TW527413B - Method of reducing the sulfur content of a catalytically cracked petroleum fraction, fluid catalytic cracking process and fluidizable catalytic cracking product sulfur reduction catalyst composition for reducing the sulfur content - Google Patents

Abstract

The sulfur content of the liquid cracking products of the catalytic cracking process is reduced by the use of a sulfur reduction catalyst composition comprising a porous molecular sieve which contains a metal in an oxidation state above zero within the interior of the pore structure of the sieve as well as a rare earth component which enhances the cracking activity of the cracking catalyst. The molecular sieve is normally a faujasite such as USY. The primary sulfur reduction component is normally a metal of Period 4 of the Periodic Table, preferably vanadium. The preferred rare earth metal is cerium. The sulfur reduction catalyst may be used in the form of a separate particle additive or as a component of an integrated cracking/sulfur reduction catalyst.

Description

527413 Amendment No. 88123132 V. Description of the invention (1) The present invention relates to the reduction of sulfur in gasoline and other petroleum oil products produced by the catalytic cracking method. The present invention provides a catalytic composition for reducing product sulfur and a method for using the composition to reduce product sulfur.

Catalytic cracking is a petroleum refining method that is commercially used on a very large scale, especially in the United States. Most refinery gasoline blending tanks are produced by catalytic cracking, and almost all of them are produced by fluids. Chemical catalytic cracking (FCC) method. In the catalytic cracking method, heavy hydrocarbon fractions are converted into lighter products through reactions carried out at high temperatures and in the presence of catalysts. Most of the conversion or cracking occurs in the gas phase. The feedstock is thus converted into gasoline, distillates and other liquid cracking products, as well as lighter gaseous cracking products containing 4 or fewer carbon atoms per molecule. The gas system consists partly of olefins and partly of saturated hydrocarbons. During the cracking reaction, a heavy substance, called coke, is deposited on the catalyst. This reduces the catalytic activity and requires regeneration. After self-waste cracking catalyst removes adsorbed hydrocarbons, regeneration is completed by burning off coke, and then the catalyst activity is restored. Therefore, the three characteristic steps of catalytic cracking can be distinguished: the cracking step of converting hydrocarbons into lighter products, the desorption step of removing hydrocarbons adsorbed on the catalyst, and the regeneration step of burning coke from the catalyst. The regenerated catalyst is then reused in the cracking step.

Catalytic cracking feedstock typically contains sulfur in the form of organic sulfur, such as mercaptans, sulfides, and thiophenes. The product of the cracking method correspondingly contains sulfur impurities. Even if about half of the sulfur is converted into hydrogen sulfide during the cracking process, it is mainly due to the catalytic decomposition of non-thiophene sulfur compounds. The distribution of sulfur in the cracked product depends on many factors, including feed, dissolution type, additives, conversion and other operating conditions, but in any case, some proportion of sulfur will still be

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Case No. 88123132 V. Description of the invention (2) The light or heavy gasoline distillate is passed through the product tank. As more and more environmental regulations are imposed on oil products, such as in the Reformed Gasoline Regulations (= RF ^, Reformulated Gasoline regulations), sulfur oxides and other sulfur compounds are emitted to the air center after a combustion process Concerns' The sulfur content in the product has generally been reduced. Gasoline sulfur reduction ^ Only M SOX emissions are also important for sulfur poisoning of automotive catalytic converters. Catalytic converter poisoning can cause other emissions issues such as NOx. In view of the significant position of Power A / used as fuel for wheels of manned vehicles in the United States, environmental concerns have been widely focused on the sulfur content of power gasoline. However, these concerns have also been extended to high boiling point fractions including light cycle oils (LC0) and fuel oil fractions (light fuel oils, Lf0, and Renjin fuel oils' HF0). These products have long used hydrodesulfurization to reduce the sulfur content of the product fractions, which has generally proven effective. However, the boiling point fraction is not as easy to remove from the bowl as the low boiling point fraction. It is ^ in sulfur = compound-especially the substituted benzothiophene with increasing boiling point. The reason for the shell. During the LC 0 deaeration process, the substitution of methyl and / or thiol groups of benzophenone and dibenzothiophene will substantially reduce the desulfurization reactivity of organic sulfur, and become "hard sulfur π" or "heat resistant sulfur" π. Fig. 1 is an example of LCO sulfur GC shown by sulfur GC classification. In the review of Ind. Eng. Chem., 30, 1991, 2021-2 0 58 by Girgis and Gates, the substitution of fluorenyl radicals into the 4 _ position or 4 _ and The 6-position reduces the desulfurization activity by an order of magnitude. Hou Yala (Η 〇 a 1 1 a) and others have reported activity differences on the order of 1-10 (M. Houalla et. Al., Journal of Catalysis, 61, 1980, 523-527). Lamure-Meille and others have suggested that the steric hindrance of alkyl groups will cause the

O: \ 62 \ 62040.ptc Page 7 527413 --- 188123132 91 ^ ln (Jb amendment _ V. Description of the invention (3) " || Substituted dibenzo_phen with low reactivity ((Lamure-Meille et al. People, Applied,

Catalysis A: General 131, 1995, 143-157). In terms of using high f-point catalytic cracking products as feedstock for the hydrodesulfurization process, the move to reduce the range of more thermally resistant organic sulfur compounds in these cracked fractions is clear. & τ, the method is to desulfurize by feeding from Fcc by hydrotreating before cracking starts. Although very effective, this approach would be expensive in terms of capital cost of the equipment and J = cost, because the hydrogen consumption is high. Another process is to remove sulfur from the cracked product by hydroprocessing. Similarly, although it is very important, the disadvantage of this method is that when the high-octane olefin is saturated, the valuable product octane may be lost. From the perspective of ff, it is necessary to complete the sulfur removal in the cracking process itself "without additional processing", which is the main group that can effectively change the gasoline exchange tank ^ f. The sulfur removal during the FCC process cycle has been developed A variety of re-substances have been developed, but so far 'most of the development has focused on removing sulfur from early ^ gas. A @i 糸 developed by Chevron uses alumina compounds as additives to cracking catalyst stock to The sulphur oxides in your bioreactor are absorbed by the stone; the adsorption that enters the process in the feed ΐ Ϊ Ϊ 7 in the cracking part of the cycle is released with hydrogen sulfide and passed to the person of the device Add.f 'and then removed from it Please see Prórp_ltlVeS imP " 〇ve FCC Process, Hydrocarbon, etc. by Hishna, etc., No.Vember 1991, pp. 5-9-6. Sulfur-based self-regenerator sounds. I * Go 'and The sulfur content of the product is not greatly affected. Even if there is another technology for removing sulfur oxides from the regenerator, it is based on the use of magnesium.

527413 Amendment _ Case No. 88123132 V. Description of the invention (4) Aluminum spinel is used as an additive to the circulating catalyst stock in F C C U. Under the code name DESOXTM used as a process additive, the design technology has achieved significant commercial success. Representative patents related to this desulfurization additive include US 4,963,520, 4,957,892, 4,957,718, 4,790,982 and others. However, the sulfur content of the product did not decrease significantly. The catalyst additive for reducing the sulfur content in the liquid-phase cracked product is Omex Bay-Kee and Gold 001 1 1 13 6 (116 116 & 11 (11 (1111) in U.S. Patent No. 5,376,608 and No. 5, 525, 210 proposed that it is made of low-sulfur gasoline using a pyrolytic catalyst additive with alumina as the carrier. However, this system has not yet achieved significant commercial success. Therefore, there is still a need for a ' Effective additive to reduce sulfur content in fluidized catalytic cracking products. _ US Patent Application No. 09/144, 607 (filed on August 31, 1998; Republic of China Patent Application No. 8 8 1 1 4 9 5 1) I have described the catalytic material used in the catalytic cracking method, which can reduce the sulfur content of the liquid phase products in the cracking process. These sulfur reduction catalysts include, in addition to the porous molecular sieve component, the oxidation state inside the pore structure of the molecular sieve Metals above zero. Molecular sieves are zeolites in most cases, and they can be zeolites that are consistent with large pore zeolites such as zeolite beta or zeolite USY or are consistent with intermediate pore size zeolites such as ZSM_5. Non-zeolite molecular sieves such as M eAPO -5, Me APS 0-5 and mesoporous crystalline substances such as MCM-4 1 can be used as catalyst molecular sieve components. Metals such as vanadium, zinc, iron, cobalt and gallium have been found to effectively reduce Sulfur, and hunger is the preferred metal. When used as separate particle additive catalysts, these materials are combined with active catalytic cracking catalysts (usually octagonal stones such as Buddha Y, especially zeolite USY) in combination to use Processing low-sulfur products by processing hydrocarbon feedstocks in a fluidized catalytic cracking- (FCC) unit. Due to sulfur reduction

O: \ 62 \ 62040.ptc Page 9 527413 Amendment No. 88123132 V. Description of the invention (5) The molecular sieve component of the catalyst itself can be an active cracking catalyst, such as zeolite USY, so it can also be used as a whole cracking / A sulfur reduction catalyst in the form of a sulfur reduction catalyst system, for example, containing USY as an active cracking component and a molecular sieve component of the sulfur reduction system and added matrix materials such as silica, clay and metals, such as vanadium, which can provide sulfur reduction Features. Another consideration in the manufacture of FCC catalysts has always been catalyst stability, especially hydrothermal stability, as cracking catalysts are exposed to repeated reduction cycles (in the cracking step) during use, followed by steam stripping Then, it is oxidatively regenerated, which generates a large amount of steam from the combustion of coke, a carbon-rich hydrocarbon deposited on the catalyst particles during the cracking portion of the cycle. Early in the development of zeolite cracking catalysts, it has been found that not only for optimum cracking activity but also for stability, the sodium content must be low; and rare earth elements such as selenium and lanthanum will give greater hydrothermal stability. See, for example, F 1 u i d Catalytic Cracking with Zeolite Catalysts, Venuto et al., Marcel Dekker, New York, 1979, ISBN 0-8 2 4 7- 6 8 7 0- 1 °

We have now developed catalytic materials for catalytic cracking processes that can improve the liquid phase products of the cracking process, including, in particular, the reduction of sulfur content in gasoline and middle distillate cracked fractions. The sulfur reduction catalyst is similar to that described in the U.S. application 0 9/1 4 4, 6 0 7 because the pore structure of the molecular sieve component in the catalyst composition has the presence of a metal component with an oxidation state above zero. At the same time, hungry is better. However, in this case, the composition also contains one or more rare-earth elements, preferably rhenium. I have found that the presence of rare earth components will enhance the stability of the catalyst, while those containing only vanadium or another metal component will not, and in some advantageous cases, especially when rhenium is a rare earth component ,Less

O: \ 62 \ 62040.ptc Page 10 527413 Amendment No. 88123132 V. Description of the invention (6) The sulfur activity will also be increased due to the presence of rare earth elements. This is surprising because rare earth cations themselves do not have sulfur reduction activity. The sulfur reduction catalyst can be used in a cracking device in the form of a combination of an additive catalyst and an active cracking catalyst, that is, combined with a conventional main component of a circulating cracking catalyst stock; the catalyst stock is usually an anthracene zeolite. Zeolite Y is usually used as the base plus zeolite-containing catalyst. Alternatively, they can be used in the form of an overall cracking / product sulfur reduction catalyst system. According to the present invention, the sulfur-removing catalyst composition includes a porous molecular sieve, which contains (i) a metal having an oxidation state above zero within the pore structure of the molecular sieve and (i i) a rare earth component. Molecular sieves are zeolites in most cases and can be characterized as zeolites that are compatible with macroporous zeolites such as zeolite beta or zeolite USY or with intermediate pore size zeolites such as ZS M-5. Non-zeolitic molecular sieves such as Me A P 0-5, MeAPSO-5 and mesoporous crystalline materials such as MCM-41 can be used as catalyst molecular sieve components. Metals such as vanadium, zinc, iron, cobalt, and gallium are all effective. If the selected molecular sieve material has sufficient cracking activity, it can be used as an active catalytic cracking catalyst component (usually faujasite such as zeolite Y), or it can be used in combination with an active cracking component regardless of whether it has any cracking active.

