KR20000048453A - Gasoline sulfur reduction in fluid catalytic cracking - Google Patents

Abstract

PURPOSE: Provided is a method for reducing sulfur from gasoline or other petroleum products produced from a catalytic cracking process using a sulfur reduction catalyst which is able to improve the reduction rate of the sulfur content from the products of the catalytic process. CONSTITUTION: To reduce the sulfur content from a catalytic cracked petroleum fraction, a supplied petroleum fraction containing an organic sulfur compound is catalytically cracked with raising the temperature under the sulfur reduction catalyst comprising (i) a first metallic component which is placed inside a porous structure of a molecular body such as a zeolite having large or medium size of pores and contains a metal in an oxidized state of more than 0 such as vanadium, zinc, iron, cobalt and gallium; and (ii) a second metallic component which is place inside a porous structure of a molecular body and contains at least one rare-earth element such as lanthanum, cerium or a mixture of lanthanum with cerium.

Description

Gasoline sulfur reduction in fluid catalytic cracking

The present invention relates to a method for reducing sulfur in gasoline and other petroleum products produced by catalytic cracking processes. The present invention provides a contact composition for reducing product sulfur and a method of reducing product sulfur using the composition.

Catalytic cracking is a petroleum refining process that is commercially employed on a large scale in the United States, in particular where most refinery gasoline mixing pools are manufactured by catalytic cracking, which is almost all by fluid catalytic cracking (FCC) processes. In the catalytic cracking process, the reaction is carried out at elevated temperature in the presence of a catalyst to convert the heavy hydrocarbon fraction into a lighter product, with most of the conversion or contact proceeding to the vapor phase. The feedstock is converted to gaseous, distillate and other contact products as well as light gaseous contact products having 4 or less carbon atoms per molecule. The gas is partly composed of olefins and partly saturated hydrocarbons.

During the decomposition reaction some heavy material, known as coke, is deposited on the catalyst. This reduces its contact activity and requires regeneration. After removing the occluded hydrocarbon from the spent cracking catalyst, the coke is burned to perform regeneration and then the catalytic activity is returned. Thus, the three characterization stages of catalytic cracking can be divided into a cracking step in which hydrocarbons are converted into light products, a stripping step for removing hydrocarbons adsorbed on the catalyst, and a regeneration step in which coke is burned from the catalyst. The regenerated catalyst is then reused in the decomposition step.

Catalytic cracking feedstocks generally contain sulfur in the form of organic sulfur compounds such as mercaptans, sulfides and thiophenes. Correspondingly, the products of the cracking process are likely to contain sulfur impurities during the cracking process even though half of the sulfur has been converted to hydrogen sulfide mainly by catalytic cracking of the non-thiophenic sulfur compounds. The sulfur distribution in cracked products depends on the number of factors, including feed, catalyst type, additive status, conversion and other operating conditions, but in some cases a certain proportion of sulfur is included in the light or heavy gasoline fraction and transferred to the product pool. There is this. For example, in the revised Gasoline (RFG) regulations, as the environmental enforcements applied to petroleum products become stronger, the sulfur content in the product generally decreases due to the risk of sulfur oxides and other sulfur compounds being released into the air after the combustion process. It is becoming. Gasoline sulfur reduction not only SO _x emissions, it is important due to the sulfur dokhwa (poisoning) of the automotive catalytic converter. Poisoning of the catalytic converter will cause other emission problems such as NO _x .

Environmental concerns have focused on the sulfur content of automobile gasoline, considering that gasoline occupies a significant place as a vehicle fuel for passenger cars in the United States. However, this interest also extends to high boiling distillation fractions, including light cycle oil (LCO) and fuel oil fractions (light fuel oil LFO and heavy fuel oil HFO) obtained by catalytic cracking processes. For these products hydrodesulfurization has been used for a long time to reduce the sulfur level in the product fraction, and this method has generally proved effective. However, since sulfur compounds, especially substituted benzothiophenes, become increasingly fire resistant as their boiling points increase, high boiling fractions do not desulfurize as in the case of low boiling fractions. In LCO hydrodesulfurization, the methyl and / or alkyl substitutions of benzothiophene and dibenzothiophene substantially degrade the desulfurization reactivity of organic sulfur, which is referred to as "hard sulfur" or "refractory sulfur." ". An example of LCO sulfur GC is shown in FIG. 1 showing sulfur GC composition. Grigis and Gates are described in Ind. Eng. Chem., 30, 1991, 2021-2058, reported that substitution of methyl groups at the 4- or 4- and 6-positions reduced the desulfurization activity in size order. Houalla et al. Reported active debits in size order of 1 to 10 (M. Houalla et al., Journal of Catalysis, 61, 1980, 523-527). Lamure-Meille et al. Have suggested that steric hindrance of alkyl groups can reduce the reactivity of methyl-substituted dibenzothiophenes (see Lamure-Meille et al., Applied Catalysis A: General). 131, 1995, 143-157). Given that high boiling point catalytic cracking products are useful as feeds for the hydrodesulfurization process, it is clear that reducing the amount of more refractory organosulfur compounds in these cracking fractions is encouraging.

Attempts have been made to remove sulfur from the FCC feed by hydrotreating prior to decomposition. While this approach is very effective, it is expensive due to the high consumption of hydrogen, not only operationally but also because of expensive equipment. Another attempt has been made to remove sulfur from the product decomposed by hydrotreating. This solution is also effective but has the disadvantage that expensive octane products may be lost when the high octane olefins are saturated.

From an economic point of view, removal of sulfur in the decomposition process itself is preferred because it can effectively desulfurize the main components of the gasoline mixing pool without further treatment. Various contact materials have been developed to remove sulfur during the FCC process cycle, but so far most developments have focused on removing sulfur from regenerator stack gas. An early approach developed by Chevron adsorbed sulfur oxides in FCC regenerators using alumina compounds as additives to the inventory of cracking catalysts; Adsorbed sulfur compounds entering the process as feed are released as hydrogen sulfide at the point of decomposition of the cycle and then enter the product recovery unit and are removed therefrom (Krishna et al, Additives Improve FCC Process, Hydrocarbon Processing, November 1991, pages 59-66). Sulfur is removed from the flue gas of the regenerator, but the sulfur level of the product is hardly affected.

Another technique for removing sulfur oxides from regenerators is based on the use of magnesium-aluminum spinels as an additive to the circulating catalyst inventory in the FCCU. The use of the trade name DESOX ^™ as an additive in this process has resulted in notable commercial performance. US Patent Nos. 4,963, 520 to patents illustrating sulfur removal additives of this type; 4,957,892; 4,957,718; 4,790,982, and the like. However, they also did not significantly reduce sulfur levels.

Catalyst additives for reducing sulfur levels in liquid cracking products have been proposed in US Pat. Nos. 5,376,608 and 5,525,210 by Wormsbecher and Kim (here alumina supported to produce sulfur-reduced gasoline). (supported) Decomposition catalyst additives of Lewis acid were used but this system did not have significant commercial success). Thus, there remains a need for effective additives to reduce the sulfur content of liquid catalytic cracking products.

In U.S. Patent Application No. 09 / 144,607 filed in the United States on August 31, 1998 (Korean Patent Application No. 10-1999-0036279), the inventors found that catalytic cracking can reduce the sulfur content in the liquid product of the decomposition process. Catalyst materials for use in the process have been described. These sulfur reduction catalysts contain, in addition to the porous sieve component, metals in the oxidation state greater than zero inside the pore structure of the sieve. Molecular sieves are in most cases zeolites and may be zeolites having properties consistent with large pore size zeolites such as zeolite beta or zeolite USY or mesoporous zeolites such as ZSM-5. Non-zeolitic molecular sieves such as MeAPO-5, MeAPSO-5 and mesoporous crystalline materials such as MCM-41 can be used as the sieve component of the catalyst. Metals such as vanadium, zinc, iron, cobalt and gallium have been found to be effective for reducing sulfur in gasoline, with vanadium being the preferred metal. When used as separate particle additive catalysts, these materials are used in conjunction with active catalytic cracking catalysts (usually pausites such as zeolite Y, in particular zeolite USY) to treat hydrocarbon feedstocks in fluid catalytic cracking (FCC) units. To form a low sulfur product. Since the sieve component of the sulfur reduction catalyst can itself be an active decomposition catalyst (e.g. zeolite USY), the sulfur reduction catalyst is an additive matrix, for example metals such as silica, clay and vanadium which provide sulfur reduction functions. It is also possible to use together with the substance in the form of an integrated decomposition / sulfur reduction catalyst system containing USY as a sieve component and active decomposition component of the sulfur reduction system.

In the production of FCC catalysts, the cracking catalyst is exposed to repeated reduction cycles (in the cracking stage) during use and stripped off with steam, followed by oxidative regeneration (burning of coke (carbon-rich hydrocarbons) deposited on the catalyst particles during the cracking cycle). Catalytic stability, in particular hydrothermal stability, is also considered. Early in the development of zeolitic cracking catalysts, it was found that sodium content should be low for stability as well as optimum cracking activity, and rare earth elements such as cerium and lanthanum provide greater hydrothermal stability (see, for example, Fluid Catalytic Cracking with Zeolite Catalysts, Venuto et al., Marcel Dekker, New York, 1979, ISBN 0-8247-6870-1).

The inventors have developed catalyst materials for use in catalytic cracking processes that can improve the rate of reduction of sulfur content, particularly in liquid products of cracking processes including gasoline and intermediate distillation cracking fractions. The sulfur reduction catalyst of the present invention is similar to that described in US Application 09 / 144,607 in that a metal component in an oxidation state greater than zero is present in the pore structure of the molecular sieve component of the catalyst composition and vanadium is preferred. In this case, however, the composition also comprises one or more rare earth elements, preferably cerium. The present inventors have found that the presence of rare earth components improves the stability of the catalyst compared to catalysts containing only vanadium or other metal components, and in certain cases cerium is particularly advantageous as rare earth components, and the presence of rare earth elements also provides sulfur reduction activity. It was found to increase. This phenomenon is surprising because the rare earth cation itself does not have sulfur reducing activity.

