2 C2 benzothiophenes 12 C3 + benzothiophenes 128 86 Dibenzothiophenes 65 54 C1-dibenzothiophenes 361 312 C2-dibenzothiophenes 537 480 C3-dibenzothiophenes 475 425 C4 + -dibenzothiophenes 378 322 Total 1957 1687 The sulfur reduction catalyst is active in the reduction of benzothiophene and dibenzothiophenene wings. The reduction of sulfur occurs mainly in substituted benzothiophenes and substituted dibenzothiophenes. These results suggest that the C-S bonds in alkyl-substituted thiophenes are more reactive and susceptible to cracking.

The simple sulfur reduction of substituted thiophenes, substituted benzothiophenes and substituted dibenzothiophenes is quite unexpected and improves the efficiency of the subsequent LCO hydrogen desulfurization process. It is well known for the LCO hydrogen desulfurization process that methyl 523 251. . a> nu 58 and / or alkyl substitution of benzothiophene and dibenzothiophene causes a significant reduction in the desulfurization reactivity of the organic sulfur compounds and leads to "hard sulfur" or "resistant sulfur". Our LCO containing a small amount of substituted benzo- and dibenzothiophenes gives a diesel fuel with a lower sulfur content after a hydrogen desulfurization process compared to the LCO formed using a conventional FCC catalyst.

Claims (32)