The composition can be used to process hydrocarbon feedstocks in a fluidized catalytic cracking (FCC) unit to produce low-sulfur gasoline and other liquid products. For example, it can be used as a light cycle oil for blending components of low-sulfur diesel or as a heating oil. In addition to the extremely significant reduction in the sulfur content of cracked gasoline fractions, this sulfur reduction catalyst can also reduce the sulfur content in light cycle oils and fuel oil products (light fuel oil, heavy fuel oil). The reduction of sulfur in LCO occurs mainly with substituted benzothiophenes and substituted dibenzothiophenes; the removal of these more heat-resistant species will improve the efficiency of sulfur reduction in the subsequent LCO hydrodesulfurization process. The reduction in HFO sulfur allows

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Coker products are upgraded from oil to high-grade coke. Except for ίί :; "Organic sulfur is usually present in the substance, and the compound is converted to none", so the process is in the form of: in shape and salty ... Other large sieve screens are attached. ¥ tw τ = metal position in the stone Provide sulfur species adsorption sites. The FCC process illustrates the performance of this sulfur reduction composition. ： Sulfur catalyst is used as catalyst in catalytic cracking process

Resolve CFCC) process. For convenience, the present invention will be referred to the FCC process plus the child months. Although the additives can be used in the older f moving bed type (TCC) cracking process with appropriate adjustments in particle size, to suit their needs. Except for the addition of additives to the catalyst storage and some possible changes to the product recovery section discussed below, the operation of the process will remain unchanged. Therefore, conventional FCC catalysts can be used, such as zeolite-based catalysts with faujasite cracking components, such as Venu to and Habib in Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker , New York 1 9 7 9, ISBN 0- 82 4 7- 6 8 7 0-1 and basic reviews of Fidad Catalytic Cracking Handbook, Gulf Pub 1. Co · in many other sources such as Sadegbebe

Houston, 1995, as described in ISBN 0- 8 84 1 5 -2 9 0-1. In a nutshell, the fluidized catalytic cracking process of heavy hydrocarbon feed containing organic sulfur compounds to be cracked into lighter products is a cyclic catalyst cycle cracking process-the feed in and the size from 20 to 100 The cycle of micron particles can be

527413 — Case No. 88123132, month f amendment V. Description of the invention (8) The fluidized catalytic cracking catalyst stock was contacted. The important steps of the cyclic process are: (i) A catalytic cracking zone operating under catalytic cracking conditions, usually in a riser cracking zone, by contacting the feed with a thermal, regenerative cracking catalyst source, the Catalytic cracking of the feedstock to produce an effluent containing cracked products and waste catalyst containing carbon and strippable hydrocarbons; (ii) discharging and separating the effluent, usually in one or more cyclones to separate into rich The gas phase containing the cracked product and the solid-rich phase containing the spent catalyst; (iii) the gas phase is removed as the product and fractionated in the FCC main column and its connected side columns to form a liquid phase including gasoline Pyrolysis products; (iv) the spent catalyst, usually steam stripped to remove the adsorbed hydrocarbons from the catalyst, and then oxidized and regenerated by the stripped catalyst to produce a thermal regeneration catalyst, and then returned to the cracking zone for further Amount of cracked feed. The feed for the FCC process will generally be a feed of a high boiling point mineral oil source, usually with an initial boiling point of at least 290 ° C (550 ° F) and in most cases 3 15 ° C (600 ° F) Above. The FCC feed fractionation point for most refineries will be at least 3 4 5 ° C (650 ° F). The end point will vary depending on the correct characteristics of the feed or operating characteristics of the refinery. The feed can be a distillate, typically with an end point of 5 5 0 ° C (1 0 2 0 ° F) or higher, such as 5 9 0 ° C (1 0 9 5 ° F) or 6 2 0 ° C (1 150 ° F), or residual (non-distillable) substances may be included in the feed and may even include all or a substantial part of the feed. Distillable feeds include virgin feeds such as gas oils, such as heavy or light atmospheric gas oils, heavy or light vacuum gas oils, and cracked feeds such as light coker gas oils and re-coker gas oils. It is possible to use hydrotreated feeds, such as hydrotreated gas oils, especially hydrotreated heavy gas oils, but because

O: \ 62 \ 62040.ptc Page 13 527413 Amendment No. 88123132 V. Description of the invention (9) The medium can achieve a substantial reduction in sulfur. When the purpose is to reduce sulfur and still achieve the improvement of crackability, the preliminary can be eliminated. Its hydrotreating. In this process, the sulfur content of the gasoline portion of the liquid-phase cracking product can be effectively reduced to a lower and more acceptable level by catalytic cracking in the presence of a sulfur reduction catalyst. F C C Cracking Catalyst This sulfur reduction catalyst composition can be used in the form of individual particle additives added to the main cracking catalyst in the FCC, or they can crack the components of the catalyst to provide an overall cracking / sulfur reduction catalyst system. The cracking component of the catalyst that is conventionally used to carry out the desired cracking reaction and produce a low-boiling-point cracking product is usually based on the faujasite active cracking component, which is conventionally a zeolite Y, which is one of the following forms: The rare-earth exchange Y-type zeolite (CREY), the preparation of which has been disclosed in US Patent No. 3,402,996, and the ultra-stable Y-type zeolite (USY), such as the US Patent No. 3, 2 93, 1 92 Revealed; and various partial exchange Y-zeolites, as described in U.S. Patent Nos. 3,607,043 and 3,676,368. Cracking catalysts like these are available in large quantities from various commercial suppliers. Active cracking components are conventionally mixed with matrix materials such as silica or alumina and clay to provide the mechanical characteristics (wear resistance, etc.) and activity control required for very active zeolite components. The particle size of the cracking catalyst is generally in the range of 10 to 100 microns for effective fluidization. If used as an individual particle additive, the sulfur reduction catalyst (and any other additives) is usually chosen to have a particle size and density equivalent to the cracking catalyst to prevent the components from separating during the cracking cycle. Sulfur reduction system-molecular division component According to the present invention, the sulfur removal catalyst includes a porous molecular sieve, which contains a metal having an oxidation state above zero within the pore structure ·. Molecular sieve in most cases

O: \ 62 \ 62040.ptc Page 14 527413 -f / year / month If the amendment number is 881231 ^ V. Description of the invention (10) Form zeolite 'and can be characterized with large pore zeolites such as zeolite γ, preferably The zeolite USY 'or zeolite beta or a zeolite consistent with a mesoporous zeolite such as zs M-5, and the former is preferred. The molecular sieve component of the sulfur reduction catalyst may be a zeolite or a non-zeolite molecular sieve, as described above. When used, zeolites can be selected from macroporous zeolites or mesoporous zeolites (see Shape Se ective Cata 1 ysisi η Industria 1 Applications, Chen et a 1, Marcel Dekker, New York 1 9 8 9, ISBN 0-8 247-78 5 6-1, discussions on the classification of zeolites by pore size based on the basic plan designed by Frilette et al. J Catalysis 67, 2 1 8-22 2 (19 8 1)). Small pore zeolites, such as zeolite A and erionite, have inadequate stability for use in catalytic cracking processes and are generally poor due to their repulsive nature of molecular size; this repellent property will crack the components and cracks of the feedstock Many components of the product are excluded. However, the pore size of molecular sieves does not seem to be important because, as described below, both medium and large pore zeolites have been found to be very effective in comparison with mesoporous crystalline materials such as MCM-4 1. The properties are consistent with the existence of a large pore (12 ring) structure. The zeolites that can be used to make this sulfur reduction catalyst include various forms of zeolites, such as Y, REY, CREY, USY, with the last being preferred; and other zeolites such as It boils like L, zeolite beta, mordenite (including dealuminous mordenite) and zeolite ZSM-18. Generally speaking, large pore zeolites are characterized by a pore structure with ring openings of at least 0.7 nm, while medium or intermediate pore zeolites have pore openings of less than 0.7 nm but greater than 0.5 6 nm. Suitable mesoporous zeolites that can be used include pentasilite such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-50'ZSM-57, MCM-22, MCM-49, MCM-56, all of which are Is a known substance. Zeolite is compatible with

O: \ 62 \ 62040.ptc Page 15 527413 jf year / month / .f amendment number 881231 ^ V. Description of the invention (11) Gallium, iron, and chromium together use frame metal elements other than the inscription, for example, for side use . Fossil U S Y is particularly suitable for use. Therefore, zeolite is generally used as the active cracking component of the cracking catalyst, and therefore the sulfur reduction catalyst can be used in the form of an overall cracking / sulfur reduction catalyst system. USY zeolite used for cracking components can also be advantageously used as the molecular sieve component of individual particle additive catalysts, as it will continue to contribute to the cracking activity of the entire catalyst in the device. The stability is related to the low single-pore chamber size of the USY, and is the optimal result. The UCS (single-pore chamber size) of the USY zeolite in the finished catalyst should be 2.420 to 2.460 nm, preferably 2.420 to 2.455 nm 'and the range 2.420 to 2.445 nm, preferably 2.435 to 2.440 nm is very suitable. After repeated steaming of the kFCC cycle, further reduction of ucs will proceed to a final value usually in the range of 2.42 to 2.43 nm. Other molecular sieves than zeolites can also be used, although they may not be all the same, because optimal performance seems to require some acidic activity (conventionally measured at = hair value). The test data show that an AFA value exceeding 丨 0 (no metal-containing molecular sieve) is suitable for sufficient desulfurization activity, and an AFA value in the range of 0.2 to 2,000 is usually suitable for 1. Afa values from 0.2 to 2 represent the normal range of acidic activity of these substances when used as additives. The Afa test is a convenient method for measuring the total acidity (including internal and external acidity) of solid substances such as molecular sieves. This test has been described in U.S. Patent No. 3,354,078, journal Cat Catlysis, Vol. 4, ρ 527 (1965); Vol. 6, ρ 278 (1966); and Vol. 61, ρ 395 (1 9 8 0). The Afar value reported in this manual is measured at a constant temperature of 5 3 8.

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Page 16 527413 _ Case No. 88123132 ff car 丨 Month Amendment _ V. Description of the invention (12) Representative non-zeolitic molecular sieve materials that can provide appropriate carrier components to this sulfur reduction catalyst metal component include various silica-aluminum Soil silicates (such as metal silicates and titanosilicates), metal aluminates (such as germanium aluminates), metal phosphates, aluminum phosphates such as silicon-and metal aluminophosphates are called metal monoliths Aluminophosphate (MeAPO and ELAPO), metal monolithic silicoaluminophosphate (MeAPSO and ELAPS0), silicoaluminophosphate (SAP0), gallium germanate and combinations of these. Discussions on the structural relationships of SAPO's, AIPO's, MeAPO's, and MeAPSO's can be found in many sources, including Stud. Surf. Catal. 37 13-27 (1987) ° AIP0's contain aluminum and phosphorus, while in SAPO's Some phosphorus and / or some phosphorus and aluminum are replaced by silicon. In MeAPO's, in addition to aluminum and stone dance, various metals exist, such as Li, B, Be, Mg, Ti, Mn, Fe, Co 5 An, Ga, Ge, and As, while MeAPSO's contains additional stone Xi. The negative charge of the MeaAlbPcSidOe lattice is made up by cations, where Me is magnesium, manganese, cobalt, iron and / or zinc. MexAPS0's has been described in U.S. Patent Nos. 4, 7 9 3, 9 84. SAP0 molecular sieve substances have been described in US Patent No. 4,44 0, 8 71; MeAPO catalysts have been described in US Patent Nos. 4,544, 143 and 4, 5 6 7, 02 9; ELAP0 catalysts have been described The US patent 4,500,6 51 and the ELAPSO catalyst have been described in the European patent application 159, 6 2 4. Specific molecular sieves have been described, for example, in the following patents: MgAPSO or MAPS 0-US Patent No. 4,758,419, Mn APS 0-US Patent No. 4,686,092; CoA PS 0-US Patent No. 4,744,970 No.? 6 eight? 80-US Patent No. 4,683,217 and 21 ^ 30-US Patent No. 4, 9 3 5, 2 16. Specific silicoaluminophosphates that can be used include SAP0-1 1, SAP0-17, SAP0-34, SAP0_37; other specific molecular sieve materials include MeAPO-5, MeAPSO-5 0