1 shows LCO sulfur GC.

2 shows the surface area retention of V / USY, RE + / V / USY and Ce + V / USY catalysts.

3 shows the active retention states of V / USY, RE + / V / USY and Ce + V / USY catalysts.

4 shows sulfur species of LCO.

5 shows hard LCO sulfur species.

6 shows heavy LCO sulfur species.

The sulfur reduction catalyst of the present invention is an addition catalyst with an active cracking catalyst in a cracking unit, i.e. with a conventional main component of the circulating cracking catalyst inventory which is generally a matrix zeolite containing catalyst based on faujasite zeolites, usually zeolite Y. It can be used in the form of. Sulfur reduction catalysts may also be used in the form of integrated cracking / product sulfur reduction catalyst systems.

According to the invention, the sulfur removal catalyst composition comprises a porous molecular sieve containing (i) a metal in oxidation state greater than zero inside the pore structure of the sieve and (ii) a rare earth component. The molecular sieve is in most cases a zeolite and may be a zeolite having properties consistent with a large pore size zeolite such as zeolite beta or zeolite USY or a mesoporous zeolite such as ZSM-5. Non-zeolitic molecular sieves such as MeAPO-5, MeAPSO-5 and mesoporous crystalline materials such as MCM-41 can be used as the sieve component of the catalyst. Metals such as vanadium, zinc, iron, cobalt and gallium are effective. If the selected sieve material has sufficient degradation activity, it can be used as an active catalytic cracking catalyst component (usually a fausite, such as zeolite Y), or with active decomposition components whether or not having decomposition activity by itself. Can be used.

The compositions of the present invention are useful for treating hydrocarbon feedstocks in fluid catalytic cracking (FCC) units to produce light cycle oils that can be used as low sulfur gasoline and other liquid products, such as low sulfur diesel mixed components or heating oils. In addition to significantly reducing the sulfur content in the cracked gasoline fraction, the sulfur reducing catalyst material of the present invention can reduce the sulfur levels of light cycle oils and fuel oil products (light fuel oil, heavy fuel oil). Sulfur reduction in LCO occurs primarily with substituted benzothiophenes and substituted dibenzothiophenes, and removal of these more refractory species may improve the sulfur reduction efficiency in subsequent LCO hydrodesulfurization processes. HFO sulfur reduction enables the coke product to be upgraded from oil to higher coke.

While the mechanisms for removing the sulfur component normally present in hydrocarbon products in which the metal-containing zeolite catalyst composition is degraded are not exactly understood, this is in fact a contact process by including converting organic sulfur compounds in the feed to inorganic sulfur. In this process, zeolites or other molecular sieves provide morphological selectivity of various pore sizes, and it is believed that the metal sites in the zeolite provide adsorption sites for sulfur species.

The figure is a graph showing the performance of the sulfur reducing composition of the present invention as described below.

FCC process

The sulfur removal catalysts of the present invention are used as contact components in the circulating inventory of catalysts in catalytic cracking processes (which today are almost all necessarily flow catalytic cracking (FCC) processes). For convenience, the present invention will be described on the basis of an FCC process, although the additives of the present invention may be used in existing moving bed type (TCC) decomposition processes by appropriately adjusting the particle size to meet the conditions of the process. There will be no change in the method of operation of the process, except that the additives of the present invention are added to the catalyst inventory and there may be minor changes in the product recovery portion described below. Thus, seminar reviews by conventional FCC catalysts such as Venuto and Habib [Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1] and Sarde Fluid Catalytic Cracking Handbook, Gulf Publ. By Sadeghbeigi. Co. Houston, 1995, ISBN 0-88415-290-1] zeolite-based catalysts with pausiteite decomposition components as described in many other sources can be used.

More briefly, the fluid catalytic cracking process in which a heavy hydrocarbon feed containing an organosulfur compound is cracked into a light product is carried out in a circulating catalytic catalytic cracking catalyst inventory consisting of 20 to 100 micron sized feeds of the cyclic catalyst recycle cracking process. It is carried out by contact with. The main steps in the cyclic process are:

(i) contacting and cracking the feed with a source of hot regeneration cracking catalyst in a catalytic cracking zone, usually a riser cracking zone, operating under catalytic cracking conditions to produce waste catalysts and cracked products containing coke and strippable hydrocarbons. To obtain an effluent comprising;

(ii) discharge the effluent and separate in one or more cyclones into a solid-rich phase containing a cracked product rich in cracked products and a spent catalyst;

(iii) the vapor phase is separated as a product and fractionated in an FCC main column and a side column coupled thereto to give a liquid decomposition product including gasoline;

(iv) the spent catalyst is generally stripped off in a stream to remove occluded hydrocarbons from the catalyst, and then the stripped catalyst is oxidatively regenerated to obtain a hot regenerated catalyst, which is then subjected to a cracking zone to decompose additional feed. Recycle.

Feeds for the FCC process are generally high boiling feeds of mineral oil origin having an initial boiling point of at least 290 ° C. (550 ° F.), in most cases at least 315 ° C. (600 ° F.). Most refinery cut points for FCC feeds will be at least 345 ° C (650 ° F). The end point will depend on the exact nature of the feed or the operating characteristics of the refinery. The feed may be a distillate having an endpoint generally of 550 ° C. (1020 ° F.) or above, for example 590 ° C. (1095 ° F.) or 620 ° C. (1150 ° F.), or residue (non-distilled) material may be included in the feed. And even make up all or most of the feed. Feeds which can be distilled are virgin feeds, for example gas oils such as heavy or light atmospheric gas oils, heavy or light vacuum gas oils and cracked feeds, for example light coke gas oils, heavy coke Gas oils. Hydrotreated feeds, such as hydrotreated gas oils, in particular hydrotreated heavy gas oils, may be used, although the catalyst of the present invention can significantly reduce sulfur, although there is still room for degradability improvement. Initial hydrotreating with the aim of reducing sulfur may not be carried out.

In the process of the present invention, the catalytic cracking is carried out in the presence of a sulfur reducing catalyst to effectively bring the sulfur content in the gasoline portion of the liquid cracking product to lower and more acceptable levels.

FCC decomposition catalyst

The sulfur reduction catalyst of the present invention may be used in the form of separate particle additives added to the main cracking catalyst of the FCCU, or may be used as a component of the cracking catalyst to provide an integrated cracking / sulfur reducing catalyst system. The cracking component of the catalyst is generally a faujasite zeolite active cracking component, usually zeolite Y, for example a calcined rare earth exchanged type Y zeolite (CREY), which is one of its forms, the process of which is described in US Pat. No. 3,402,996 Superstable type Y zeolites (USY) described in US Pat. No. 3,293,192 and various partially exchanged type Y zeolites described in US Pat. Nos. 3,607,043 and 3,676,368. Cracking catalysts such as these can be purchased in large quantities from various commercial sources. Actively decomposing components are routinely combined with matrix materials such as silica or alumina to provide the desired mechanical properties (such as wear resistance) and to control the activity of highly active zeolite components or components. Particle sizes of cracking catalysts generally range from 10 to 100 microns for effective fluidization. When used as discrete particle additives, sulfur reduction catalysts (and other additives) are generally selected to have a particle size and density equivalent to that of the decomposition catalyst to prevent components from separating during the decomposition cycle.

Sulfur Reduction System-Sieve Ingredients

According to the invention, the sulfur removal catalyst comprises a porous molecular sieve containing a metal in an oxidation state greater than zero inside the pore structure of the sieve. The molecular sieve is in most cases a zeolite and may be zeolite Y, preferably a zeolite having a property consistent with a large pore size zeolite such as zeolite USY or zeolite beta or a medium pore size zeolite such as ZSM-5, the latter Is preferred.

The molecular sieve component of the sulfur reduction catalyst according to the invention may be a zeolite or non-zeolitic molecular sieve as described above. In use, the zeolite can be selected from either large pore size zeolites or medium pore size zeolites. Shape Selective Catalysis in Industrial Applications, Chen et al, Marcel Dekker Inc., New York 1989, ISBN 0-8247-7856- 1, classifying zeolites by pore size according to the basics described in Frilette et al. (J. Catalysis 67, 218-222 (1981)) Pore sizes, in addition to having insufficient stability for use in catalytic cracking processes Zeolites such as small zeolite A and erionite are generally undesirable because their molecular size exclusion properties can exclude many components of the degraded product as well as components of the decomposition feed. Pore-sized zeolites have been found to be as effective as mesoporous crystalline materials such as MCM-41. Because of this, the pore size of the sieve turned out to be insignificant.

Zeolites having properties consistent with the presence of large pore (12 ring) structures that can be used to prepare the sulfur reduction catalysts of the present invention include various types of zeolite Y such as Y, REY, CREY, USY As well as zeolite L, zeolite beta, mordenite, including dealuminated mordenite, and zeolite ZSM-18. In general, large pore size zeolites are characterized by a pore structure with ring openings of at least 0.7 nm, and medium or middle pore size zeolites will have pore openings of at least 0.56 nm and less than 0.7 nm. Suitable mesoporous zeolites that can be used include pentasils such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-50, ZSM-57, MCM-22, MCM-49 and MCM-56. Zeolites are included, all of which are known materials. Skeletal metal elements other than aluminum, such as zeolites having boron, gallium, iron, chromium, can be used.

