JPH01500250A - Metal-containing spinel composition and method of using the same - Google Patents

Abstract

A composition of matter comprising at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of the first metal, a minor amount of at least one-third metal component effective to promote the oxidation of sulfur dioxide to sulfur trioxide at sulfur dioxide oxidation conditions, and a minor amount of at least one-fourth metal component effective to promote the reduction of first metal sulfate at first metal sulfate reduction conditions. These compositions are useful, e.g., in hydrocarbon conversion processes, to reduce sulfur oxide and/or nitrogen oxide atmospheric emissions.

Description

[Detailed description of the invention] Metal-containing spinel compositions and methods of use thereof are directed against the release of sulfur oxides into the atmosphere. and/or improved metals for use in reducing nitrogen oxide emissions. The present invention relates to a composition containing Subiyoru. In one specific embodiment, the present invention provides carbonization Sulfur oxides and/or sulfur oxides emanating from the regeneration zone of the hydrogen catalytic cracking unit For MM clugging of A-containing hydrocarbon feedstocks with vertical reduction of elementary oxides Compositions and methods are included.

Typically, hydrocarbon catalytic cranking is a reaction zone under hydrocarbon cracking conditions. carbonaceous stomate, producing at least one hydrocarbon product, and producing at least one hydrocarbon product; ) is deposited on the eyebrows. Additionally, some ions present in the feedstock hydrocarbon C is also deposited on the catalyst, for example as a component of coke.

Sulfur-containing coke deposits tend to deactivate the catalytic catalyst. Contact J! ! ! The catalyst exhibits satisfactory performance when it is recycled into the reactor or regeneration area. combustion with oxygen-containing gas at low coke levels, typically around CL 4! It is advantageous to regenerate continuously to less than kX. In the playback area, At least a portion of the sulfur is oxidized together with the carbon and hydrogen deposited on the catalyst, producing iodine. It is produced in the form of sulfur oxides (sulfur dioxide and sulfur trioxide, hereinafter referred to as "SOx"). It leaves with IX amounts of carbon monoxide, carbon dioxide and water. coke deposits and/or or at least some nitrogen present in the oxygen-containing gas is subject to conditions in the regeneration zone. oxidized to nitrogen oxides, which also leave with the exhaust gas from the regeneration zone.

Considerable recent research efforts have e.g. Directed to reducing atmospheric emissions of sulfur and nitrogen oxides. Such oxidized ions One technique that has been proposed to reduce sulfur emissions is the association of sulfur with oxides. It is possible to circulate more than one metal oxide with the catalyst in the regeneration zone. It includes. Particles containing associated sulfur oxides enter the reduction zone of the cranking region. When circulated throughout the area, the associated sulfur compounds combine with gaseous sulfur-containing substances such as hydrogen fumide. It is discharged along with the products from the cranking area and is typically The equipment is in a form that can be easily handled at oil refineries. metal reaction The material is regenerated into active form and further associated with sulfur oxides when recycled to the regeneration area. I can do something.

Introduced as catalyst particles or present on any of a variety of "inert" supports. The global components present are Noxalos and Vasalos’ Jlf (Vasalos), respectively. and Vasalos et al.) to U.S. Patent No. 4.15 to 534 and 4.154535 to reduce sulfur oxide emissions from the regenerator gas. In order to reduce the Alternately exposed to surrounding air. Ruthenium, rhodium, palladium and um, platinum, osmium, iridium, platinum, (nadium, uranium, di A metal oxidation promoter consisting of conium, rhenium, iron, and their mixed components. It is also present when carbon oxide emissions are to be reduced. Vassalos et al. are more preferable. Metal promoters include ruthenium, rhodium, palladium, osmium, iridium, white The gold and rhenium components are helpful. These allowances are alkaline earth floor, na ) Reduces the emission of sulfur oxides and 8 substances such as IJium, heavy metals, and rare earths. It discloses 19 different metal components including suitable reactions to produce a metal.

Particularly preferred metal reactions @negative are sodium, magnesium, manganese, and copper. Ru. The carrier for these metal reactants is preferably at least 50 per duram. It has a surface area of m2. A specific example of a support that is said to be "inert" is There are silica, alumina and silica-alumina.

These percentages of basalos and basalos, etc. are furthermore due to the presence of certain lumps of metal reactants (e.g. oxides of iron, manganese or cerium) are used to scavenge sulfur oxides. If desired, such total components may be prepared in the form of a finely ground powder. Ar) It indicates what you can get.