O: \ 62 \ 62040.ptc Page 17 527413 Amendment No. 88123132 V. Description of the invention (13) Another type of crystalline carrier material that can be used is a group of mesoporous crystalline materials, represented by MCM-41 and MCM-48 materials . These mesoporous crystalline materials have been described in U.S. Patent Nos. 5,098,684, 5,102,643 and 5,119,203. MCM-41, which has been described in U.S. Patent No. 5,0 9,8,6,84, is a microstructure characterized by pores with a diameter of at least 1.3 nm, arranged in a uniform hexagon; after calcination, it appears to have at least one d -X-ray diffraction patterns with intervals greater than 1.8 nm and hexagonal electron diffraction patterns with indices of dl 00 greater than 1.8 nm; the indices correspond to the d-intervals of the peaks in the X-ray pattern. The preferred catalytic form of this material is aluminosilicate, although other metal silicates can also be used. MCM-48 has a cubic structure and can be made by similar preparation procedures

Made. Metal components

The molecular sieve carrier material is composed of two metal components to form the present catalytic composition. One component is a rare earth group such as lanthanum or a mixture of rare earth elements such as rhenium and lanthanum. Another metal component can be regarded as the main sulfur reduction component, although the way it affects sulfur reduction is not clear, as discussed in application number 0 9/1 4 4, 6 0 7, this document is included for reference and is included for this purpose Description of effective vanadium and other metal component sulfur reducing catalyst compositions. For convenience, this component of the composition will be referred to as the main sulfur reduction component in this specification. To be effective, this metal must be present inside the pore structure of the molecular sieve component. Metal-containing zeolites and other molecular sieves can be prepared by: (1) metal is added to molecular sieves or catalysts containing molecular sieves, (2) synthesis of molecular sieves containing metal atoms in the framework structure and (3) large metals are trapped in the zeolite Synthesis of ionic molecular sieves. After adding metal components, washing out unbound ion species and drying them, they should be calcined. These techniques are known per se. Metal ions are added after because it is simple and easy

O: \ 62 \ 62040.ptc P.18 527413 _ Case No. 88123132 f (year (month, / revised amendment_) V. Description of the invention (14) Economical, allowing existing molecular sieve materials to be converted for use in this additive. There are a variety of metal post-addition methods that can be used to make the catalysts of the present invention, such as water exchange of metal ions, solid state exchange using metal alkali salts, impregnation with metal salt solutions, and vapor deposition of metals. However, in In each case, it is important to add metal, and the rhenium metal component enters the pore structure of the molecular sieve component. It has been found that when the metal of the main sulfur reduction component is exchanged for the presence of cationic species in the pores of the molecular sieve component, For the preferred metal component, the hydrogen transfer activity of the metal component is reduced to the hydrogen transfer reaction performed during the cracking process, which will generally be maintained at an acceptable low level. Therefore, coke and light gas manufacturing tips during cracking Slight increase but still within the allowable range. Since unsaturated light ends can be used as alkylation feed anyway and can be returned to the gasoline pool in this way, the use of this additive will not cause gas Significant loss of hydrocarbons in the oil range. Due to concerns over excessive coke and hydrogen production during the cracking process, the metals incorporated in the additives must not exhibit hydrogenation activity to a significant extent. For this reason, precious metals such as those with strong hydrogenation-dehydrogenation The rhyme and period of the function are not suitable. Combinations of alkali metals and alkali metals with strong hydrogenation functions, such as record, key, record-yan, start-key, and record-molybdenum, are not suitable for the same reason. Preferred alkali metals are metals in the fourth cycle of the periodic table, Groups 5, 8, 9, 12, 13 (I UPAC classification, formerly VB, VI II, I IB, IIIA). Hunger, zinc, iron, starting Both gallium and gallium are effective, and hunger is the preferred metal component. Surprisingly, vanadium can be used in FCC catalyst compositions in this way, because vanadium is generally considered to have a very significant effect on zeolite cracking catalysts, Efforts have been made to develop thorium inhibitors. See, for example, W ommsbecher et al. 5 Vanadium Poisoning of Cracking Catalysts:

0: \ 62 \ 62040.ptc Page 19 527413 _ Case No. 88123132 Year / Month H__ 5. Description of the invention (15)

Mechanism of Poisoning and Design of Vanadium Tolerant Catalyst System, J. Catalysis 100, 1 3 0-1 3 7 (1 9 8 6). It is believed that the position of vanadium in the molecular pore structure will stabilize Syria and prevent it from becoming an acid species, which can be harmfully combined with the molecular sieve component; however, the present zeolite-based sulfur reduction containing vanadium as a metal component The catalyst has been repeatedly cycled between the reduction and oxidation / steaming conditions that represent the FCC cycle, while still retaining the characteristic zeolite structure, showing that the metal has a different environment. Vanadium is particularly suitable for gasoline sulfur reduction when zeolite USY is used as a carrier. The yield structure of ν / USY sulfur reduction catalyst is particularly interesting. Although other zeolites show gasoline sulfur reduction after metal addition, they can convert gasoline into C3 and (: 4 gas, even if many of the converted c3 = and c4 = can be burned and re-blended into the gasoline pool, but High c4_ wet gas yield can be a concern, as many refineries are limited by their wet gas compressor energy. Metal-containing USY has a yield structure similar to existing FCC catalysts; this advantage Allows the V / USY zeolite content in the catalyst blend to be adjusted to the target desulfurization level without restrictions from the FCC device. The vanadium Y zeolite catalyst, whose zeolite is represented by USY, is therefore the FCC gasoline gasoline sulfur reduction Particularly advantageous combination. It has been found that the USY which can produce particularly good results is a single-porous chamber with a size in the range of 2. 4 2 to 2. 4 60 nm, preferably 2.4 2 0 to 2.4 5 0, such as 2. 43 USY in the range of 5 to 2.45 0 nm (after treatment). Combinations of alkali metals such as vanadium / sulphur as the main sulfur reduction component may also be advantageous in terms of total sulfur reduction. The main sulfur reduction metal component The amount in the sulfur reduction catalyst is normally 0.2 to 5 weight ° / 〇, generally 0.5 to 5% by weight (in relation to Ingredients parts by weight of the molecular sieve of the group concerned), but in an amount outside this range, for example, 0.1 to 1 wt% billion, according to

O: \ 62 \ 62040.ptc Page 20 527413 Case No. 88123132 Month Amendment 5. Description of the invention (16) It was found that some desulfurization effects could still be produced. When the molecular sieve has a matrix, the amount of the main sulfur-reducing metal component expressed relative to the total weight of the catalyst composition is generally increased from 0.1 to 5, and more generally, for the actual purpose of formulation. Increased from 0.2 to 2% by weight. The second metal component of the sulfur reduction catalyst composition contains a rare earth metal that exists in the pore structure of the molecular sieve and is considered to exist in the form of a cation that is exchanged into an exchangeable position existing in the molecular sieve component. Rare earth (RE) components significantly improve the stability of hungry catalysts. For example, R E + V / U S Y catalyst can achieve higher cracking activity, but V / U Y Y is not, although the same gasoline sulfur reduction can be obtained. Rare earth metals such as lanthanum, europium, ytterbium, ytterbium, #, osmium, this, mirrors, and pins can be used in this way, but from the viewpoint of commercial universality, Lanthanum and mixtures of rhenium and lanthanum will generally be preferred. From the viewpoint of sulfur reduction and catalyst stability, it has been found that thorium is the most effective rare earth component, so its use is better, although good results can be obtained with other rare earth elements, as shown below. The amount of the rare earth group is generally 1 to 10% by weight of the catalyst composition, and most cases are 2 to 5% by weight. The amount of rare earths relative to the weight of the molecular sieve will usually be 2 to 20% by weight of the molecular sieve and 4 to 10% by weight in most cases, depending on the molecular sieve: matrix ratio. The sieve can be used in an amount of 0.1 to 10 of the catalyst composition, usually 0.2 to 5 to 5% by weight, and relative to the molecular sieve, it will usually be 0.2 to 20, and in most cases 0. 5 to 10% by weight. The rare earth component can be appropriately incorporated into the molecular sieve component by exchanging it on a molecular sieve-either in the form of crystals without a matrix or in the form of a catalyst with a matrix. When the composition is formulated with a better U S Y zeolite sieve, a very effective way of incorporation is to add rare earth ions to the USY molecular sieve (generally

O: \ 62 \ 62040-911217.ptc page 21 527413 The metal component is incorporated into the catalyst composition in a manner to ensure that it enters the pore structure inside the molecular sieve. Metals can be directly incorporated into crystals or matrix-added catalysts. Case No. 88123132 132 月 / 7 月 _ ^ V. Description of the invention (17) 2 · 4 4 5-2 · 4 6 5 nm single hole chamber size), followed by In addition, steam calcination is used to reduce the size of the single pore chamber of the USY to a value generally in the range of 2.420 to 2.46 nm. If the value does not exist, the main metal component can be added. For stability and ideal cleavage activity, USY should have a low alkali metal (mainly sodium) content; this will usually be achieved by exchanging ammonium on the molecular sieve during the superstabilization process to a desired low sodium content of not more than 1% by weight It is preferably obtained not more than 0.5% by weight. . in. When a better USY zeolite is used as the molecular sieve component, it can be appropriately calcined as described above, that is, the USY cracking catalyst containing the rare earth component is recalcined to ensure a low single pore size, and then the cation exchange is permitted Under the conditions of 'incorporation of metals such as vanadium by ion exchange or impregnation, rhenium metal ions immobilize the pore structure of t. Alternatively, the main sulfur-reducing component and the rare-earth metal component can be calcined to remove any organic matter from synthesis, and then incorporated into the gaseous component, such as USY zeolite or ZSM_5 crystal, and the metal-containing component may be The finished catalyst composition is prepared by adding lysis and matrix components, and the formulation is spray-dried to form the final catalyst. When the catalyst is modulated into an overall catalyst system, it is preferable to use the active cracking component of the catalyst as the molecular sieve component of the debossing system, preferably in the form of faujasite such as Buddha such as USY. For the sake of retention of cleavage properties. However, another active cracking molecular sieve material such as ZSM-5 can be incorporated into the overall catalyst system ', and such a system may be useful when the properties of a second active molecular sieve material, such as the properties of ZSM-5, are needed. The impregnation / exchange process should be carried out with a controlled amount of metal in both cases.