Since zeolite USY is usually used as the active decomposition component of the cracking catalyst, it is particularly preferable to use the zeolite USY, thus making it possible to use a sulfur reducing catalyst in the form of an integrated cracking / sulfur reducing catalyst. The USY zeolites used to decompose the component can also be used as a sieve component for the separated particle additive catalyst because it more advantageously continues to contribute to the decomposition activity of the entire catalyst present in the unit. The stability is related to the low unit cell size of USY, and for optimal results the UCS should be 2.420-2.460 nm, preferably 2.420-2.455 nm for USY zeolites of the processing catalyst, Very suitable is a range from 2.420 to 2.445 nm, preferably 2.435 to 2.440 nm. After exposure to repeated steaming of the FCC cycle, UCS will typically be further reduced to a final value of 2.420-2.430 nm.

In addition to zeolites, other molecular sieves may be undesirable but may be used because some acidic activity (usually measured by alpha value) has been shown to be necessary for optimal performance. Experimental data indicate that alpha values above 10 are suitable for proper desulfurization activity, and alpha values in the range of 0.2 to 2,000 are usually suitable; (Alpha tests are a common method of measuring total acidity, including both internal and external acidity of solid materials such as molecular sieves. This test is described in US Patent No. 3,354,078; Journal of Catalysis, Vol. 4, p. 527. (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), where alpha values were measured at a constant temperature of 538 ° C.). Alpha values of 0.2 to 300 represent a normal range of acidic activity for the materials used as additives.

Exemplary non-zeolitic body materials capable of providing suitable supported components for the metal component of the sulfur reduction catalyst according to the present invention include silicates of various silica-alumina ratios (eg metallosilicates and titanosilicates), metalloaluminas. Silico- referred to as nates (eg germanium aluminate), metallophosphates, metal integrated aluminophosphates (MeAPO and ELAPO), metal integrated silicon aluminophosphates (MeAPSO and ELAPSO), silica aluminophosphates (SAPO) And aluminophosphates, such as metalloaluminophosphates, gallogerates, and combinations thereof. For a description of the structural relationships of SAPO's, AIPO's, MeAPO's and MeAPSO's, see Stud. Surf. Catal. 37 13-27 (1987)]. AIPO's contain aluminum and phosphorus, while in SAPO's some of the phosphorus and / or aluminum and some of the phosphorus have been replaced with silicon. In MeAPO's various metals such as Li, B, Be, Mg, Ti, Mn, Fe, Co, An, Ga, Ge and As are present in addition to aluminum and phosphorus, while MeAPSO'S further contains silicon. The negative charge of the Me _a Al _b P _c Si _d O _e lattice is canceled by cations (where Me is magnesium, manganese, cobalt, iron and / or zinc). Me _x APSO's is described in US Pat. No. 4,793,984. SAPO-type sieve materials are described in US Pat. No. 4,440,871; MeAPO-type catalysts are described in US Pat. Nos. 4,544,143 and 4,567,029; ELAPO catalysts are described in US Pat. No. 4,500,651; And ELAPSO catalysts are described in European Patent Application No. 159,624. Specific molecular sieves are described, for example, in the following patents: MgAPSO or MAPSO-US Patent 4,758,419, MnAPSO-US Patent 4,686,092, CoAPSO-US Patent 4,744,970, FeAPSO-US Patent 4,683,217 and ZnAPSO- United States Patent No. 4,935,216. Specific silicoaluminophosphates that may be used include SAPO-11, SAPO-17, SAPO-34, SAPO-37; Other specific body materials include MeAPO-5 and MeAPSO-5.

Another class of crystalline supported materials that can be used are the mesoporous crystalline material groups exemplified by the MCM-41 and MCM-48 materials. Such mesoporous crystalline materials are described in US Pat. No. 5,098,684; 5,102,643 and 5,198,203. MCM-41, described in US Pat. No. 5,098,684, is characterized by a microstructure with a uniform hexagonal arrangement with a pore diameter of at least 1.3 nm: it is X- having a d-spacing of at least one greater than 1.8 nm after calcination. Hexagonal electron diffraction patterns that can be indexed to d100 values greater than 1.8 nm corresponding to the d-spacing of the peaks in the line diffraction pattern and the X-ray diffraction pattern. Other metallosilicates may also be used but the preferred form of contact of this material is aluminosilicate. MCM-48 has a cubic structure and can be manufactured by a similar manufacturing method.

Metal

The catalyst composition of the present invention is prepared by impregnating two metal components into a molecular sieve supported material. One component is a rare earth such as lanthanum or a mixture of rare earth elements such as cerium and lanthanum. Although the manner in which sulfur is reduced is not clear, the other metal components described in U.S. Application Serial No. 09 / 144,607 (see the section describing sulfur reduction catalyst compositions containing vanadium and other metal components effective for sulfur reduction purposes) are the main sulfur. Can be considered as a reducing component. For convenience, the components of the composition will be referred to herein as the main sulfur reducing component. For effectiveness, the metal or metals must be present inside the pore structure of the sieve component. Metal-containing zeolites and other molecular sieves (1) post-add metal to a catalyst containing a sieve or sieve (s), and (2) sieve (s) containing metal atoms in the framework structure And (3) a sieve in which bulky metal ions are trapped in the zeolite pores. After the metal component has been added, it must be washed to remove unbound ionic groups, and to be dried and calcined. All of these techniques are known per se. Post-addition of metal ions is preferred because it is simple and economical and can be converted to the sieve material for use in the additives of the invention. Post-addition of various metals to prepare the catalysts of the present invention, such as aqueous exchange of metal ions, solid-state exchange with metal halide salt (s), impregnation with metal salt solutions, and vapor deposition of metals This can be used. However, in each case, it is important to carry out the metal (s) addition so that the metal component enters the pore structure of the sieve component.

When the metal of the main sulfur reducing component is present as an exchange cation species in the pores of the sieve component, the hydrogen transfer activity of the metal component can be maintained at a satisfactorily low level by which the hydrogen transfer reaction that occurs during the decomposition process is usually desired. It was found to decrease to the point. Thus, coke and light gases increase slowly during decomposition but remain within acceptable levels. In some cases serious loss of gasoline range hydrocarbons formed by using the additives of the present invention does not occur because unsaturated light fractions are used as alkylation feeds and can thus be recycled to the gasoline pool.

Due to the concern that excessive coke and hydrogen will be produced during the decomposition process, the metals impregnated with the additives should not exhibit a significant degree of hydrogenation activity. For this reason, precious metals such as platinum and palladium with strong hydrogenation-dehydrogenation functionality are undesirable. Combinations of base metals and base metals with strong hydrogenation functionality, such as nickel, molybdenum, nickel-tungsten, cobalt-molybdenum and nickel-molybdenum, are not preferred for the same reason. Preferred base metals are metals of Groups 5, 8, 9, 12, 13 (IUPAC classification, preferably Groups VB, VIII, IIB, IIIA) of the four cycles of the periodic table. Vanadium, zinc, iron, cobalt and gallium are effective and vanadium is the preferred metal component. It is surprising that vanadium can be used in FCC catalyst compositions in this manner because vanadium is usually thought to have a very dangerous effect on zeolite cracking catalysts and a great deal of effort must be spent in developing vanadium inhibitors. See, eg, Wormsbecher et al. Vanadium Poisoning of Cracking Catalysts: Mechanism of Poisoning and Design of Vanadium Tolerant Catalyst System, J. Catalysis 100, 130-137 (1986)]. The vanadium position in the pore structure of the sieve is believed to prevent vanadium from becoming vanadium acid species that may bind adversely to the sieve component; In any case, the sulfur reduction catalysts based on the zeolites of the present invention containing vanadium as the metal component maintain a characteristic zeolite structure between the typical reducing and oxidation / steaming conditions of the FCC cycle, representing different environments for the metal. It is circulated repeatedly.

Vanadium is particularly suitable for reducing gasoline sulfur when supported on zeolite USY. The yield construction of the V / USY sulfur reduction catalyst is of particular interest. Other zeolites after metal addition show a reduction in gasoline sulfur, but tend to convert gasoline to C ₃ and C ₄ gases. The switch C ₃ ^- and C ₄ ^- even though much of this can be alkylated and can be remixed back pool gasoline, higher C _4, because the majority of the refineries are limited his habits gas compressor ^capacity-wet gas yield is concerned Can be. Metal-containing USY has a similar yield configuration to current FCC catalysts; An advantage of this is that the V / USY zeolite content in the catalyst mixture can be adjusted to the desired desulfurization level without FCC unit restraint. Thus, vanadium on the Y zeolite catalyst, in which the zeolite is represented by USY, is particularly preferred for reducing gasoline sulfur in the FCC. USY found to give particularly good results is USY having a unit cell size in the range of 2.420 to 2.460 nm, preferably 2.420 to 2.450 nm, for example 2.435 to 2.450 nm (after treatment). Combinations of base metals such as vanadium / zinc may also be preferred in terms of total sulfur reduction.

The amount of the first sulfur reducing metal component in the sulfur reducing catalyst is generally 0.2 to 5% by weight, typically 0.5 to 5% by weight (relative to the weight of the sieve component as metal), but an amount outside this range, for example It has been found that 0.10 to 10% by weight can still exhibit some degree of sulfur reduction effect. If the sieve is matrixed, the amount of the first sulfur reducing metal component shown relative to the total weight of the catalyst composition will typically be from 0.1 to 5% by weight, more typically from 0.2 to 2% by weight of the total catalyst for the practical purpose of the formulation.

The second metal component in the sulfur reducing additive catalyst composition comprises rare earth metal (s) present within the pore structure of the molecular sieve and is believed to be in cation form exchanged on exchangeable positions present on the sieve component. do. The rare earth (RE) component significantly improves catalyst stability in the presence of vanadium. For example, with the RE + V / USY catalyst, the gasoline sulfur can be comparably reduced while the V / USY catalyst is used, while the cracking activity can be higher. For this purpose, lanthanides of the element number 57 to 71 such as lanthanum, cerium, dysprosium, praseodymium, samarium, europium, gadolinium, ytterbium and lutetium can be used, but considering the commercial availability, lanthanum and cerium Mixtures of and lanthanum will generally be preferred. From the standpoint of sulfur reduction and catalyst stability, cerium has been found to be the most effective rare earth component and, therefore, it is preferable to use cerium, although excellent results can be obtained using other rare earth elements as described below.