10 15 20 25 30 35 nunnan n I nu n n an an - n. N av nn nnn n n ~ nn n n s v nu n o n n I I: v In w o n n o n n n n n n n n n n * nnn nn n I n K n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n n t n 59 A process for reducing the sulfur content of a liquid catalytically cracked petroleum fraction, which process comprises catalytic cracking of a petroleum flow fraction containing organosulfur compounds at elevated temperature in the presence of a cracking catalyst and a product sulfur reduction molar catalyst. i) a first metal component located within the pore structure of the molecular sieve and comprising vanadium in an oxidation state in excess of zero, and (ii) a second metal component located within the pore structure of the molecular sieve and comprising at least one rare earth metal, positioning of liquid cracking products with reduced (i) and introduced into the molecular sieve as a cation material as sulfur content, the metal components (ii) having been subjected to ion exchange in the pores of the molecular sieve. The process of claim 1, wherein the product sulfur reduction catalyst comprises a large or medium pore size zeolite as a molecular sieve component. A process according to claim 2, wherein the large pore size zeolite is a faujasite zeolite. A method according to claim 2, wherein the second metal component consists of the lantern separately or in combination with cerium. A method according to claim 2, wherein the second metal component is cerium. A process according to claim 1, wherein the second metal component is present in an amount of from 1 to 10% by weight based on the catalytic composition. The process of claim 1, wherein the product sulfur reduction catalyst comprises a USY zeolite having a UCS value of from 2.420 to 2.460 nm and a bulk ratio of silica to alumina of at least 5.0 as a molecular sieve component, and as other metal component cerium separately or in combination with lanthanum. ïfíšff 'líš - v14 få: "", l * š3: f' \ »íTí'3š <ï: ï.HSt = ííïiàüï Lšüíšílöïë 10 l5 20 25 30 35 = 523 251 60 The process of claim 1, wherein the sulfur reduction catalyst is a separate catalyst particle additive. The method of claim 1, wherein the reduced sulfur liquid cracking products comprise a gasoline fraction, a fraction of oil from the cycle therefor, and a fuel oil fraction, the oil from the cycle therefor and the fuel oil boiling at a temperature exceeding that of the gasoline fraction. A process for catalytic cracking in a suspended bed, wherein a heavy hydrocarbon feed stream containing organosulfur compounds is catalytically cracked into lighter products in a cyclic cracking process with catalyst recycling by contact with a set of circulating fluidizable catalytic cracking catalyst with a size consisting of ranging from 20 to 100 μm, (i) catalytic cracking of the feed stream in a catalytic cracking zone operated at catalytic cracking conditions by contact between the feed stream and a source of regenerated cracking catalyst for the production of a cracking zone effluent including products and spent catalyst including coke and stripping hydrocarbons; (ii) discharging and separating the effluent mixture into a vapor phase rich in cracked products and a phase rich in solids including spent catalyst; (iii) removing the vapor phase as a product and fractionating the steam to produce liquid cracking products including gasoline, (iv) evaporating the solid phase with vaporized catalyst to remove absorbed hydrocarbons from the catalyst, (v) transporting catalyst subjected to evaporation from the evaporator to a catalyst regenerator COI, LLLwä-í S: 10 15 20 25 30 35 523 251 a 1 un: n. 61 (vi) regeneration of catalyst subjected to evaporation by contact with oxygen-containing gas to produce regenerated catalyst; and (vii) recycling the regenerated catalyst to the cracking zone for contact with additional amounts of raw hydrocarbon feedstock, wherein the sulfur content of the liquid cracking products is reduced by performing the catalytic cracking in the presence of a product sulfur reaction catalyst, which includes a porous first metal component located within the pore structure of the molecular sieve and comprising vanadium in an oxidation state in excess of zero, and (ii) a second metal component located inside the pore structure of the molecular sieve and comprising at least one rare earth metal, wherein (metal) components and ii) has been introduced into the molecular sieve as a cationic material which has been subjected to ion exchange in the pores of the sieve. A process according to claim 10, wherein the cracking catalyst is a matrix bound faujasite zeolite. The process of claim 11, wherein the product sulfur reduction catalyst comprises a large or medium pore size zeolite such as molecular sieve component and cerium, separately or in combination with at least one other rare earth metal, such as second metal component. A process according to claim 12, wherein the large pore size zeolite of the product sulfur reduction catalyst is a faujasite zeolite. A method according to claim 10, wherein the second metal component consists of the lantern separately or in combination with cerium. A method according to claim 10, wherein the second metal component is cerium. A process according to claim 10, wherein the second metal component is present in an amount of from 1 to 10% by weight based on the catalyst composition_G2 12244 Q: Fa? Cbkïè fi ßïïravïïš I¿ï1í§.: - i:. = L0 15 20 25 30 35 en -o 62 A method according to claim 10, wherein the liquid cracking products comprise a gasoline fraction with reduced sulfur content and a fraction of oil from the cycle thereof having reduced sulfur content and boiling at a temperature in excess of that of the gasoline fraction. A fluidizable catalyst composition for sulfur reduction in a catalytic cracking product for reducing the sulfur content of a liquid catalytically cracked gasoline fraction in the catalytic cracking process, which composition comprises fluidizable particles having a size ranging from 20 to 100 μm of a pore molecular sieve component, and (i) a first metal component including vanadium in a state of oxidation in excess of zero and located within the pore structure of the porous molecular sieve component, and (ii) a second metal component comprising a rare earth metal pore component ) and (ii) have been introduced into the molecular sieve component as a cationic material which has been subjected to ion exchange in the pores of the molecular sieve. A fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 18, wherein the porous molecular sieve component comprises a porous hydrocarbon cracking sieve component. The fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 19, wherein the porous molecular sieve component comprises USY zeolite having a UCS value of from 2,420 to 2,460 nm and a bulk ratio of silica to alumina of at least 5.0. The fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 20, wherein the porous molecular sieve component comprises USY zeolite having a UCS value of from 2,420 to 2,435 and a bulk ratio of silica to alumina of at least 5.0. 10 15 20 25 30 35 »» = n n 523 251 63 A fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 18, wherein it contains from 0.1 to 5% by weight of vanadium as the first metal component, based on the weight of the molecular sieve. A fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 22, wherein it comprises a combination of cerium and at least one other rare earth metal as a second metal component. A fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 18, wherein it comprises cerium as a second metal component. A fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 18, wherein it is formulated with a matrix component as a catalyst additive for fluidized bed cracking. The fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 18, wherein it is formulated as an integrated fluidizable catalyst composition for sulfur reduction in a catalytic cracking product for cracking a raw material flow of heavy hydrocarbons to produce liquid cracking products. and reducing the sulfur content of the catalytically cracked gasoline fraction during the catalytic cracking process, comprising fluidizable particles, ranging in size from 20 to 100 microns, of a hydrocarbon cracking component comprising a zeolite molecular sieve containing in the zeolite porous structure a first metal component comprising vanadium, and (ii) a second metal component comprising at least one rare earth metal, wherein components (i) and (ii) have been introduced into the zeolite molecular sieve as a cationic material which has been subjected to ion exchange in the sieve pore. l0 15 20 25 30 35 s2s 251 64 An integrated, fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 26, wherein it contains from 0.1 to 5% by weight of vanadium as the first metal component, based on the weight of zeolite. An integrated, fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 26, wherein the second metal component is a combination of cerium and at least one other rare earth metal in an amount of from 1 to 5% by weight, based on the catalyst. An integrated, fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 26, wherein the second metal component is a combination of cerium in an amount of from 1 to 5% by weight, based on the catalyst. An integrated, fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 26, wherein the zeolitic molecular sieve consists of a USY zeolite with a UCS value from 2.420 to 2.460 nm and a bulk ratio of silica to alumina of at least 5.0. The fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 20, wherein the zeolitic molecular sieve component is a UCY zeolite having a USC value of from 2,420 to 2,435 nm and a bulk ratio of silica to alumina of at least 5.0. The fluidizable catalyst composition for sulfur reduction in a catalytic cracking product according to claim 26, wherein it is formulated as an integrated fluidized bed cracking / sulfur reduction catalyst having a matrix component and a faujasite zeolite as the cracking component. nn '* Ef: z fl,: ~ -. 'alm mon: .VL-lf