527413 q 1 year 丨 & Amendment No. 88123132 V. Description of the invention (18) Leave the number of positions necessary to catalyze the active cracking component or any secondary cracking components present such as Z SM-5 may be expected Cleft response. Use of sulfur-reducing catalyst compositions The most convenient way to generally use sulfur-reducing catalysts is to add individual particulate additives to the catalyst inventory. In its preferred form using Jishi U S Y as a molecular sieve component, the addition of catalyst additives to the total catalyst inventory of the device will not cause a significant reduction in total cracking due to the cracking activity of USY zeolite. The same is true when another active lysing substance is used as the molecular sieve component. When used in this manner, the composition can be used in the form of crystalline granules of pure molecular sieve (without matrix but with added metal components) to correct the size for FCC use. However, usually metal-containing molecular sieves will be added to the matrix in order to obtain sufficient particle abrasion resistance and maintain ideal fluidization. Conventional cracking catalyst substrate materials such as Ming soil or Shi Xi stone-ming soil, usually with clay, will be suitable for this purpose. The amount of matrix relative to the molecular sieve will typically be from 20:80 to 80:20 weight ratio. Conventional plus matrix techniques can be used. The use of individual particle catalyst additives allows the ratio of sulfur reduction and cracking catalyst components to be optimized based on the amount of sulfur in the feed and the degree of desulfurization required; when used in this way, the general amount used is The total catalyst inventory in FCCU is 1 to 50% by weight; in most cases, this amount will be 5 to 25% by weight, such as 5 to 15% by weight. About 10% is the standard representing most practical uses. Additives can be added in a conventional manner, added to the regenerator with a supplemental catalyst, or in any other convenient manner. Additives can retain sulfur removal activity for a long time, although very high sulfur feeds will cause sulfur removal activity to disappear in a short period of time. Another way to use individual particle additives is to incorporate a pyrolysis catalyst

O: \ 62 \ 62040.ptc Page 23 527413 Amendment No. 88123132 5. In the description of the invention (19), the sulfur reduction catalyst that forms the overall FCC cracking / gasoline sulfur reduction catalyst. If the sulfur-reducing metal component is combined with a molecular sieve other than the active cracking component, such as on ZSM-5 or zeolite beta (when the main active cracking component is USY), the sulfur-reducing component (molecular sieve plus metal) The amount will generally be as high as 25% by weight or less of the entire catalyst, which is equivalent to the amount that can be used for individual particle additives as described above. In addition to cracking catalysts and sulfur removal additives, other catalytically active components may be present in the catalytic substance In circulating stock. Examples of these other substances include sintering enhancement catalysts based on zeolite ZSM-5, C0 combustion accelerators based on carrier precious metals such as #, flue gas desulfurization additives such as DESOXTM (magnesium aluminum spinel), Starch and bottom cracking additives, such as in K rishna,

Sadeghbe i g i, op cit and Scherzer, Octane Enhancing Zeolitic FCC Catalysts, Marcel Dekker, New York, 1990, ISBN 0-8247-8399-9. These other components can be used in customary amounts. The effect of this additive is to reduce the sulfur content of liquid phase cracking products, especially light and heavy gasoline fractions, although higher boiling point distillates, including light cycle oils and light and heavy fuel oil fractions, are also available. The reduction makes it easier to carry out the hydrodesulfurization technology by removing more thermally resistant sulfur compounds. The distillate can then be hydrodesulfurized under less severe, more economical conditions to produce a distillate suitable for use as a diesel or household heating oil blending component.

The cracking process itself will be carried out in the normal way, and sulfur reduction catalysts will be added in the form of additives or overall catalytic cracking / sulfur reduction catalysts (single particle catalysts). The cleavage conditions will be customary in nature. The sulfur system removed by the use of catalyst during the cracking process is converted into inorganic

O: \ 62 \ 62040.ptc Page 24 527413 Amendment No. 88123132 V. Description of the invention (20) It is released as hydrogen sulfide in the same way as the conventional release of hydrogen sulfide in the cracking process, which can be released in the FCCU The product recovery section recovers. The increased load of hydrogen sulfide will increase the demand for additional acid gas / water treatment, but these can not be considered as limiting due to the significant reduction in gasoline sulfur.

The significant reduction of sulfur in the cracked product can be achieved by using this catalyst, in some cases up to 50% (compared to the use of conventional cracking catalysts), and using the above-mentioned preferred catalyst under constant conversion. A 25% reduction in gasoline sulfur can easily be achieved with many additives according to the invention, as shown in the following example. In the case of middle distillate fractions including LCO fractions, a reduction of up to 25% can also be achieved, as shown in the following example, plus the content of heat-resistant sulfur compounds including alkyl-substituted benzothiophenes and dibenzothiophenes Its reduction. The degree of sulfur reduction depends on the original organic sulfur content in the cracked feed, with the highest reduction achieved with high sulfur feeds. The metal content of the balance catalyst in the device will also affect the degree of desulfurization achieved. To balance the low metal content on the catalyst, especially the hunger content, is conducive to large desulfurization.

When the E catalyst has a vanadium content below 1,000 ppm, the desulfurization will be extremely effective, although the catalyst will remain effective at higher vanadium content. Sulfur reduction can not only effectively improve product quality but also effectively increase product yield, provided that the end point of cracked gasoline in refineries is limited by the sulfur content of heavy gasoline fractions; by providing effective and Economically, the gasoline end point can be extended without relying on expensive hydroprocessing, with the result having a beneficial effect on the economy of the refinery. If subsequent hydrotreating is expected, various thiophene derivatives must also be removed, which are difficult to remove under less severe conditions by hydrotreating. Example 1 Preparation of Catalyst Series 1

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527413 Amendment_Case No. 88123132 V. Description of the invention (22) Table 1 V, RE + V, and Ce + V USY / silica sol catalyst (series 1) V / USY catalyst AV / USY catalyst B RE + V / USY catalyst C RE + V / USY catalyst D Ce + V / USY catalyst E Calcined catalyst V content, wt% 0.36 0.37 0.39 0.38 0.39 RE2 03 content, Wt% Ν · Α. Ν.Α. 2.0 4.1 5.1 Ce203? Wt% Ν.Α. Ν.Α. 0.49 0.95 * 4.95 La2〇3, wt% Ν.Α. Ν.Α. 0.96 1.83 0.03 Na2〇, wt% 0.30 0.24 0.42 0.21 0.19 single cell size, nm 2.433 2.433 2.442 2.443 2.442 Inactivated catalyst (CPS 770 ° C20hrs) Surface area mY1 255 252 „249 248 284 Single cell size 2.425 2.424 2.426 2.428 2.428 Example 2 Preparation of catalyst series 2

V / U SY catalyst, catalyst F, was prepared using USY zeolite with a silica-alumina ratio of 5.4 and a single cell size of 2. 4 35 nm. The liquid-phase catalyst was prepared by spray-drying an aqueous slurry containing 50% by weight of 2USY crystal / silica sol / clay matrix. The matrix contains 22% by weight silica sol and 28% by weight kaolin. By exchanging with ammonium sulfate solution, the spray-dried catalyst was exchanged with N H4 + and then dried. Then, the U S Y catalyst was impregnated with a solution of vanadium oxalate to achieve the target 0.5% by weight V. 5 RE + V / USY catalyst, namely catalyst G, uses a silica-alumina ratio of 5.5

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5. Description of the invention (23) and preparation of USY zeolite with a single pore chamber size of 2. 54 nm. Swap usy with nh4 + by swapping with sparse &. Then, the nh4 + exchanged usy;, l, acid ^ an was exchanged with the solution of the mixed rare earth chloride, and exchanged with the rare earth ion (such as La3 +, Ce3 +, etc.). Most of the rare earth solution used (= has been extracted, so it contains only a small amount of Ce. The USY exchanged by RE is fed into ^ all washed, dried, and rotated and calcined in the presence of steam + v (.: (1 4 0 0 T) calcination. Steam sintering makes the single pores of zeolite; 222 7 ^ 2 4 · 4 〇 A and improve its stability in the presence of hunger. Liquid phase catalyst Prepared by spray-drying an aqueous polymer containing 50% by weight of iRE-USY crystal / silica sol / clay matrix. The matrix contains 22% by weight of Shixishi sol and 28% by weight of kaolin. It is exchanged with a solution of ammonium sulfate , The spray-dried catalyst was exchanged with NiV, then dried and calcined at 5 40 ° C (100 ° F) for 2 hours, and then the RE / USY catalyst was impregnated with 〃0304 solution. The catalyst was prepared using a similar procedure as Catalyst G, but USY was exchanged with a mixed RECI3 solution containing most of CeCl3. The catalyst was prepared using a stone-stone-ming soil ratio of 5.5 and a single cell size. A commercial USY zeolite was prepared at 2.454 nm. USY was exchanged with NH4 + by exchange with ammonium sulfate solution. Then, the USY exchanged with NV and some containing Exchange of CeCl3 solution. The exchanged USY was further washed, dried, and calcined in a rotary calciner in the presence of steam at 7 60 ° C (1400 ° F). Steam calcination made zeolite ^ The size of the pore chamber was reduced to 2.440 nm. The liquid-phase catalyst was prepared by spray-drying an aqueous polymer containing 50% by weight of a rare-earth group containing a USY catalyst crystal / silica sol / clay matrix. The matrix contained 22% by weight Silica sol and 28% by weight kaolin. By exchanging the solution with sulfuric acid, spray-dried catalyst was exchanged with NH4 +, then dried and calcined at 5 40 ° C (100 ° F) 2 hours. Calcined

O: \ 62 \ 62040.ptc Page 28 527413 -_ Case No. 88123132 Year / Month // Revision_ V. Description of the invention (24) After burning, the catalyst is impregnated with V0S04 solution. The physical properties of the calcined catalyst are summarized in Table 2. Table 2 Physical properties of V / USY, RE + V / USY silica-sol catalyst (series 2) V / USY catalyst F RE + V / USY catalyst G RE + V / USY catalyst H Calcination catalyst \ , V content, wt% 0.5 0.43 0.44 'content, Wt% Ν · Α · 1.93 2.66 Ce02 content, wt% Ν · Α. 0.21 2.42 Na205 wt% 0.13 0.16 0.20 surface area, n ^ g · 1 327 345 345 single cell chamber Size 2.435-Example 3 Preparation of Catalyst Series 3 V / U SY catalyst, Catalyst I, is a commercial H with a single-cell chamber size of 5.4 and 2. 4 35 nm with a loose silica-alumina ratio -Type USY (crystalline) preparation. The liquid-phase catalyst was prepared by spray-drying an aqueous slurry containing 40% by weight of U S Y crystals, 25% by weight of silica, 5% by weight of alumina, and 30% by weight of kaolin. The spray-dried catalyst was calcined at 5 40 ° C (1000 T) for 3 hours. The resulting Η-type

The U S Υ catalyst was impregnated with a vanadium oxalate solution to achieve the target 0.4 weight by the initial wetting impregnation. The impregnated V / USY catalyst was further air-calcined at 5 40 ° C (1000 T) for 3 hours. The final catalyst contained 0.39% V. C e + V / U S Y catalyst, namely catalyst J, is prepared from spray-dried H-type USY catalyst intermediate which is the same as catalyst I. H-type USY catalyst system using initial wet dip

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Page 29 527413 _Case No. 88123132 IFA Amendment 5. Description of the invention (25) Crushing method, impregnating with Ce (N〇3) 3 solution to the target Ce content of 1.5% by weight. The obtained Ce / USY catalyst was subjected to air sintering at 5 40 ° C (100 ° F) for 3 hours, followed by steaming at 5 40 ° C (100 ° F) for 3 hours. Then, the catalyst was impregnated with vanadium oxalate by initial wetting and impregnation to reach the target 0.4 wt% V. The impregnated & Ce + V / USY catalyst was further air calcined at 540 ° C (1000 ° F) for 3 'hours. The final catalyst contained 1.4% Ce and 0.43% V. Table 3 Physical properties of V and Ce + V USY / silica-alumina_clay catalyst (series 3) ν / USY Ce + V / USY Catalyst I, Catalyst j Content of calcined catalyst V, wt% Ce content , Wt% surface area, m2g4 Afa UCS, nm 039 0.43 NA 1.4 302 250 130 12 2.436 2.437

Preparation of Catalyst Series 4 All samples of Catalyst Series 4 were prepared from a single spray-dried material source consisting of 50% USY, 2% silica sol, and 29% clay. ^ The ratio of loose silica to alumina is "4 and 2.4 35㈣single-hole chamber size. Thinking / Issue with

(NH4) 2S04 & NH40H solution, spray-dried catalyst was slurried at pH 6 to remove Na +, followed by washing with water and calcination at 65 ° C and air for 2 hours. v m V / USY catalyst, catalyst κ, is prepared using the above-mentioned Η-type USY catalyst

527413-No. 1 88123132 (month [7: repair not ____ V. Description of the invention (26) H-type USY catalyst is impregnated to the target 0.5 with a vanadium oxalate solution by initial wetting and impregnation) 53% v。 Weight% V. The impregnated V / USY catalyst was further air calcined at 65 ° C (uld ° F) for 2 hours. The final catalyst contained 0.53% v.