The amount of rare earths is typically from 1 to 10%, in most cases 2 to 5% by weight of the catalyst composition. By weight of the sieve, the amount of rare earths will generally be from 2 to 20% by weight and in most cases from 4 to 10% by weight, depending on the sieve: matrix ratio. Cerium may be used in an amount of 0.1 to 10% by weight, generally 0.25 to 5% by weight of the catalyst composition, and will generally be 0.2 to 20% by weight and in most cases 0.5 to 10% by weight relative to the sieve.

The rare earth component may be impregnated into the molecular sieve component, suitably in the form of crystalline or matrixed catalyst that is not matrixed by exchange on a sieve. When the composition is formulated with a preferred USY zeolite sieve, a very effective impregnation method is to add rare earth ions to the USY sieve (typically 2.445 to 2.465 nm unit cell size), followed by further steam calcination to achieve a unit cell size of USY. To a value of 2.420 to 2.460 nm (the first metal component can then be added if not present). USY should have a low alkali metal (primarily sodium) content not only for stability but also for satisfactory decomposition activity; This will usually be done by performing an ammonium exchange during the ultrastabilization process to lower the sodium to the desired level on the body to less than 1% by weight, preferably less than 0.5% by weight.

Metal components are impregnated into the catalyst composition such that they are introduced into the internal pore structure of the sieve. The metal may be impregnated directly, in crystallized or matrixed catalyst. If a preferred USY zeolite is used as the sieve component, it is suitably calcined to a low unit cell size of the USY cracking catalyst containing the rare earth component, and then under conditions such that cation exchange of metals such as vanadium occurs. Impregnation by ion exchange or incorporation may be performed to immobilize metal ions within the pore structure of the zeolite. In addition, after the calcining, the first sulfur reducing component and the rare earth metal component are impregnated into a sieve component such as USY zeolite or ZSM-5 crystals to remove organics from the composite, and then the decomposition and matrix components are added to form the metal-containing component. The final catalyst can be formulated into the processed catalyst composition and the formulation spray dried.

When the catalyst is formulated into an integrated catalyst system, the active decomposition component of the catalyst, in the form of faujasite, preferably zeolite USY, is used as a sieve component of the sulfur reduction system for ease of manufacture and maintenance of controlled decomposition properties. It is preferable. However, it is possible to impregnate an integrated catalytic system with other active decomposer materials, such as zeolite ZSM-5, which can be useful when the properties of the second active material, such as the properties of ZSM-5, are desired. The incorporation / exchange process should be carried out in both cases by adjusting the amount of metal to leave the required number of sites on the sieve to facilitate the degradation reactions that may occur from the active degradation components or the secondary degradation components present, for example ZSM-5. .

Use of Sulfur Reduction Catalyst Composition

In general, the most convenient way to use sulfur reducing catalysts would be to use them as separate particle additives for catalyst inventories. In its preferred form, when using zeolite USY as a sieve component, adding catalyst additives to the total catalyst inventory of the unit will not significantly reduce the total degradation due to the decomposition activity of the USY zeolite. The same applies to the case where other active decomposition substances are used as the sieve component. When used in this way, they can also be used in the form of pure body crystals that have been sized and pelletized (without the matrix but added with a metal component) for FCC use. Metal-containing materials will generally be matrixed to achieve sufficient particle wear resistance to maintain satisfactory fluidization. In general, conventional cracking catalyst matrix materials such as clay-added alumina or silica-alumina will be suitable for this purpose. The amount of matrix replacement may generally be in a 20:80 to 80:20 weight ratio. Conventional matrixing techniques can be used.

Use as a separate particle catalyst additive allows the ratio of sulfur reducing component and cracking catalyst component to be optimized depending on the amount of sulfur in the feed and the desired degree of desulfurization. When used as such, additives are typically used in FCCU in amounts of 1-50% by weight relative to the total catalyst inventory; In most cases the amount will be between 5 and 25% by weight, for example between 5 and 15% by weight. 10% represents the standard for most practical purposes. The additives may be added by conventional methods or other conventional methods of make-up of the catalyst to the regenerator. Although very much sulfur feed may lose sulfur reducing activity in a short time, the additive exhibits sulfur removal activity for a long time.

Another method of using separated particle additives is to form an integrated FCC decomposition / gasoline reduction catalyst using a sulfur reduction catalyst impregnated with the decomposition catalyst. When a sulfur reducing metal component is used in combination with a sieve other than the active decomposition component, such as ZSM-5 or zeolite beta, the amount of sulfur reduction component (sieve + metal) is typically added to the total catalyst if the main active decomposition component is USY. 25 wt% or less, which corresponds to the amount that can be used as the discrete particle additive as described above.

In addition to cracking catalysts and sulfur removal additives, other catalytically active ingredients may be present in the circulation inventory of the catalytic material. Examples of such other materials include Krishna, cited earlier in Sardebei, and Scherzer, Octane Enhancing Zeolitic FCC Catalysts, Marcel Dekker, New York, 1990, ISBN 0-8247. Bottom decomposition additives, vanadium traps, flue gas desulfurization additives such as DESOX ^™ (magnesium aluminum spinel), CO combustion promoters and supported zeolites based on supported precious metals such as platinum Octane enhancement catalysts based on ZSM-5 are included. These other ingredients can be used in their usual amounts.

The effect of the additives of the present invention is to reduce the sulfur content of liquid cracking products, in particular light and heavy gasoline fractions, although reductions have also been made in light cycle oils and high boiling distillation products including light and heavy fuel oil fractions. This makes the hydrodesulfurization easier by removing more refractory sulfur compounds. The distillation fraction can then be hydrodesulfurized under less stringent and more economical conditions to form a distillation product suitable for use as an oil mixing component for diesel or home heating.

The cracking process will be carried out in a general manner by adding the sulfur reducing catalyst in the form of an additive or as an integrated cracking / sulfur reducing catalyst (single particle catalyst). Decomposition conditions will be substantially conventional.

Sulfur removed during the cracking process using a catalyst is released as hydrogen sulfide, which can be converted to inorganic form and recovered in a typical manner in the product recovery portion of the FCCU, as is hydrogen sulfide normally released during the cracking process. Increased hydrogen sulphide loadings may require additional sour gas / water treatment, but this is unlikely to be accepted as a constraint because sulfur in gasoline is significantly reduced.

The gasoline sulfur can be significantly reduced by using the catalyst of the present invention in the form of a preferred catalyst as described above with a constant conversion rate (in some cases in an amount of up to 50% relative to the control with a conventional cracking catalyst). As illustrated in the examples below, the majority of additives according to the invention can be used to easily achieve a gasoline sulfur reduction of 25%. In the case of an intermediate distillation fraction comprising an LCO fraction, as shown in the examples below, the level of refractory sulfur compounds, including alkyl substituted benzothiophenes and dibenzothiophenes, may be reduced and sulfur may be reduced to 25% by weight or less. . The degree of sulfur reduction may depend on the initial organic sulfur content of the cracking feed, with the greatest reduction occurring when the sulfur feed is higher. The metal content of the equilibrium catalyst in the unit can also affect the desulfurization achievement, and more desulfurization occurs when the metal content, especially vanadium content, is low on the equilibrium catalyst. Although the catalyst of the present invention remains effective even when the E-catalyst vanadium content is above 1,000 ppm, desulfurization will be very effective when the E-catalyst vanadium content is below 1,000 ppm. If the cracked gasoline end point of the refinery is limited by the sulfur content of the heavy gasoline fraction, sulfur reduction can be effective not only in improving product quality but also in increasing product yield; By providing an effective and economical way to reduce the sulfur content of the heavy gasoline fraction, it is possible to extend the gasoline endpoint without performing expensive hydrotreatment, which can provide a beneficial effect on the refinery economy. If subsequent hydrotreatment is expected, it is also desirable to remove various thiophene derivatives that are difficult to hydrotreat under less severe conditions.

Example 1

Preparation of the First Catalyst

All samples of the first catalyst system were made from a single source of spray dried material consisting of 50% USY, 21% silica sol and 29% clay. The USY has a starting unit cell size of 2.454 nm, a SiO ₂ / Al ₂ O ₃ molar ratio of 5.46 and a total surface area of 810 m ² g ⁻² .

The spray dried catalyst mentioned above was slurried with NH ₄ OH at pH 6, filtered, ammonium sulfate exchange was performed and washed with water to prepare a V / USY catalyst (catalyst A). The catalyst was calcined for 2 hours in the presence of steam at 1300 ° F. and then impregnated with vanadil oxalate. Steam calcination reduces the unit cell size of the zeolite and improves its stability in the presence of vanadium.

A V / USY catalyst (catalyst B) was prepared in the same manner as catalyst A, except that initial slurrying of the catalyst was performed at pH 3.2 to 3.5.

After ammonium exchange sulfuric acid catalyst was exchanged with a solution of rare earth chloride, respectively 2 and 4 except that the addition of% of RE ₂ O ₃ by weight and the RE + V / USY catalyst in the same way as catalyst B (catalyst on the catalyst C and D ) Was prepared. The rare earth solution used contains only a small amount of Ce ions because part of its Ce ³⁺ has been extracted.

After ammonium sulfate exchange, the catalyst was exchanged with a solution of cerium chloride to prepare a Ce + V / USY catalyst (catalyst E) in the same manner as for catalyst B, except adding 5% of cerium (as CeO ₂ ) on the catalyst. .

These catalysts were then steam deactivated at 770 ° C. (1420 ° F.), 50% in an FCC unit using steam for 20 hours with a fluidized bed steamer to simulate catalyst deactivation. The physical properties of the calcination and steam deactivated catalysts are summarized in Table 1 below.