Ce + V / USY catalyst ', i.e. catalyst L', was prepared from the above-mentioned H-type USY catalyst. The CeCh solution was exchanged with the H-type USY catalyst to reach the target Ce content of 75.5% by weight. The obtained Ce + V / U S Y catalyst was calcined in air, and impregnated with an oxalic acid solution > Shell 'to obtain a target of 0.5% by weight v from the initial wet impregnation. The impregnated Ce + V / USY catalyst was further air-calcined. The final catalyst contains 0.7 2 ^ Ce and 0.5 2 0 / 〇V.

The Ce + V / USY catalyst, namely catalyst M, is derived from the above-mentioned Η-type USY catalyst and is exchanged with CeCls solution to achieve the target Ce content of 3% by weight. The obtained Ce / USY catalyst was calcined and impregnated by initial wetting, and impregnated with a vanadium oxalate solution to a target weight of 0.5. The impregnated ce + V / USY catalyst was further air calcined. The final catalyst contains 丨 .5% Ce and 0.53% v.

Ce + V / USY catalyst, namely catalyst N, is impregnated from the above η-type USY catalyst by initial wetting and impregnation with a C e C 13 solution to reach the target 1.5% by weight Ce content. The obtained Ce / USY catalyst was calcined in air and impregnated with an oxalic acid solution to the target 0.5% by weight V by initial wetting. The wetting and impregnating c e / U S Y catalyst was further calcined by air. The final catalyst contained 15% Ce & 0 53% v.

These catalysts were then placed in a fluidized-bed steamer, using 50% steam and 50% gas, and steaming at 77 0 ° C (142 0 ° F) for 20 hours to deactivate them to simulate FCC The catalyst in the device is inactive. The gas vapor is changed from air, &, a mixture of propylene and N2 to 10 every 10 minutes, and then recycled to air 'to simulate the coking / regeneration cycle (cycle steaming) of the FC plant. Two sets of inactive catalyst samples were generated: the steam inactivation cycle of a batch of catalysts was

O: \ 62 \ 62040.ptc Page 31 527413 --- Case No. 88123132 _ί /. __Year _ month / f is amended V. Description of the invention (27) bundle-oxidation) to terminate, the other batch is propylene (End_return) is termination. The coke content of the catalyst is less than 0.05% c. The physical properties of the calcined and steamed (end-oxidized) catalysts are summarized in Table 4. Table 4 Physical properties of V and Ce + V USY / silica sol catalyst (series 4) V / USY catalyst κ Ce + VAJSY catalyst L Ce + V / USY catalyst M Ce + V / USY catalyst N Calcination Catalyst ~ " V content, wt% 0.53 0.52 0.53 0.53 Ce content, wt% Ν · Α. 0.72 1.5 1.5 Na, ppm 890 1190 1190 1260 Inactive catalyst (CPS 770 ° C? 20 hrs) Surface area, n ^ g · 1 237 216 208 204 2.425 Single-well chamber size, nm '2.425 2.423 2.425 Example 5 Preparation of catalyst series 5 All samples of catalyst series 5 are free 40% u SY, 30% colloidal silica A single spray-dried material source consisting of sol and 30% clay. The initial η-type USY catalysts have single-porous chamber sizes of loose silica-alumina ratios of 5 · 4 and 2 · 435 nm. Spray-dry the catalyst at 540. (: (100 ° F)) for 3 hours.

Ce / USY catalyst, catalyst 0, is prepared from ± H-type USY catalyst. The initial wetting and impregnation method was used to impregnate the H_-type "Ya catalyst" with a solution of Ce (N03) 3 to achieve the target Ce content of 1.5% by weight. The obtained Ce / USY catalyst was 540 ° C (1 0 Calcined at 0 0 ° F), followed by steaming at 5 40 ° F (100 ° F) for 3 hours.

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527413 I _Case No. 88123132 V. Description of the invention

Ce + V / USY catalyst, catalyst P, was prepared from catalyst 0. By initial wetting and impregnation, the Ce / USY catalyst was impregnated with a vanadium oxalate solution to a target 0.5% V by weight. The impregnated Ce + V / USY catalyst was dried and air calcined at 5 40 ° C (100 ° F) for 3 hours. The final catalyst contains 1.4% Ce and 0.49% V.

Ce + V / USY catalyst, namely catalyst Q, is prepared by exchanging distillate 0 and V0S04 solution at a pH of ~ 3 to a target V content of 0.5% by weight. The obtained Ce + V / USY catalyst was dried and air-calcined at 540 ° C (100 ° 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. table 5

Physical properties of Ce and Ce + V USY / silica-clay catalyst (series 5)

Ce / USY Ce + V / USY Ce + V / USY Catalyst 0 Catalyst P Catalyst 蛘 Calcined catalyst · V content, wt% Ce content, wt% Na, ppm surface area, π2 ^ 1 Afa single cell size nm Ν.Α. 0.49 〇47 1.6 1.4 〇9-940 284 281 272 10 14, 2.435 2.436? " -------- · τ J VZ

Example 6 Preparation of RE + V / USY / silica-sol catalyst RE + V / USY catalyst, namely catalyst R, uses a silica-alumina ratio of 5.5 and a single cell chamber size of 2 · Preparation of 4 6 5 nm NaY zeolite. With ammonium sulfate

O: \ 62 \ 62040.ptc Page 33 527413 _ Case No. 88123132 Ίί 年 ί 月 ί / 日 倏 正 __ V. Description of the invention (29) A ^-solution exchange, the zeolite Υ and ΝΗ / exchange. The NΗ / exchanged γ is then exchanged with a rare earth gaseous solution (most of Ce3 + has been removed / extracted, so the solution contains very little Ce), and exchanged with rare earth cations (such as y La3 + , Ce3 +, etc.) exchange. The re-exchanged γ was further washed, dried and calcined in the presence of steam at 70 5 ° C (130 0 T) for 2 hours. Steam / calcination reduces the size of the single pore chamber of the zeolite and improves its stability in the presence of vanadium. The liquid-phase catalyst was prepared by spray-drying an aqueous slurry containing 50% by weight of iRE-USY crystal / silica sol / clay matrix. The matrix contains 22% by weight silica sol and 28% by weight kaolin. The spray-dried catalyst was exchanged with NH4 + by exchange with a solution of ammonium sulfate, then dried and calcined at 5 40 ° C (100 ° F) for 1 hour. After calcination, the RE / USY catalyst was impregnated with a vanadium oxalate solution. The physical properties of the calcined catalyst are summarized in Table 6. Table 6 Physical properties of RE + V / USY / silica-sol catalyst RE + VAISY catalyst R Calcined catalyst V content, wt% 0.43 RE203 content, wt% 1.93 Ce02 content, wt% 0.21 wt% 0.16 surface area, m2 / g 345 single hole chamber size, A 24.58

O: \ 62 \ 62040.ptc Page 34 527413 __Case No. 88123132 7 f year f plant said 倏 正 _ V. Description of the invention (30) Example 7

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

Ce + V / USY catalyst, catalyst S, was prepared using NaUSY zeolite with a silica-alumina ratio of 5.5 and a single-pore chamber size of 454 nm. USY was exchanged with NH4 + by exchange with ammonium sulfate solution. USY exchanged with NH4 + is then exchanged with Ce3 + cations by exchange with a solution of europium chloride; the vaporized europium solution contains a small amount of other rare earth ions (for example, La3 +, pr, Nd, Gd, etc.). Then, the Ce-exchanged IISY was further washed, dried and calcined at 7051 (130 ° F) for 2 hours in the presence of steam. Steam calcination reduces the size of the single cell of USY and improves its stability in the presence of vanadium. The liquid-phase catalyst was prepared by spray-drying a water-containing body containing 50% by weight of iCe / USY crystals / stone evening sol / clay matrix. The matrix contains 22% by weight silica sol and 28% by weight kaolin. Exchange the solution of the mist-dried catalyst with N by exchange with the solution of sulfuric acid, and then dry it, and then calcine it at 5 40 ° C (100 ° F) for hrs. After calcining, use sulfuric acid The rhenium solution impregnates the C e / USY catalyst. The physical properties of the calcined catalyst are summarized in Table 7. Table 7

Physical properties of Ce + V / USY / Shi Xishi-sol catalyst 胄

Ce + V / IJSY Catalyst S Calcined Catalyst V content, wt% 0.44 RE2O3 content, wt% 2.66 Ce〇2 content, wt% 2.42 N ^ O, wt% 0.20 surface area, m2g4 345 single cell size, nm 2.446

O: \ 62 \ 62040.ptc Page 35 527413 _Case No. 88123132 7 / 年 ί Ε ί Lei Yue _ V. Description of the invention (31) Test procedure: Evaluation of cracking performance evaluation Examples 1 to 7 of the FCC catalyst, results Reported in Examples 8 to 15. Test the gas-oil cracking activity and selectivity of the mixed catalyst (candidate + balance catalyst). The method used is a 35% ^ 1 program from 0 to 3 9 0 7 and a 5 to 3% micro activity (% 8) Test method, the feed is vacuum gas oil (VGO). In a cyclic spillover experimental setup, vacuum gas oil or hydrotreated feeds were used to evaluate some additive catalysts. The composition of the three VGO feeds and a severely catalytic feed hydrotreating feed (CFHT) used in these examples is shown in Table 8. Table 8 Properties of cracked feeds Feeding properties VGO No. 1 VGO No. 2 VGO No. 3 CFHT API Specific gravity 26.6 22.5 24.2 23.6 Propylamine point, c 83 73 187 164 CCR, wt% 0.23 0.25 0.6 0.09 sulfur, wt% 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 Xppm 0.68-0.1 0.2 Fe, ppm 9.15-0 0.3 Cu, ppm 0.05-0 0 Na, ppm 2.93-0.6 1.2 Sim, Dist · ,. C ibp5 181 217 192 172 50 wt%? 380 402 430 373 99.5%? 610 553 556 547

O: \ 62 \ 62040.ptc Page 36 527413 _ Case No. 88123132 V. Description of the invention (32) iL ± A a Correction by changing the catalyst-oil ratio at 52 7 ° C (9 8 0 ° F) The reaction is performed to obtain a range of cleavage transformations. The range of the distillation point of the cracked product is: gasoline C5 + to 22 0 ° C (1 2 5 -4 3 0 T) light LCO 2 2 0 ° to 31 0 0C (4 3 0 T- 5 9 0 T) heavy LCO 310 ° to 370 ° C (590 °-700 ° F) Light Fuel Oil (LFO) 2 2 0 ° to 37 0 ° C (4 3 0 °-7 0 0 ° F) Heavy Fuel Oil (HFO) 3 7 0 ° C + (7 0 0 ° F +) Sulfur GC (AED) was used to analyze the gas-oil range products of each substance balance to determine the sulfur concentration in gasoline. In order to reduce the experimental error of the sulfur concentration related to the fluctuation of the distillation distillation point of gasoline, the sulfur species ranging from thiophene to C4-thiophene in synthetic crude oil were quantified, and the sum was defined as " distillate-gasoline Sπ. In order to determine the sulfur content of distillate fractions with boiling points above the gasoline range (Examples 14 and 15), the synthetic crude oil was subjected to atmospheric distillation to separate gasoline. The bottoms were then further vacuum distilled to produce two LFO / LCO fractions (light LCO and heavy LCO) and HFO. Quantification of sulfur species in the L C 0 sample was performed using G C equipped with a J & W 100 m DB-Petro column and a Sieve s 3 5 5 B sulfur detector. Based on the percentage of sulfur species obtained by GC, the concentration of each sulfur species of LCO was calculated, and the total sulfur content was measured by the XPS method. Example 8 Evaluation of Liquid Phase Catalytic Cracking of Series 1 Catalyst

The catalyst of Example 1 was placed in a fluidized bed steamer, and 50% of the steam and 50% of the gas described in Example 4 were used, and the steam was deactivated at 7 70 ° C (1 4 20 T) for 20 hours. Terminated by gas burning (end-oxidation). 25% by weight of the steamed additive catalyst was blended with an extremely low metal content (120 ppm V and 60 ppm N i) balanced catalyst obtained from the F C C plant.

O: \ 62 \ 62040.ptc Page 37 527413 Amendment No. 88123132 V. Description of the invention (33) V G 0 # 1 is used as the cracking feed for the microactivity test to evaluate the catalytic cracking performance of the catalyst. The properties of the catalysts are summarized in Table 9, where the product selectivity is interpolated to constant conversion and 65.5% by weight of the feed is converted to 220 ° C or below (430 ° F). Table series 1 catalyst, VG 〇 N 〇1 catalytic cracking performance E catalyst + 25% + 25% + 25% + 25% + 25% V / USY V / USY RE + V / RE + V / RE + V / USY USY USY Basic example Catalyst A Catalyst B Catalyst C Catalyst D Catalyst E MAT Product yield conversion rate, Wt ° / o 65 65 65 65 65 65 Catalyst / oil, 3.0 3.3 3.3 2.9 3.0 2.9 Increasing yield H2 yield, wt% 0.03 +0.05 +0.05 +0.04 +0.02 +0.04 q + q gas, wt% 1.1 +0.1 +0.1 +0 +0.1 +0 total C3 gas, wt% 4.3 +0.1 +0.1- 0.1 +0 -0.2 C3 = yield, wt% 3.7 +0.1 +0.1 +0 +0 -0.1 total c4 gas, wt% 9.3 +0.1 +0.2 -0.1 +0 -0.3 c4 = yield, wt% 4.7 +0.3 +0.4 +0.4 +0.1 +0 C5 + gasoline, wt% 47.6 -0.6 -0.4 +0.4 +0 +0.5 LF〇, wt% 29.6 +0 +0.2 +0 +0.1 +0 HF05 wt% 5.4 +0 -0.2 +0 -0.1 +0 Coke, wt% 2.4 '+0.3 +0.0 -0.2 -0.1 -0.1 Distillate gasoline S5 ppm 618 377 366 369 382 352% distillate gasoline S reduction Basic 39.0 40.8 40.4 38.3 43.1

O: \ 62 \ 62040.ptc Page 38 527413

Ping κ i inactivated v / usy _ catalyst was more than 10. %. m C5 · U catalyst / oil, gp, tongue 竑 φ] n 〇,, said last time; f ^, v / usv ^ ^,;, ν ^; r〇w = '′ + v: USY does not Will increase oil-to-oil tb and reach 65% conversion. The results of these two media-to-oil ratios show that RE + V / USY catalyst maintains better cracking activity.媒 The catalyst is more% 疋

Compared with the basic example of balanced catalyst, add V / USY & RE + V

The same percentage also shows changes in the yield of C: 4 gas, gasoline, light cycle oil, and heavy fuel oil. Adding V / USY and RE + V / USY catalysts makes the gasoline s concentration ^ =

change. When 25% by weight of the catalyst A * B (V / USY basic catalyst) was blended with each of the toilet FCC catalysts, the reduction in gasoline sulfur concentration reached 39.0 and 40. &. ♦ When 25% by weight iRE / USY catalyst (catalysts c and D) is added to the equilibrium catalyst, the sulfur reduction activity of ^, and Yuta is equivalent to the basic catalyst (38-4 0%). RE + V / USY catalyst containing most of the rare earth metals (catalyst E) can reduce gasoline sulfur by 43.1%, and make gasoline S content higher than V / USY and mixed RE / USY catalyst. Another reduction is 4%, that is, an improvement of 10%. All catalysts have the same vanadium content (0.36-0.39%). These results show that the addition of rare earth elements will improve the cracking activity of V / USY catalysts. There was little change in the yield of the cracked product. In the rare-earth ion house, 钸 has unique properties, because Ce + V / USY catalyst has not only higher cracking activity but also increased gasoline depletion in liquid-phase catalytic cracking conditions. The rare earth RE / USY catalysts that do not contain a large amount of plutonium have no additional benefit compared to V / USY when gasoline S is reduced, while the existence of plutonium further makes V / USY or RE / USY (excluding a large amount of钸 content) The sulfur content of gasoline in catalyst ^ 进 一

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Step down. Example 9 Comparison of catalyst cracking activity of Series 2 Catalyst ^ re / v / usy of Example 2 (Series 2 Catalyst 'catalyst F, G, H) at 7 7 0 C (1 4 2 0 F) Strips were inactivated for different lengths of time to compare catalyst stability. In a fluidized bed steamer, 50% tritium is used (the end of the cycle steaming-returning, as described in Example 4 above) "'steam-based 2.3' 5.3, 20, and 3. Hours ... retention of the catalyst is plotted in the figure 2. Use the ASTM micro-activity test (ASTM procedure D-3 907) and vacuum gas oil # 2 (2 · 6 weight τ% S or more) to test the gas-oil cracking activity of the steam deactivation catalyst. In 30 seconds Contact time and reaction temperature at 54 5 ° C (9 80 ° F), measuring the conversion ratio of the strange catalyst-oil ratio of 4: 1 to 220 ° C ~ (430 T-)% by weight. The conversion rate as a function of steam inactivation time is plotted in Figure 3. The surface area retention shown in Figure 2 shows that V / USY and RE + V / USY catalysts show equivalent surface area retention under various hydrothermal inactivation conditions. That is, all three catalysts have the same frame structure stability. However, the conversion curve shown in Figure 3 clearly shows that 'RE + V / USY has more improved cleavage activity retention when the severity of hydrothermal inactivation is increased. During hydrothermal inactivation, the cleavage activity from V / USY to RE + V type was improved to 15% conversion rate. Among the RE types with different amounts No obvious difference is seen. These results are consistent with Example 8, where RE + V / USY achieves the target conversion rate at a lower catalyst-oil ratio than V / USY. These conversion rate results show that RE + V / USY catalyst is more stable and maintains better cracking activity than V / USY catalyst. Adding rare-earth ions to USY, followed by steam calcination to reduce the size of single-hole chambers of Fr.

O: \ 62 \ 62040.ptc Page 40 527413 Amendment No. 88123132 V. Description of the invention (36) Example of stability in the presence of 1 1 Liquid phase catalytic cracking evaluation of 0 series 3 catalysts Example 3 (catalysts I, J The V and Ce + V USY catalysts were placed in a fluidized bed steamer, using 50% steam and 50% gas as described in Example 4 above at 7 7 0 ° C (1 2 2 0 ° F). The steam is deactivated for 20 hours and ends with gas-burning (end-oxidation). 25% by weight of the steamed additive catalyst was blended with a low-metal FCC equilibrium catalyst (120 p p m V and 60 p p m Ni). The blended catalyst was then evaluated using the above-mentioned M A T test using VGO # 1 feed.

The performance of Series 3 catalyst using VGO # 1 feed is summarized in Table 10, where the product selectivity is interpolated to a constant conversion rate, and the 70% by weight feed is converted to 2 2 0 ° C-(4 3 0 ° F-) Substance.

O: \ 62 \ 62040.ptc Page 41 527413 Case No. 88123132 f / year / month, / Amendment V. Description of invention (37) Table 10 Catalytic cracking performance of series 3 catalyst E Basic example of catalyst + 25% V / USY Catalyst C Catalyst I) + 25% Ce + V / USY Catalyst (Catalyst J) MAT Product Yield Conversion Rate, wt ° / 〇70 70 70 Catalyst / Oil 3.3 3.8 3.7 Increasing Yield H2 Rate, wt% 0.03 +0.04 +0.13 Q + q gas, wt% 1.4 +0.1 +0.1 total C3 gas, wt% 5.4 +0.1 -0.1 C3 = yield, wt% 4.5 +0.1 -0.1 total C4 gas, wt% 10.9 +0.2 -0.2 C4 = yield, wt% 5.2 +0,4 +0.2 iC4 yield, wt% 4.8 -0.2 -0.4 C5 + gasoline, wt% 48.9 -0.3 -0.3 LFO, wt% 24.6 +0.5 +0.3 HFO , wt% 4.7 -0.2 -0.1 Coke, wt% 2.7 · +0 +0.5 distillate gasoline S, PPM 529 378 235% distillate gasoline S minus 29 56 less

O: \ 62 \ 62040.ptc page 42 527413 __case level 88123132 f / year, month day, day five, invention description (38) 'Table 10 compares V / USY and Ce + V / USY / silica-aluminum Soil-clay catalysts, each of which is blended with a balanced FCC catalyst (E-catalyst), F CC performance after circulating steam deactivation ('stem beam oxidation). Compared with the basic example of E solution, the addition of v / us γ and Ce + V / USY catalysts only slightly changed the yield structure of the total product. The yields of gas, gasoline, light cycle oil, and heavy fuel oil all changed little. A moderate increase in nitrogen $ coke yield was seen. Although the product yield is small, the V / USY and… C e + V / U S Y catalysts actually change the gasoline s concentration. When 25% by weight of Catalyst I (V / USY benchmark catalyst) was blended with a balanced FCC catalyst, the sulfur concentration in gasoline reached 29%. In comparison, the Ce + V / USY catalyst (catalyst J) produces a f6% reduction in gasoline sulfur. Adding Ce to the V / USY catalyst reduced the gasoline sulfur content by an additional 2 7%, that is, 9 3% improvement over the V / USY benchmark catalyst. Both catalysts had the same hunger content (0.39% vs. 0.43% V). In view of the fact that Ce itself does not have any gasoline 'sulfur reduction activity (see Example 1 1 below), these results are quite unexpected and clearly demonstrate the benefits of the addition. Example 1 Evaluation of Liquid Phase Catalytic Cracking of Catalysts 1 1 and 2 4 after Cyclic Steaming The properties of the v and Ce + V catalysts of Example 4 will be summarized in this example. The series 4 catalyst was deactivated by cyclic steaming (end-return) as described in Example 4 above, and then the catalyst was balanced with low metal (120 ppm V and 60 ppm N i) FCC catalyst. Blended in a 25:75 weight ratio and tested using VGO # 1 feed. The results are summarized in Table 丨 丨.

O: \ 62 \ 62040.ptc Page 43 527413 _ Case No. 88123132 V. Description of the invention (39) 9 / year / month / ^ Amendment Table 11 V Catalytic cracking performance of V on V / USY / silica-dissolved catalyst E catalyst + 25% Basic example V / USY catalyst (catalyst κ) + 25% Ce + V / USY (catalyst M) + 25% Ce + V / USY (catalyst N) MAT product yield conversion rate , Wt ° / o 65 65 65 65 Catalyst / oil 3.0 3.4 3.2 3.3 Increasing yield H2 yield, wt% 0.03 +0.02 +0.02 +0.02 (^ · Κ: 2 gas, wt% 1.1 +0 +0 +0.1 Total C3 gas, wt% 4.4 -0.1 -0.1 +0 c3 = Yield, wt% 3.7 +0 -0.1 +0 Total C4 gas, wt% 9.5 -0.1 -0.2 -0.1 C4 = Yield, wt% 4.8 +0.1 +0.1 +0.1 iC4 yield, wt% 4.1 -0.2 -0.3 -0.1 C5 + gasoline, wt% 47.4 +0.1 +0.5 +0.1 LFO? Wt% 29.7 -0.2 +0 -0.1 HF〇, wt% 5.3 +0.2 +0 +0.1 Coke, wt% 2.3 +0.1 -0.1 +0 distillate gasoline S, PPM 516 489 426 426% distillate soot S reduction of basic 5.2 17.4 17.4

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Table 11 compares the FCC performance of V / USY and Ce + V / USY Shi Xiite-sol addition catalysts-after steam deactivation (end-return). Compared with the basic example of E catalyst, the change in the total product yield structure of adding v / uy and CeK / USY catalysts = very small. The yield of hydrogen, C4 gas, gasoline, light fuel oil, heavy fuel oil and 隹 · is less than 0.2% by weight. The addition of V / USY and Ce + ^ and f catalysts changes the gasoline S concentration to different degree. When 25% by weight of catalyst K (V / USY-base catalyst) is blended with balanced FCC catalyst, gasoline sulfur concentration is reduced by 5.2%. For comparison, Ce + V / USY catalyst (catalysts μ and ^ reduce gasoline S by 17.4% respectively. Add Ce to V / USY catalyst compared to V / USY benchmark. The catalyst makes gasoline S content again Decrease 1 2 · 3%, ie, 2 37% improvement. Example 1 Evaluation of liquid phase catalytic cracking of catalysts after circulating steaming in 2 series = 4 catalysts (= Example 4 V and ce + V catalysts in circulating steam loss The performance after activation will be summarized in the present example. The catalyst of Example 4 was deactivated by the cycle steaming (end-oxidation) described in Example 4 above, and then the catalyst was mixed with low metal (120 ppm ¥ and 6). 〇ppm Ni) FCC equilibrium catalyst was blended at a weight ratio of 25:75. The evaluation results obtained by feeding VG0 are summarized in Table 12.