Table 1

Physical Properties of V, RE + V and Ce + V USY / Silica Sol Catalysts (First Series)

Example 2

Preparation of Second Catalyst System

V / USY catalyst (catalyst F) was prepared using USY zeolite with a silica-to-alumina ratio of 5.4 and a unit cell size of 2.435 nm. A flow catalyst was prepared by spray drying an aqueous slurry containing 50% by weight USY crystals in a silica sol / clay matrix. The matrix contains 22 wt% silica sol and 28 wt% kaolin clay. The spray dried catalyst was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ , followed by drying. The USY catalyst was then impregnated with a vanadium oxalate solution to incorporate V by 0.5 weight percent.

RE + V / USY catalyst (catalyst G) was prepared using USY zeolite with a silica-to-alumina ratio of 5.5 and a unit cell size of 2.454 nm. US ₄ was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ . NH ₄ ⁺ exchanged USY was then exchanged with a solution of mixed rare earth chlorides to rare earth cations (eg, La ³⁺ , Ce ^3+, etc.). The rare earth solution used contains almost no Ce since most of its Ce ³⁺ has been extracted. The RE-exchanged USY was further washed, dried and then calcined at 760 ° C. (1400 ° F.) in the presence of steam in a rotary calciner. Steam calcination reduced the unit cell size of the zeolite to 24.40 mm 3 and improved its stability in the presence of vanadium. A flow catalyst was prepared by spray drying an aqueous slurry containing 50% by weight of RE-USY crystals in a silica sol / clay matrix. The matrix contains 22 wt% silica sol and 28 wt% kaolin clay. The spray dried catalyst was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ , then dried and calcined at 540 ° C. (1000 ° F.) for 2 hours. After calcination, the RE / USY catalyst was impregnated with VOSO ₄ solution.

Catalyst H was prepared in a similar manner to Catalyst G, except that a mixed RECl ₃ solution containing mainly CeCl ₃ was used for USY exchange. Catalyst H was prepared using commercially available USY zeolites with a silica-to-alumina ratio of 5.5 and a unit cell size of 2.454 nm. US ₄ was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ . The NH ₄ ⁺ -exchanged USY was then exchanged with a CeCl ₃ solution containing some lanthanum. The exchanged USY was further washed, dried and then calcined at 760 ° C. (1400 ° F.) in the presence of steam in a rotary calciner. Steam calcination reduced the unit cell size of the zeolite to 2.440 mm 3. A flow catalyst was prepared by spray drying an aqueous slurry containing 50% by weight rare earth-containing USY crystals in a silica sol / clay matrix. The matrix contains 22 wt% silica sol and 28 wt% kaolin clay. The spray dried catalyst was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ , then dried and calcined at 540 ° C. (1000 ° F.) for 2 hours. After calcination, the catalyst was impregnated with VOSO ₄ solution. The physical properties of the calcined catalyst are summarized in Table 2 below.

TABLE 2

Physical Properties of V / USY and RE + V / USY Silica Sol Catalysts (Second Series)

Example 3

Preparation of the Third Catalytic System

V / USY catalyst (catalyst I) was prepared using an available H-type USY (crystal) with a bulk silica-to-alumina ratio of 5.4 and a unit cell size of 2.435 nm. A fluidized catalyst was prepared by spray drying an aqueous slurry containing 40 wt% USY crystals, 25 wt% silica, 5 wt% alumina, and 30 wt% kaolin clay. The spray dried catalyst was calcined at 540 ° C. (1000 ° F.) for 3 hours. The resulting H-type USY catalyst was impregnated with vanadium oxalate solution to incorporate 0.4 wt% V by incipient wetness impregnation. The impregnated V / USY catalyst was calcined at 540 ° C. (1000 ° F.) for 3 hours. The final catalyst contains 0.39% V.

Ce + V / USY catalyst (catalyst J) was prepared from the same spray dried H-type USY catalyst intermediate as catalyst I. Ce (NO ₃ ) ₃ solution was impregnated with H-type USY catalyst to incorporate 1.5 wt% Ce by an initial wet impregnation method. The resulting Ce / USY catalyst was calcined at 540 ° C. (1000 ° F.) for 3 hours and then steamed at 540 ° C. (1000 ° F.) for 3 hours. The vanadium oxalate solution was impregnated into the catalyst to incorporate V by 0.4 wt% by the initial wet impregnation method. The impregnated Ce + V / USY catalyst was further calcined at 540 ° C. (1000 ° 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 / Silica-Alumina-clay Catalysts (Third Series)

Example 4

Preparation of the fourth catalyst system

All samples of the fourth catalyst system were prepared from a single source of spray dried material consisting of 50% USY, 21% silica sol and 29% clay. The starting USY has a bulk silica-to-alumina ratio of 5.4 and a unit cell size of 2.435 nm. The spray dried catalyst was slurried with NH ₄ OH and (NH ₄ ) ₂ SO ₄ solution at pH 6 to remove Na ⁺ , then washed with water and calcined at 650 ° C. (1200 ° F.) for 2 hours.

V / USY catalyst (catalyst K) was prepared using the H-type USY catalyst. The vanadium oxalate solution was impregnated with H-type USY catalyst to incorporate V wt. The impregnated V / USY catalyst was air calcined at 650 ° C. (1200 ° F.) for 2 hours. The final catalyst contains 0.53% V.

Ce + V / USY catalyst (catalyst L) was prepared from the H-type USY catalyst. The CeCl ₃ solution was exchanged into the H-type USY catalyst to be 0.75% by weight Ce. The resulting Ce / USY catalyst was calcined air and the vanadium oxalate solution was impregnated to incorporate V by 0.5 wt% by initial wet impregnation. The impregnated Ce + V / USY catalyst was further air calcined. The final catalyst contains 0.72% Ce and 0.52% V.

Ce + V / USY catalyst (catalyst M) was prepared by exchanging the H-type USY catalyst with CeCl ₃ solution to impregnate 3 wt. The resulting Ce / USY catalyst was calcined air and the vanadium oxalate solution was impregnated to incorporate V by 0.5 wt% by initial wet impregnation. The impregnated Ce + V / USY catalyst was further air calcined. The final catalyst contains 1.5% Ce and 0.53% V.

Ce + V / USY catalyst (catalyst N) was prepared by impregnating the H-type USY catalyst with 1.5 wt% of CeCl ₃ solution by initial wet impregnation. The resulting Ce / USY catalyst was calcined air and the vanadium oxalate solution was impregnated to incorporate V by 0.5 wt% by initial wet impregnation. The impregnated Ce + V / USY catalyst was further air calcined. The final catalyst contains 1.5% Ce and 0.53% V.

These catalysts were then steam inactivated with a fluidized bed steamer for 20 hours using 50% steam and 50% gas at 770 ° C. (1420 ° F.) FCC unit to simulate catalyst deactivation. The gas stream was changed from air, N ₂ , propylene and N ₂ mixtures every 10 minutes to N ₂ and the air was circulated again to simulate the coking / regeneration cycle (cyclic steaming) of the FCC unit. Two sets of inactivated catalyst samples were regenerated; Steam inactivation cycles were end-aired (end-oxidized) for one catalyst batch and the other end was end-reduced with propylene (end-reduced). The coke content of the "ending-reducing" catalyst has a C of less than 0.05%. The physical properties of the calcination and steam (ending oxidation) catalysts are summarized in Table 4 below.

Table 4

Physical Properties of V and Ce + V USY / Silicazol Catalysts (Fourth Series)

Example 5

Preparation of the fifth catalyst system

All samples of the fifth catalyst system were prepared from a single source of spray dried material containing 40% USY, 30% colloidal silica sol and 30% clay. The starting H-type USY has a bulk silica-to-alumina ratio of 5.4 and a unit cell size of 2.435 nm. The spray dried catalyst was air calcined at 540 ° C. (1000 ° F.) for 3 hours.

Ce / USY catalyst (catalyst O) was prepared using the H-type USY catalyst. Ce (NO ₃ ) ₃ solution was impregnated into the H-type USY catalyst by 1.5 wt% incorporation by initial wet impregnation. The resulting Ce / USY catalyst was calcined at 540 ° C. (1000 ° F.) and then steamed at 540 ° C. (1000 ° F.) for 3 hours.

Ce + V / USY catalyst (catalyst P) was prepared from catalyst O. The Ce / USY catalyst was impregnated with a vanadium oxalate solution to incorporate V by 0.5 wt% by initial wet impregnation. The impregnated Ce + V / USY catalyst was dried and then calcined at 540 ° C. (1000 ° F.) for 3 hours. The final catalyst contains 1.4% Ce and 0.49% V.

Ce + V / USY catalyst (catalyst Q) was prepared by exchanging catalyst O with 0.5 wt% of V in a VOSO ₄ solution at pH about 3. The resulting Ce + V / USY catalyst was dried and then calcined at 540 ° C. (1000 ° F.) for 3 hours. The final catalyst contains 0.9% Ce and 0.47% V. The physical properties of the calcined catalyst are summarized in Table 5 below.

Table 5

Physical Properties of Ce and Ce + V USY / Silica Clay Catalysts (Fifth Series)

Example 6

Preparation of RE + V / USY / Silicazol Catalysts

RE + V / USY catalyst (catalyst R) was prepared using NaY zeolite with a silica-to-alumina ratio of 5.5 and a unit cell size of 2.465 nm. Zeolite Y was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ . The NH ₄ ^{+ -exchanged} Y was exchanged for a rare earth cation (e.g., La ³⁺ , Ce ^3+, etc.) by exchange of a solution of mixed rare earth chlorides containing almost no Ce ³⁺ by extraction and almost no cerium. . The RE-exchanged Y was further washed, dried and then calcined at 705 ° C. (1300 ° F.) for 2 hours in the presence of steam. Steam calcination reduced the unit cell size of the zeolite and improved its stability in the presence of vanadium. A flow catalyst was prepared by spray drying an aqueous slurry containing 50% by weight of RE-USY catalyst in a silica sol / clay matrix. The matrix contains 22 wt% silica sol and 28 wt% kaolin clay. The spray dried catalyst was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ , then dried and calcined at 540 ° C. (1000 ° F.) for 1 hour. After calcination, the RE / USY catalyst was impregnated with the vanadium oxalate solution. The physical properties of the calcined catalyst are summarized in Table 6 below.