527413 Case No. 88123132 Amendment Month, ^ Day Amendment V. Description of Invention (41) Table 12 Catalytic cracking performance of V on Ce + V / USY / silica-sol catalyst

E catalyst + 25% Basic example V / USY catalyst (catalyst K) + 25% Ce + V / USY (catalyst L) + 25% Ce + V / USY (catalyst M) MAT product yield conversion rate , Wt% 70 70 70 70 catalyst / oil 2.8 3.7 3.6 3.4 H2 yield, wt ° > 〇0.03 +0.12 increasing yield +0.13 +0.12 Ci + Q gas, wt% 1.5 +0.2 +0.2 +0.1 total C3 Gas, wt% 5.5 +0.1 +0 -0.1 C3 = Yield, wt% 4.7 +0 +0 -0.1 Total C4 gas, wt% 11.1 +0 +0 -0.2 C4 = Yield, wt% 5.8 +0.1 +0.1 +0 iC4 yield, wt% 4.6 -0.1 -0.2 -0.2 C5 + gasoline, wt% 49.4 -1.0 -0.9 -0.5 LFO, wt% 25.6 -0.1 +0 +0.2 HFO, wt% 4.4 +0.1 +0 -0.2 coke , Wt% 2.3 +0.6 +0.5 +0.5 distillate gasoline S, PPM 579 283 243 224% distillate gasoline S reduced by 51.1 58.1 61.3 O: \ 62 \ 62040.ptc page 46 527413 _ case number 88123132 V. Description of the invention (42) y Guangnian / Monthly Modified Table 1 2 Compare the FCC performance of V / USY and Ce + V / USY / Shi Xishi-I Lu geosol additive catalyst after steam deactivation (end-oxidation). Compared with the basic example of the E catalyst, the addition of V / USY and Ce + V / USY catalysts caused this slight change in the yield of the total product. The yield of hydrogen and coke increased moderately. We also saw small changes in the yields of (: 4 gas, two gasoline, light cycle oil, and heavy fuel oil. Adding v / U $ γ and Ce + V / USY catalysts changed the gasoline S concentration considerably. When 25% by weight of media K (V / USY-base catalyst) is blended with a balanced FCC catalyst, the gasoline concentration is reduced by 51.1%. In comparison, Ce + V / USY catalyst (catalyst / And ^) produced 5 8 · 1% and 6 1 · 3% gasoline S reduction respectively. Adding ce to v / us γ catalyst reduced gasoline S content by 7 · 0-1 compared with V / USY benchmark catalyst. 〇2%, that is, up to 20% improvement. · The yield data of ', VMSY and Ce + V / USY catalysts show that the yield change of e-catalyst is due to the addition of 鈒 to USY catalyst. V The yield of the / USY catalyst is equivalent to that of Ce + V / USY catalysts except for the gasoline s content. These surnames clearly indicate that Ce will increase the gasoline activity of V / USY additive catalysts and has little effect on the yield. Preliminary example of τ seat 1 3 series 5 catalysts for liquid phase catalytic cracking evaluation, research on the promotion effect-^ 列 5 ^ 1 and. + ¥ The catalyst is deactivated in the cycle steaming as described above. In this example. The low catalytic metal i v "PnPmiM ί WPPm Ni) FCC equilibrium catalyst in a 25: 75 weight ratio obtained from a pick feed fool Mixed results are shown in Table engagement .VGO # j 3 in.

527413 _ Case No. 88123132 V. Description of the invention (43) Year, month / fa amendment Table 13

Catalytic cracking performance of Ce on Ce + V / USY / silica-clay catalyst

E catalyst + 25% Basic example V / USY catalyst (catalyst 0) + 25% Ce + V / USY (catalyst P) + 25% Ce + V / USY (catalyst Q) MAT product yield conversion rate , Wt ° / o 70 70 70 70 Catalyst / oil 3.2 3.4 3.7 3.9 H2 yield, wt% 0.04 +0 Increasing yield +0.07 +0.07 Ci + C2 gas, wt% 1.5 +0.1 +0.1 +0.1 total C3 gas , Wt% 5.7 +0.1 -0.1 +0 C3 = yield, wt% 4.8 +0 +0 +0 total C4 gas, wt% 11.5 +0 -0.3 -0.1 yield, wt% 5.7 +0 +0.1 +0.1 iC4 Yield, wt% 4.9 +0 -0.3 -0.2 C5 + gasoline, wt% 48.8 -0.2 -0.2 -0.7 LFO? Wt% 25.5 +0 +0.1 +0.1 HF〇, wt% 4.5 +0 -0.1 -0.1 coke, wt % 2.4 * +0 +0.3 +0.6 distillate gasoline S, PPM 486 487 341 351% distillate gasoline S reduced by 0 29.8 27.7 O: \ 62 \ 62040.ptc page 48 527413

O: \ 62 \ 62040.ptc Page 49 527413 _ Case No. 88123132 V. Description of the invention (45) f / year, month /./ s Amend Table 14 RE + V / USY / silica-sol catalyst catalytic cracking Performance E catalyst + 25% RE + V / USY Basic example (catalyst R) Yield conversion rate of overflow product, wt% 75 75 Catalyst / oil 7.0 6.7 Increasing yield H2 yield, wt% 0.03 +0.01 Total C3, wt% 6.5 -0.1 Total C4, wt% 12.1 -0.1 C5 + gasoline, wt% 49.4 -0.1 LFO, wt% 18.3 -0.1 HF〇, wt% 6.7 +0.1 coke, wt% 4.1 +0.3 hepar gasoline S, ppm 735 589 LC〇sulfur, wt% 2.36 2.16% gasoline sulfur reduction Basic 20% LC〇 sulfur reduction. Basic 9 Compared with the basic example, adding 25% by weight of RE + V / USY catalyst on the structure of the total product yield The changes produced are small. The increase in H2 and coke yields is negligible. Slight changes in the yield of C4-gas, gasoline, light cycle oil and heavy fuel oil were also seen. The addition of RE + V / USY catalyst changed the gasoline sulfur concentration considerably. The sulfur concentration of gasoline reached 20%. In addition to the reduction in gasoline sulfur, a considerable reduction in sulfur in the LCO was also seen, which is equivalent to a 9% reduction in LCO sulfur.

O: \ 62 \ 62040.ptc Page 50 527413 Amendment __ Case No. 88123132 V. Description of the invention (46)

The sulfur species in LjO are shown in Table 15 and Figure 4. LC0 contains a considerable range of benzothiophene and dibenzothiophene sulfur species. Substituted benzothiophene and substituted dibenzo, the reduction of sulfur of phenols such as CV-benzothiophene and Ci to ^ +-dibenzothiophene is more significant. The results were quite unexpected, as the substituted dibenzothiophene is relatively large and it is expected to be more difficult to crack and desulfurize in the FCC. Table 15 From the VG0 feed! The sulfur classification of LC0 (sulfur in wt% LCO) E catalyst + 25% RE + V / US Y Basic example (catalyst D benzothiophene 0.04 0.04 Cr benzothiophene 0.22 0.24 c2-benzothiophene 0.39 0.38 c3 + -Benzothiophene 0.47 0.38 dibenzothiophene 0.10 0.09 cv dibenzothiophene 0.36 0.32 c2-dibenzothiophene 0.39 0.35 c3-dibenzothiophene 0.24 0.22 c4 + -dibenzothiophene 0.16 0.14 total 2.36 2.16

Evaluation of Ce + V / USY Shi Xiite-sol-catalyzed liquid-phase catalytic cracking In a circulating fluidized cracking unit, the severe hydrotreating f CC feed (CFHT feed) in Table 8 is used together with a typical FCC catalyst Evaluation Example 7 Ce + V / USY catalyst (catalyst S) for 40 days' basic FCC balanced catalyst with extremely low metal content (200 ppm V and 130 ppm Ni). For the first 15 days, a daily blend of 5 0/50 of a fresh FCC catalyst and Example 7 Ce + V / USY catalyst was used as catalyst inventory.

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Page 527 413

1.4% is added to the FCC regenerator. From day 15 to day 40, a 85/15 blend of fresh FCC catalyst and Ce + V / USY catalyst was added to the FCC regenerator at 1.4% daily. During the entire evaluation process, the catalyst storage temperature was maintained at about 70 5 1 3 0 0 T). Collect two balanced touch = regenerator samples. The first sample was collected before Ce + V / USY was added (basic example). The second sample was collected on the 40th day. According to Ce and v analysis, the content of ce + V / USY touching the media shoulder was estimated to be 12%. The F C C performance of the catalyst is summarized in Table 16. The product selectivity is interpolated. The conversion rate is determined. 70% by weight of the feed is converted to 2 2 0 (4 3 0 ° F-).

Page 52 O: \ 62 \ 62040.ptc 527413 Case No. 88123132 V. Description of the invention (48) _ Amendment Table 16 Catalytic cracking performance of sol catalyst

Ce + V / USY / Silica E catalyst + 12% Ce + V / USY Basic example (catalyst S) Overflow product yield conversion rate, wt% 70 70 Catalyst / oil 6.5 6.4 Increasing yield H2 yield , Wt% 0.02 +0.0 total C3, wt% 4.8 +0.0 total C4, wt% 9.3 +0.1 C5 + gasoline, wt% 51.9 -0.2 LF〇, wt% 24.0 -0.2 HF〇, wt% 6.1 +0.1 coke, wt% 2.6 +0.1 crane parts gasoline S, ppm 100 79 light LC0 sulfur, ppm 815 599 heavy LCO sulfur, ppm 1957 1687 HFO sulfur, ppm, 2700 1700% gasoline sulfur reduction is basically 21% light LC〇S reduction * basic 27% weight 1 > (: 〇3 reduction of basic 14% HF sulphur reduction of basic 37 Wt% waste catalyst sulfur < 0.06 < 0.06

1BB O: \ 62 \ 62040.ptc Page 53 527413 V. Description of the Invention (49) Compared with the basic example of E catalyst, the addition of Ce + V / USY catalyst produces a small change in the structure of the total product f. H2 and coke yields did not increase. Also see slight changes in the yield of C4_ gas, gasoline, light cycle oil and heavy fuel oil. The addition of C e + V / US Y catalyst greatly changes the gasoline s concentration. When 2% by weight of Ce + V / USY catalyst is added to the balanced FCC catalyst, the gasoline sulfur concentration decreases to 21%. In addition to the reduction of gasoline sulfur, a large amount of sulfur reduction was also seen! ^^ & HF〇 0 Sulfur G C was used to analyze sulfur species in the light L C 0 fraction. The concentration of each organic sulfur is shown in Table 17 and the light LCO is shown in Figure 5. Table 17 (PPM light carbon in LCO) E catalyst + 12% Ce + V / uSY basic example abdominal media J) C3 + thiophene 4 1 benzothiophene 20 14 cv benzothiophene 141 106 c2-benzothiophene 237 174 c3 +- Benzothiophene 295 215 Dibenzothiophene '17 14 cr Dibenzothiophene 47 34 c2-Dibenzothiophene 32 25 c3-Dibenzothiophene 20 13 C / -Dibenzothiophene / 3 1 Total 815 599 Tellurium Extinction is equivalent to a light LC 0 sulfur reduction of 27% in total. In substituted benzothiophenes such as Γ% less 1 to C,

527413 _Case No. 88123132 Amended / Month_ V. Description of the invention (50) Benzothiophene is more significant, and the result is quite unexpected, because the substituted benzothiophene is larger and it is expected that it will be more difficult to crack and Desulfurization. The sulfur species in the heavy LCO fraction are shown in Table 18 and FIG. 6. Heavy LCO contains the major dibenzothiophene sulfur species. Sulfur reduction (14% by weight of LCO in total) is more pronounced in substituted dibenzothiophenes such as G to (: 4 + -dibenzothiophene. The results are quite unexpected, as substituted dibenzothiophenes are larger and expected It will be more difficult to crack and desulfurize in FCC. Table 18 Sulfur classification of heavy LCO from CF.HT feed (PPM heavy sulfur in LCO) Basic example of E catalyst + 12% Ce + V / USY (catalyst S) Benzothiophene 0 0 cv Benzothiophene 2 1 c2- Benzothiophene. 12 7 c3 +-Benzothiophene 128 86 Dibenzothiophene 65 54 Cp Dibenzopyrene 361 312 c2-Dibenzothiophene '537 480 c3 -Dibenzothiophene 475 425 c4 + -Dibenzothiophene ^ 378 322 Total _ 1957 1687 Sulfur reduction catalysts are very active in reducing benzothiophene and dibenzothiophene species and thiophene sulfur species. Sulfur The reduction mainly occurred in substituted benzothiophene and substituted dibenzothiophene. These results show that the C-S bond of alkyl-substituted thiophene is more reactive and easily cleaved.