Table 6

Physical Properties of RE + V / USY Silica Sol Catalysts

Example 7

Preparation of Ce + V / USY / Silicazol Catalysts

Ce + V / USY catalyst (catalyst S) was prepared using NaUSY zeolite with a silica-to-alumina ratio of 5.5 and a unit cell size of 2.454 nm. US ₄ was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ . The NH ₄ ⁺ exchanged USY small amounts of other rare earth ions: to exchange the cerium chloride solution containing (for example, La ^3+, Pr, Nd, Gd, and so on) was exchanged for Ce ³⁺ cations. The Ce-exchanged USY was further washed, dried and then calcined at 705 ° C. (1300 ° F.) for 2 hours in the presence of steam. Steam calcination reduced the unit cell size of the zeolite and improved its stability in the presence of vanadium. A flow catalyst was prepared by spray drying an aqueous slurry containing 50% by weight Ce / USY crystals in a silica sol / clay matrix. The matrix contains 22 wt% silica sol and 28 wt% kaolin clay. The spray dried catalyst was exchanged with ammonium sulfate solution to exchange NH ₄ ⁺ , then dried and calcined at 540 ° C. (1000 ° F.) for 1 hour. After calcination, the Ce / USY catalyst was impregnated with the vanadium oxalate solution. The physical properties of the calcined catalyst are summarized in Table 7 below.

TABLE 7

Physical Properties of Ce + V / USY / Silicazol Catalysts

Experimental Method: Evaluation of Degradation Performance

The catalysts of Examples 1-7 were evaluated for FCC and the results are shown in Examples 8-15. Mixed catalysts (candidate + equilibrium catalysts) were tested for gas oil decomposition activity and selectivity with an ASTM microactivity (MAT) test that modified ASTM method D-3907 using a vacuum gas oil (VGO) feed. Tested. Some additive catalysts were evaluated with a circulatory riser pilot unit using vacuum gas oil or hydrotreated feed. The composition of one severely cat feed hydrotreated feed (CFHT) and three VGO feeds used in these examples is shown in Table 8 below.

Table 8

Properties of cracking feed

The reaction was carried out at 527 ° C. (980 ° F.) with varying catalyst to oil ratios to obtain a range of decomposition conversions. The cut point range for degradation products is as follows:

Gasoline C ₅ ⁺ to 220 ° C (125 to 430 ° F)

Hard LCO 220-310 ° C. (430-590 ° F.)

Heavy LCO 310-370 ° C (590-700 ° F)

Light Fuel Oil (LFO) 220-370 ° C. (430-590 ° F.)

Heavy Fuel Oil (HFO) 370 ° C (700 ° F)

Gasoline range products from each mass balance were analyzed by sulfur GC (AED) to determine gasoline sulfur concentrations. To reduce the experimental error in sulfur concentrations due to fluctuations in the distillation cutoff of gasoline, sulfur species ranging from thiophene to C ₄ -thiophene (except benzothiophene and S species boiling at higher temperatures) in synthetic crude oil Quantify and sum to "cut-gasoline S".

In order to determine the sulfur content of the distillate fractions boiling at temperatures above the gasoline range (Examples 14 and 15), the crude oil was atmospheric distilled to separate gasoline. The bottom fraction was vacuum distilled to give two LFO / LCO fractions (light LCO and heavy LCO) and HFO. Sulfur species in the LCO samples were quantified using a GC equipped with a J & W 100 m DB-Petro column and a Sievers 355B sulfur detector. The concentration of each LCO sulfur species from GC was calculated based on the percentage of sulfur species and the total sulfur content was determined by XPS method.

Example 8

Evaluation of Flow Catalytic Decomposition of the First Catalyst

The catalyst of Example 1 was steam inactivated with a fluidized bed steamer for 20 hours using 50% steam and 50% gas at 770 ° C. (1420 ° F.) as described in Example 4 above, followed by an air-oxidation ending ( Ending-oxidation). 25 wt% of the steamed additive catalyst was mixed with an equilibrium catalyst with very low metal content (V 120 ppm and Ni 60 ppm) from the FCC unit.

Catalytic cracking performance of the catalyst was evaluated using VGO No. 1 as the cracking feed for the microactivity test. The performance of the catalyst is summarized in Table 9, where the selectivity of the product was interpolated at a constant conversion rate, ie 65% by weight conversion of the feed to materials up to 220 ° C. (430 ° F.).

Table 9

Catalytic cracking performance of the first catalyst system and the first VGO

The catalyst to oil ratios in Table 9 indicate that the mixture of V / USY and ECat inactivated for the 65% conversion requires a higher catalyst-to-oil ratio than for the 100% equilibrium catalyst control (3.3 to 3.0). Catalyst / oil, ie 10% decrease in activity). This is because the decomposition activity of V / USY is lower than that of the equilibrium catalyst. In comparison, addition of the RE + V / USY catalyst does not increase the catalyst-to-oil ratio to achieve a 65% conversion. This catalyst-to-oil ratio indicates that the RE + V / USY catalyst is more stable than the V / USY catalyst and maintains its decomposition activity much better.

Compared to the equilibrium catalyst control, the addition of V / USY and RE + V / USY catalysts slightly changes the overall product yield structure. Hydrogen and coke yields increase slightly. It has also been found that the yields of C ₄ gas, gasoline, light cycle oil and heavy fuel oil vary slightly. The addition of the V / USY and RE + V / USY catalysts substantially changes the gasoline sulfur concentration. Mixing 25% by weight of catalyst A or B (V / USY control catalyst) with the equilibrium FCC catalyst, respectively, reduces the gasoline sulfur concentrations by 39.0 and 40.8%. When 25% by weight of RE / USY catalysts (catalysts C and D) were added to the equilibrium catalyst, the gasoline sulfur reduction activity was comparable to the control catalyst (38 to 40%). The RE + V / USY catalyst (catalyst E), which mainly contains cerium as a rare earth metal, reduced the gasoline sulfur by 43.1%, further reducing the gasoline sulfur content by 4%. That is, 10% improvement over V / USY and mixed RE / USY catalysts. All catalysts have similar vanadium loadings (0.36 to 0.39%).

The above results indicate that addition of rare earth elements improves the decomposition activity of the V / USY catalyst. The change in yield of cracked products is minor. Among rare earth ions, cerium exhibits unique properties in that Ce + V / USY catalysts not only exhibit higher cracking activity but also increased gasoline sulfur reduction activity under fluid catalytic cracking conditions. Rare earth RE / USY catalysts without the addition of large amounts of cerium were less favorable than V / USY in reducing gasoline sulfur, but the presence of cerium increased the gasoline sulfur levels of V / USY or RE / USY (lower cerium levels) catalysts. Lowered.

Example 9

Comparison of Decomposition Activity of the Second Catalyst System

The V and RE / V USY catalysts from Example 2 (second catalyst system, catalysts F, G, H) were steam inactivated at various time lengths at 770 ° C. (1420 ° F.) to compare catalyst activity. The catalyst was steamed in a fluidized bed steamer for 2.3, 5.3, 10, 20 and 30 hours using 50% steam and 50% gas (cyclic steaming ending-reduction as described in Example 4 above). Surface area retention of the deactivated catalyst is shown in FIG. 2.

The steam inactivated catalyst was tested for gas oil cracking activity by ASTM microactivity test (ASTM method D-3907) using a second vacuum gas oil (mentioned above -2.6 wt% S). The weight percent conversion to 220 ° C .- (430 ° F.) at 30 seconds contact time and a reaction temperature of 545 ° C. (980 ° F.) was measured at a constant catalyst-to-oil ratio of 4: 1. The conversion is shown in FIG. 3 as a function of steam inactivation time.

Surface area retention shown in FIG. 2 shows that the V / USY and RE + V / USY catalysts exhibit similar surface area retention under various hydrothermal inactivation conditions, meaning that all three catalysts have similar framework structural stability. However, the conversion shown in FIG. 3 clearly indicates that the RE + V / USY catalyst has more enhanced degradation activity as the severity of hydrothermal destabilization increases. In hydrothermal destabilization, the degree of improvement of catalytic cracking activity was 15% when V / USY was changed to the RE + V version. There was no difference in appearance between RE versions when the amount of cerium was changed. This result is consistent with the results of Example 8, where RE + V / USY achieved the desired conversion at a catalyst-to-oil ratio lower than V / USY. The results of this conversion indicate that RE + V / USY catalysts are more stable than V / USY catalysts and maintain their decomposition stability much better. The addition of rare earth ions to USY, followed by steam calcination to reduce the unit cell size of the zeolite improves catalyst stability in the presence of vanadium.

Example 10

Evaluation of Flow Catalytic Decomposition of the Third Catalyst System

V and Ce + V USY catalysts (Catalysts I, J) from Example 3 were used for 20 hours with a fluidized bed steamer at 770 ° C. (1420 ° F.) using 50% steam and 50% gas as described in Example 4 above. After steam inactivation, it was ended (end-oxidized) with air-combustion. 25 wt% of the steamed additive catalyst was mixed with a low metal FCC equilibrium catalyst (V 120 ppm and Ni 60 ppm). The mixed catalyst was evaluated by the MAT test described above using VGO No. 1 feed.

The performance of the third catalyst system using the VGO No. 1 feed is summarized in Table 10 below, wherein the selectivity of the product is that the feed is 70% by weight converted to a constant conversion rate, ie, 220 ° C .- (430 ° F.) material. It was interpolated.

Table 10

Catalytic Cracking Performance of the Third Catalytic System

Table 10 compares the FCC performance of V / USY and Ce + V / USY / silica-alumina-clay catalysts mixed with equilibrium FCC catalysts (Ecat) after cyclic steam inactivation (end-oxidation), respectively. Compared to the ECat control, the addition of the V / USY and Ce + V / USY catalysts only slightly changed the overall product yield structure. Yield variations in C ₄ gas, gasoline, light cycle oil and heavy fuel oil are all small. Hydrogen and coke yields were moderately increased. The product yield change was small, but the V / USY and Ce + V / USY catalysts substantially changed the gasoline S concentration. Mixing 25% by weight of catalyst I (V / USY control catalyst) with the equilibrium FCC catalyst reduces the gasoline sulfur concentration by 29%. For comparison, the Ce + V / USY catalyst (catalyst J) reduced 56% of gasoline sulfur. The addition of Ce to the V / USY catalyst further reduced the gasoline sulfur content by 27%, ie 93% improvement over the V / USY control catalyst. Both catalysts have comparable vanadium loadings (0.39% vs. 0.43% V). In view of the fact that Ce itself does not have gasoline sulfur reduction activity (see Example 11 hereinafter), the above results were not unexpected at all, clearly demonstrating the advantage of cerium addition.

Example 11

Evaluation of Flow Catalytic Decomposition of the Fourth Catalytic System After Cyclic Steaming

This example summarizes the performance of the V and Ce + V catalysts from Example 4. The fourth catalyst system was steam deactivated by cyclic steaming as described in Example 4 above (ending-reduction), followed by a 25:75 weight ratio with low metal (V 120 ppm and Ni 60 ppm) FCC equilibrium catalysts. Were mixed and tested using VGO No. 1 feed. The results are summarized in Table 11 below.

Table 11

Catalytic Decomposition of V to Ce + V / USY / Silicazol Catalysts

Table 11 compares the FCC performance of the V / USY and Ce + V / USY / silicasol additive catalysts after cyclic steam inactivation (end-reduction). Compared to the ECat control, the addition of the V / USY and Ce + V / USY catalysts results in little change in overall product yield structure. Yield variations of C ₄ gas, gasoline, light cycle oil, heavy fuel oil and coke are each less than 0.2% by weight. The addition of the V / USY and Ce + V / USY catalysts changes the gasoline S concentration to a different degree. Mixing 25% by weight of catalyst K (V / USY control catalyst) with the equilibrium FCC catalyst results in a 5.2% reduction in gasoline sulfur concentration. For comparison, Ce + V / USY catalysts (catalysts M and N) reduced gasoline sulfur 17.4% respectively. Adding Ce to the V / USY catalyst further reduced the gasoline sulfur content by 12.3%, ie 237% improvement over the V / USY control catalyst.

Example 12

Evaluation of Flow Catalytic Decomposition of the Fourth Catalytic System After Cyclic Steaming

This example summarizes the performance of the V and Ce + V catalysts from Example 4 after cyclic steam deactivation. The catalyst of Example 4 was steam inactivated (ending-oxidation) by cyclic steaming as described in Example 4 above, followed by 25:75 with FCC equilibrium catalyst with low metal (V 120 ppm and Ni 60 ppm). Mix by weight ratio. The results obtained using VGO No. 1 Feed are summarized in Table 12 below.

Table 12

Catalytic Decomposition of V to Ce + V / USY / Silicazol Catalysts

Table 12 compares the FCC performance of the V / USY and Ce + V / USY / silicasol additive catalysts after cyclic steam inactivation (end-oxidation). Compared to the ECat control, the addition of the V / USY and Ce + V / USY catalysts slightly altered the overall product yield structure. Hydrogen and coke yields were moderately increased. In addition, the yields of C ₄ gas, gasoline, light cycle oil and heavy fuel oil changed slightly. The gasoline S concentration changed substantially with the addition of the V / USY and Ce + V / USY catalysts. Mixing 25% by weight of catalyst K (V / USY control catalyst) with the equilibrium FCC catalyst results in a 51.1% reduction in gasoline sulfur concentration. For comparison, Ce + V / USY catalysts (catalysts L and M) reduced gasoline sulfur by 58.1% and 61.3%, respectively. When Ce was added to the V / USY catalyst, the gasoline sulfur content was further reduced by 7.0 to 10.2%, ie up to 20% compared to the V / USY control catalyst.

Product yield data of the V / USY and Ce + V / USY catalysts indicate that the change in yield from ECat is due to the addition of vanadium to the USY catalyst. The product yield of the V / USY catalyst is comparable to that of the Ce + V / USY catalyst except for the gasoline S level. These results suggest that Ce increases the gasoline sulfur reduction activity of the V / USY additive catalyst with little effect on product yield.

Example 13

Evaluation of Flow Catalytic Decomposition of the 5th Catalytic System and Investigation of Enhancement Effect

This example summarizes the performance of Ce and Ce + V catalysts from Example 5 after cyclic steam deactivation (end-reduction) as described above. The deactivated catalyst was mixed with a low metal (V 120 ppm and Ni 60 ppm) FCC equilibrium catalyst in a 25:75 weight ratio. The results obtained using VGO No. 1 Feed are summarized in Table 13 below.

Table 13

Catalytic Cracking Performance of Ce to Ce + V / USY / Silica-Clay Catalysts

Table 13 compares the FCC performance of Ce / USY and Ce + V / USY / silica-clay additive catalysts after cyclic steam deactivation (ending-reduction). Compared with the ECat control, the addition of Ce / USY catalyst leaves little change in overall product yield structure. The addition of Ce + V / USY catalyst slightly changes the overall product yield structure. Hydrogen and coke yields were moderately increased and the yields of C ₄ gas, gasoline, light cycle oil and heavy fuel oil were slightly changed. Gasoline S concentration did not change when Ce / USY catalyst was added. In contrast, the addition of Ce + V / USY catalysts (catalysts P and Q, the invention) reduced gasoline S by 29.8% and 27.7%, respectively. This result indicates that cerium itself does not have gasoline sulfur reduction activity. Cerium has an enhancing effect of increasing the activity of the V / USY gasoline sulfur reducing additive catalyst against vanadium.

Example 14

Catalyst R was evaluated in a Circulating Riser Pilot Unit in combination with a typical FCC equilibrium catalyst using VGO No. 3 feed (Table 8). Prior to evaluation, the RE + V USY catalyst was steam deactivated for 20 hours using 50% steam and 50% gas at 770 ° C. (1420 ° F.). 25 wt% of the steamed additive catalyst was mixed with the equilibrium catalyst (V 530 ppm and Ni 330 ppm) from the FCC unit.

The FCC performance of the catalysts is summarized in Table 14, where the selectivity of the product was interpolated at a constant conversion rate, ie 75% by weight conversion of the feed to a material of 220 ° C .- (430 ° F.).

Table 14

Catalytic Decomposition of RE + V / USY / Silicazol Catalysts

Compared to the control, the addition of 25% by weight of the RE + V / USY catalyst slightly changes the overall product yield structure. H ₂ and coke yields are negligibly increased. It was also observed that the yields of C ₄ gas, gasoline, light cycle oil and heavy fuel oil hardly changed. The addition of RE + V / USY catalyst changed the gasoline sulfur concentration substantially and the gasoline sulfur concentration decreased by 20%. In addition to gasoline sulfur reductions, substantial sulfur reductions have occurred in the LCO (corresponding to a 9% total LCO sulfur reduction).

Sulfur species in LCO are shown in Table 15 and FIG. 4. LCO contains a wide range of benzothiophene and dibenzothiophene sulfur species. Sulfur reduction phenomenon ⁺ C ₃ - it was more pronounced in the dibenzothiophene and substituted benzothiophene and substituted dibenzothiophene same-benzothiophene, and C ₁ - to C ₄ ^+. This result was totally unexpected because the substituted dibenzothiophenes are expected to be bulkier and more difficult to decompose and desulfurize in the FCC.

Table 15

Sulfur Composition of LCO from Third VGO Feed

Example 15

Evaluation of Fluid Catalytic Decomposition of Ce + V / USY / Silicazol Catalysts

The Ce + V / USY catalyst from Example 7 (catalyst S) was combined with a typical FCC catalyst using a strictly hydrotreated FCC feed of Table 8 (CHFT feed) and evaluated for 40 days in a circulating flow cracking unit. . The control FCC equilibrium catalysts have very low metal levels (V 200 ppm and Ni 130 ppm). During the first 15 days, a 50/50 mixture of fresh FCC catalyst and Ce + V / USY catalyst from Example 7 was added daily to the FCC regenerator with 1.4% catalyst inventory. From 15 to 40 days, a 85/15 mixture of fresh FCC catalyst and Ce + V / USY catalyst was added daily to the FCC regenerator with a 1.4% catalyst inventory. The regenerator temperature was maintained at about 705 ° C. (1300 ° F.) during the evaluation. Two equilibrium catalyst (ECat) samples were collected: the first catalyst was the sample (control) prior to the addition of Ce + V / USY, and the second catalyst was at day 40. Based on the Ce and V analysis, the loading of Ce + V / USY catalyst was estimated to be 12%.

The FCC performance of the catalysts is summarized in Table 16 below, where the selectivity of the product was interpolated at a constant conversion rate, ie 70% by weight conversion of the feed to a material of 220 ° C .- (430 ° F.).

Table 16

Catalytic Decomposition of Ce + V / USY / Silicazol Catalysts

Compared to the ECat control, the addition of Ce + V / USY catalyst slightly changes the overall product yield structure. H ₂ and coke yields are negligibly increased. It was also observed that the yields of C ₄ gas, gasoline, light cycle oil and heavy fuel oil hardly changed. Gasoline sulfur concentrations varied substantially with the addition of the Ce + V / USY catalyst. When 12% by weight Ce + V / USY catalyst is mixed with the equilibrium FCC catalyst, the gasoline sulfur concentration is reduced by 21%. In addition to gasoline sulfur reductions, significant sulfur reductions were observed in LCO and HFO.