O: \ 62 \ 62040.ptc Page 55 527413 Amendment No. 88123132 V. Description of the invention (51) The reduction of sulfur easily available from substituted thiophene, substituted benzothiophene and substituted dibenzothiophene is quite unexpected, And will enhance the efficiency of the subsequent LCO hydrodesulfurization process. It is well known in the process of LCO hydrodesulfurization that alkyl substitution of benzothiophene and dibenzothiophene will greatly reduce the desulfurization reactivity of organic sulfur and become π hard sulfur π or "heat-resistant sulfur". We have LCOs with lower substituted benzo and dibenzothiophene. After the hydrodesulfurization process, we will produce diesel fuel with lower sulfur content than the equivalent LCO produced by conventional FCC catalysts.

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O: \ 62 \ 62040-911217.ptc Page 57

Claims (1)

527413 _ Case number 6. Scope of patent application 1. A catalyst pore molecular sieve with reduced sulfur content containing organic sulfur products. The pore structure of the catalyst is a component, which belongs to the rare earth group. It has a metal component based on oil feed. The amount ratio and the rare earth ratio. 2. If applying specifically for large pore size as the first metal 3. If applying for special octahedral stone. 4. If applying specifically for hunger. 5. If the application contains lanthanum alone, or 6. If the application contains lanthanum alone. 7. If a method for sulphur content in a catalytically cracked petroleum distillate is applied, the method comprises the step of catalytically cracking the petroleum feed fraction of the compound in the presence of a high temperature and a cracking catalyst; The medium contains mostly (i) a first metal component, which is contained within the molecular sieve and contains a metal having an oxidation state greater than zero, and (ii) a second gold in the internal pore structure of the molecular sieve, and which contains at least one sulfur content Reduced liquid cracking products, in which the stone has an initial boiling point of at least 290 ° C (550 ° F), and the first series accounts for 0.1 to 10 weight percent of the total of all catalyst compositions The method according to item 1 in the range of 0.1 to 10% by weight of the total catalyst composition, wherein the product sulfur reduction catalyst bag or a medium pore size zeolite is used as a molecular sieve component, and at least vanadium, One of zinc, iron, cobalt or gallium. The method of the second range, wherein the macroporous zeolite comprises the method of the second range, wherein the first metal component includes the method of the second range, wherein the second metal component includes a combination with #. The method of the second item of interest, wherein the second metal component covers the method of the first item of interest, wherein 1 to 10% by weight of the composition of the second metal component. O: \ 62 \ 62040-911217.ptc Page 58 527413 _ Case No. 88123132 0 丨 Month and Day__ VI. Application for patent scope 8. If the method of the first patent scope is applied, the product sulfur reduction catalyst contains UCS is 2. 420 to 2.460 nm, and U SY zeolite with a ratio of at least 5.0 of pine silica to alumina is used as the molecular sieve component, and as the first component, at least one of zinc or vanadium with an oxidation state greater than zero, and Plutonium of two metal components, alone or in combination with lanthanum. 9. The method according to item 1 of the patent application range, wherein the sulfur reduction catalyst is an individual particulate additive catalyst. 10. The method according to item 1 of the scope of patent application, wherein the liquid cracked product with reduced sulfur content includes gasoline fractions, circulating oil fractions and fuel oil fractions, wherein the boiling points of the circulating oil and fuel oil are above the gasoline fraction. . 1 1. A method for catalytic cracking, wherein a heavy hydrocarbon feed containing organic sulfur compounds is subjected to a circulating fluidized catalytic cracking process consisting of particles having a size from 20 to 100 micrometers in a cycle catalyst cycle cracking process The catalytic stock is contacted to catalytically crack into lighter products. The steps are as follows: (i) In a catalytic cracking zone operated under catalytic cracking conditions, the feed is catalytically cracked by contacting the feed with a regeneration cracking catalyst to produce a product containing cracked products. And cracking zone effluent of waste catalyst containing coke and strippable hydrocarbons; (ii) discharging and separating the effluent mixture into a gas phase rich in cracked products and a solid-rich phase containing waste catalyst; (iii) removing the gas phase with the product, and fractionating the vapor to form a liquid cracked product including gasoline, (iv) stripping the solid catalyst-rich waste catalyst phase to remove adsorbed hydrocarbons from the catalyst, (v) The stripped catalyst is sent from the stripper to the catalyst regenerator. O: \ 62 \ 62040-911217.ptc Page 59 527413 _Case No. 88123132 4 丨 Year | Revised Date_ Sixth, the scope of patent application (v 1) will be touched by stripping by contact with oxygen-containing gas Regeneration of catalysts to produce regenerating catalysts; and (vii) returning regenerated catalysts to the cracking zone to contact further heavy hydrocarbon feeds, where the sulfur content of the liquid cracked product is performed in the presence of the product sulfur reducing catalyst Reduced by catalytic cracking; the product sulfur reduction catalyst includes a porous molecular sieve, which has (i) a first metal component, which is in the internal pore structure of the molecular sieve and contains a metal with an oxidation state greater than zero and (ii) a second Metal component 'is in the internal pore structure of the molecular sieve and contains at least one rare earth group, where the feed has an initial boiling point of at least 290 ° C (550 ° F), and the amount of the first metal component It is 0.1 to 10 weight percent of the total catalyst composition and the amount of rare earth is 0.1 to 10 weight percent of the total catalyst composition. 12 Method wherein the cracking catalyst comprises a faujasite13. The method according to item 12 of the scope of patent application, wherein the product sulfur reduction catalyst includes macroporous or mesoporous zeolite as a molecular sieve component, vanadium as the first metal component and hafnium, alone or with at least one other rare earth group Metal bonding as a second metal component. 14. The method according to item 13 of the patent application scope, wherein the macroporous zeolite of the product sulfur reduction catalyst comprises faujasite. 15. The method of claim 11 in the scope of patent application, wherein the first metal component includes hunger. 16. The method according to item 11 of the patent application range, wherein the second metal component comprises lanthanum, alone or in combination with thorium. O: \ 62 \ 62040-911217.ptc Page 60 527413 _ Case No. 88123132 Θ 丨 year (monthly said amendment_) 6. Application for patent scope 1 7. The method of item 11 for patent scope, in which the second metal The component contains brocade. 1 8. The method according to item 11 of the patent application scope, wherein the second metal component is present in an amount of 1 to 10% by weight of the catalytic composition. 1 9. As item 11 in the patent application scope A method in which the liquid cracking product contains gasoline fractions with reduced sulfur content and reduced sulfur content, and circulating oils with boiling points above the gasoline fraction. 20. — A species used to reduce catalytic cracking gasoline distillation during the catalytic cracking process. Fluidized catalytic cracking product sulfur reduction catalyst composition with a sulfur content of 1 part, comprising fluidizable particles of (i) porous molecular sieve components having a size from 20 to 100 microns, and (ii) containing an oxidation state greater than zero A first metal component of a metal located in the internal pore structure of the porous molecular sieve component and (iii) a second metal component including a rare earth metal located in the internal pore structure of the porous molecular sieve component, wherein Occupancy 0.1 to 10% by weight of the total amount of the catalyst composition and the amount of the rare earth metal are 0.1 to 10% by weight of the total amount of the catalyst composition. 2 1. Fluid such as the 20th in the scope of patent application The catalytic cracking product sulfur reduction catalyst composition, wherein the porous molecular sieve component comprises a porous hydrocarbon cracking molecular sieve component. 2 2. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 21 of the patent application scope, wherein Porous molecular sieve component. It includes zeolite USY with a UCS of 2. 420 to 2. 460 nm and a pine silica: alumina ratio of at least 5.0. 2 3. As described in item 22 of the scope of patent application 4 2 0 至 Fluidized catalytic cracking product sulfur reduction catalyst composition, wherein the porous molecular sieve component comprises a UCS of 2. 4 2 0 to O: \ 62 \ 62040-911217.ptc page 61 527413 _ case number 88123132 _ year (Yueyue said _ifi_ VI. Patent application scope 2. 4 3 5 n π and pine silica: alumina ratio is at least 5. 0 zeolite USY. 2 4. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 20 of the patent application scope, which contains 0.1 to 5% by weight of hunger as the first metal component. Weight is based on 25. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 24 of the patent application scope, which comprises a combination of rhenium and at least one other rare earth group as the second metal component. 2 6. For example, the fluidizable catalytic cracking product sulfur reduction catalyst composition of the scope of patent application No. 20, which contains thorium as the second metal component. 2 7. The fluidizable catalytic cracking product of scope of the patent application No. 20 Sulfur reduction catalyst composition, in which the metal component has been introduced into the zeolite by exchanging cationic species in the pores of the zeolite. 28. For example, the fluidizable catalytic cracking product sulfur reduction catalyst composition of item 20 of the patent application scope, which Formulated with matrix components as liquid phase catalyst additives 29. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 20 of the patent application scope, which is formulated as an integral fluidizable catalytic cracking product sulfur reduction catalyst for cracking a hydrocarbon feed to produce Liquid cracking products of gasoline and reducing sulfur content in the catalytic cracking gasoline distillate during the catalytic cracking process; the catalyst contains fluidizable particles having hydrocarbon cracking components ranging in size from 20 to 100 microns, including zeolites A molecular sieve containing (i) a first metal component in the pore structure of the zeolite, which contains at least one of vanadium, zinc, iron, cobalt, and gallium, and (ii) a second metal component, which contains at least one rare earth group 3 〇 Such as the scope of the patent application of the scope of the 29th catalytic cracking product reduction O: \ 62 \ 62040-911217.ptc Page 62 527413 Amendment_Case No. 88123132 Six. Patent application scope Sulfur catalyst composition containing 0.1 to 5% by weight (based on the total amount of zeolite) vanadium As the first metal component. 31. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 29 of the patent application scope, wherein the second metal component comprises a combination of thorium and at least one other rare earth group in an amount of 1 to 5% by weight. 32. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 29 of the patent application scope, wherein the second metal component comprises a combination of rhenium in an amount of 1 to 5% by weight of the catalyst. 33. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 29 of the patent application scope, wherein the zeolite molecular sieve comprises a UCS of 2. 42 0 to 2. 4 6 0 nm and pine silica: bauxite Zeolite USY with a ratio of at least 5.0. 3 4. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 32 of the scope of patent application, wherein the porous molecular sieve component includes a UCS of 2. 40 to 2. 4 3 5 nm and pine silicon Stone: zeolite USY with a bauxite ratio of at least 5.0. 35. The fluidizable catalytic cracking product sulfur reduction catalyst composition according to item 29 of the patent application scope, which is formulated with the matrix component and faujasite as the cracking component to form an overall liquid phase cracking product sulfur reduction catalyst. . ill I O: \ 62 \ 62040-911217.ptc Page 63