Sulfur species in hard LCO were analyzed using sulfur GC. The concentration of each organic sulfur group is shown in Table 17, and the light LCO is shown in FIG.

Table 17

Sulfur Composition of Light LCO from CHFT Feed

As shown in FIG. 5, the hard LCO contains predominantly benzothiophene sulfur species. The sulfur reduction, corresponding to a total 27% reduction in light LCO, was more pronounced for substituted benzothiophenes such as C ₁ -to C ₃ ⁺ -benzothiophenes. This result was totally unexpected because the substituted benzothiophene is expected to be bulkier and more difficult to decompose and desulfurize in the FCC.

Sulfur species in the heavy LCO fractions are shown in Table 18 and FIG. 6. Heavy LCO mainly contains dibenzothiophene sulfur species. Sulfur reduction (14% total for heavy LCO) was more pronounced for substituted dibenzothiophenes such as C ₁ -to C ₄ ⁺ -dibenzothiophenes. This result was totally unexpected because the substituted dibenzothiophenes are expected to be bulkier and more difficult to decompose and desulfurize in the FCC.

Table 18

Sulfur Composition of Heavy LCO from CHFT Feed

Sulfur reduction catalysts are active in reducing benzothiophene and dibenzothiophene sulfur species as well as thiophene sulfur species. Sulfur reduction occurs predominantly in substituted benzothiophenes and substituted dibenzothiophenes. These results indicate that the C-S bonds of alkyl substituted thiophenes are more reactive and therefore more degraded.

The ease of sulfur reduction of substituted thiophenes, substituted benzothiophenes and substituted dibenzothiophenes was unexpected at all and would increase the efficiency of subsequent LCO hydrodesulfurization processes. In the LCO hydrodesulfurization process, the methyl and / or alkyl substitution of benzothiophene and dibenzothiophene substantially degrades the desulfurization reactivity of the organic sulfur and results in "hard sulfur" or "hard sulfur". Is already known. LCOs of the present invention containing small amounts of substituted benzo and dibenzothiophene form diesel fuels having a lower sulfur content than the comparable LCO produced using conventional FCC catalysts after hydrodesulfurization. something to do.

Claims (35)

(i) a first metal component located within the pore structure of the molecular sieve and containing a metal in an oxidation state greater than zero and (ii) a second metal component located within the pore structure of the molecular sieve and containing at least one rare earth. Catalytically cracked petroleum, characterized by catalytic cracking of the petroleum feed fraction containing organosulfur compounds at elevated temperatures in the presence of a product sulfur reducing catalyst and a decomposition catalyst comprising a porous molecular sieve. A method for reducing the sulfur content in fractions. 2. The process of claim 1 wherein the product sulfur reduction catalyst contains a large pore or medium pore size zeolite as the molecular sieve component and at least one of vanadium, zinc, iron, cobalt and gallium as the first metal component. . 3. The method of claim 2, wherein the large pore size zeolite comprises pauzasite zeolite. The method of claim 2 wherein the first metal component comprises vanadium. The method of claim 2 wherein the second metal component comprises lanthanum alone or in combination with cerium. The method of claim 2 wherein the second metal component comprises cerium. The method of claim 1 wherein the second metal component is present in an amount from 1 to 10 weight percent of the catalyst composition. The zinc and vanadium of claim 1, wherein the product sulfur reduction catalyst contains, as a molecular sieve component, a USY zeolite having a UCS of 2.420 to 2.460 nm and a bulk silica: alumina ratio of at least 5.0, and a first metallic component of greater than zero zinc and vanadium. At least one of the above, and containing cerium alone or in combination with lanthanum as the second metal component. The process of claim 1 wherein the sulfur reduction catalyst is a separate particle additive catalyst. 2. The process of claim 1 wherein the liquid decomposition product with reduced sulfur content comprises a gasoline fraction, a cycle oil fraction and a fuel oil fraction, wherein the cycle oil and fuel oil boiling points are higher than the gasoline fraction. (i) a cracking zone effluent comprising cracked catalyst and cracked products containing coke and strippable hydrocarbons by cracking the feed in contact with a source of regenerated cracking catalyst in a catalytic cracking zone operating under catalytic cracking conditions; To obtain; (ii) draining the effluent mixture to separate into cracked product-rich vapor phases and spent catalyst containing solids-rich phases; (iii) separating the vapor phase as a product, and then fractionating the vapor to obtain a liquid decomposition product comprising gasoline; (iv) removing the solid catalyst rich catalyst bed to remove occluded hydrocarbons from the catalyst; (v) conveying the stripped catalyst from the stripper to the catalyst regenerator; (vi) contacting the stripped catalyst with an oxygen-containing gas to regenerate the catalyst, (vii) recycle the regenerated catalyst to the cracking zone and contact with an additional amount of heavy hydrocarbon feed, A fluid catalytic cracking process wherein a heavy hydrocarbon feed containing an organosulfur compound is contacted with a fluidized cyclic catalytic cracking catalyst inventory consisting of particles of 20 to 100 microns in size in a cyclic catalytic recycle cracking process to decompose into light products. Catalytic decomposition involves (i) a first metal component located within the pore structure of the molecular sieve and containing a metal in an oxidation state greater than zero and (ii) a second metal located within the pore structure of the molecular sieve and containing at least one rare earth. A process for reducing the sulfur content of a liquid decomposition product, carried out in the presence of a product sulfur reduction catalyst comprising a porous molecular sieve having a component. The method of claim 11, wherein the decomposition catalyst comprises matrix fausite zeolite. 13. The product sulfur reducing catalyst of claim 12, wherein the product sulfur reduction catalyst contains a large pore size or a medium pore size zeolite as the molecular sieve component, contains vanadium as the first metal component and cerium alone or at least one as the second metal component. A method containing in combination with other rare earth metals. The method of claim 13, wherein the large pore size zeolite of the product sulfur reduction catalyst comprises a pausiteite zeolite. 12. The method of claim 11, wherein the first metal component comprises vanadium. The method of claim 11, wherein the second metal component comprises lanthanum alone or in combination with cerium. The method of claim 11, wherein the second metal component comprises cerium. The method of claim 11, wherein the second metal component is present in an amount from 1 to 10 weight percent of the catalyst composition. 12. The process of claim 11 wherein the liquid decomposition product comprises a gasoline fraction having a reduced sulfur content and a cycle oil fraction having a lower boiling sulfur content than a gasoline fraction. (i) a porous molecular sieve component, (ii) a first metal component located within the pore structure of the porous molecular sieve component and containing a metal component with an oxidation state greater than zero and (iii) within the pore structure of the porous molecular sieve component Catalytic cracking product sulfur reduction to reduce the sulfur content of the catalytically cracked gasoline fraction during the catalytic cracking process, characterized in that it comprises 20 to 100 micron size flowable particles of a second metal component containing a rare earth metal located therein. Flowable catalyst composition for. 21. The fluid catalyst composition of claim 20, wherein the porous molecular sieve component comprises a porous hydrocarbon cracker component. 22. The fluid catalytic composition of claim 21, wherein the porous molecular sieve component comprises a USY zeolite having a UCS of 2.420 to 2.460 nm and a bulk silica: alumina ratio of at least 5.0. 23. The fluid catalyst composition of claim 22, wherein the porous molecular sieve component comprises USY zeolite having a UCS of 2.420 to 2.435 nm and a bulk silica: alumina ratio of at least 5.0. 21. The fluid catalyst composition of claim 20, wherein the first metal component contains vanadium as 0.1 to 5% by weight, based on the weight of the zeolite. 25. The fluid catalyst composition of claim 24 comprising a combination of cerium and at least one other rare earth as a second metal component. The fluid catalyst composition of claim 20 comprising cerium as the second metal component. 21. The fluid catalyst composition of claim 20, wherein the metal components are introduced into the zeolite as cationic species exchanged in the zeolite pores. The fluid catalyst composition of claim 20 formulated with the matrix component as a fluid decomposition catalyst additive. A zeolitic molecular sieve containing in the zeolite pore structure a first metal component comprising (i) at least one of vanadium, zinc, iron, cobalt and gallium and (ii) a second metal component comprising at least one rare earth. A heavy hydrocarbon feed is decomposed to produce a liquid decomposition product including gasoline, characterized in that it comprises 20 to 100 micron size flowable particles of a hydrocarbon decomposition component comprising a sulfur content in the catalytically cracked gasoline fraction during the catalytic cracking process. A flow catalyst for catalytic cracking product sulfur reduction according to claim 20 formulated as an integrated flow catalytic cracking / product sulfur reduction catalyst for reducing. 30. The integrated fluid catalytic cracking / product sulfur reduction catalyst according to claim 29, comprising 0.1 to 5% by weight based on the zeolite weight of vanadium as the first metal component. 30. The integrated fluid catalytic cracking product sulfur reduction catalyst according to claim 29, comprising from 1 to 5% by weight of the combination of cerium and at least one other rare earth as a second metal component relative to the catalyst. 30. The integrated fluid catalytic cracking product sulfur reduction catalyst of claim 29 comprising a blend of cerium as the second metal component in an amount of 1 to 5 weight percent based on the catalyst. 30. The integrated fluid catalytic cracking product sulfur reduction catalyst of claim 29, wherein the zeolitic molecular sieve comprises a USY zeolite having a UCS of 2.420 to 2.460 nm and a bulk silica: alumina ratio of at least 5.0. The fluid catalytic cracking product sulfur reduction catalyst composition of claim 32, wherein the porous molecular sieve component comprises a USY zeolite having a UCS of 2.420 to 2.435 nm and a bulk silica: alumina ratio of at least 5.0. 30. The fluid catalytic cracking product sulfur reduction catalyst of claim 29, formulated as a fluid cracking / sulfur reducing catalyst integrated with the faujasite zeolite and matrix component as cracking components.