For desulfurization of non-FCCU exhaust gas in areas outside the unit where SOx is generated Many absorbents have been proposed.

In some such non-FCCtJ applications, adsorption warfare is performed by cranking the FCC unit. The area is being regenerated within the quay area, which is considerably more nitrogen-rich than the surrounding area. Lowell et al. Well, etal, ) publication “Metal Acids for the Removal of SOx from Exhaust Gases” Selection of CHEMICALS (5ELECI’ON OFλIETAL 0XIDES FOR TLEl+X) VING SOx F’RC! V FLTJF-GIAS) J, (lnd, Eng.

Chemical Process Design Development, Vol, 10.

November 3, 1971) disclosed 15 adsorbents for flue gas desulfurization. It is. In U.S. Patent No. 4.001.575 to Longo 572-1472''F, preferably using cerium on an alumina support. or non-FCCU exhaust gas flow fluctuation at temperatures between 932 and 1100'F''. It absorbs SO2 from car exhaust.

D, W, Deberry + et al. [SO 2 and the reaction rate of metal oxide (RATES OF R Tomoe CTl0N OF 802 WIT) (λ1ETAI bar: 1XIDES) J, (Canadian Jo Urnal of Chemical Engineering, 49, 7 81 (1971)) is similar to cerium oxide or most other oxides tested. reported that it was found that 4A acid salts were formed more rapidly than limo. But long , the temperature used was less than 900 °C, which is suitable for use in catalyst regenerators in FCC units. The temperature was below the desired temperature.

Many of the zeolites used in 1) F CCpB media have a 4″X oxide content. , rare earths are used to stabilize zeolites and give them increased activity. . For example, see U.S. Pat. No. 4,950.987 to Grand. Light. These rare earths include La 20, CeO2, Pr60,1, Nd, 0. So It is most often used as a mixture of

Certain botanicals are obtained by removing substantial cerium from rare earth mixtures. It is produced by using a lanthanum-rich mixture. zeolite crack The mere presence of rare earth elements in the catalyst is not necessarily sufficient to evaluate SOx emission. It turns out that it doesn't decrease to a certain extent (・ru.

Gladrow (U.S. %8 soil & 825.092 specification) Following the teachings significantly more rapidly than prior art rare earth-exchanged zeolite catalyst compositions. A certain food source of zeolite that can be regenerated at a fast rate, the product is made of rare earth The number of dilution baths containing cerium cations (or (・ is a mixture of rare earth elements enriched with cerium). . The fPL final boiling medium is preheated with a rare earth orthogonal theobite catalyst before the final flow, irrigation, and formation. The particles contain 0.5 to 49 cerium cations. Cerium is monoacid It is explained and explained as ``Promoting Shun''.

In this way, inputs from each Tokukasu stream, including those from the FCC unit recovery profit stack, A considerable amount of violet revenge and research efforts are being directed towards reducing sulfur oxide emissions.

Many metal compounds are FCC-based (and other descaling applications) due to sulfur oxidation. It is proposed to be used as a material for picking up leaves. Many proposed all-polar firsts In other words, the reactants lose their effectiveness when subjected to repeated cycles. That is, Group II gold When group oxides are impregnated onto the FCC catalyst or respective ellipsoidal supports, the Activity affects rapidly under the influence of circulatory conditions. Discrete alumina particles are combined with catalytic converter particles, and high temperature examples are present in the FCC unit regenerator. of limited effectiveness in emitting SOx when subjected to steam at temperatures Become.

Introducing enough ROM on the alumina support to completely eliminate SOx absorption Undesirable coke and gas production increases. Carbonization into catalytic cranking units The presence of vanadium in the hydrogen feedstock can have a detrimental effect on cranking operations. Are known. For example, this vanadium deposited on the catalyst can cause the catalyst to become brown. ie tend to inhibit the ability of the catalyst to promote the desired cranking chemical reaction.

This is one thing that makes us reluctant to consider the use of vanadium in cracking operations. This is the reason.

The U.S. waiting Fi No. 4,469.589 and No. 4.47λ267 four honors are subject to combustion conditions. ~・One or more types capable of promoting the oxidation of sulfur dioxide to sulfur trioxide Spinel may contain other metal components, preferably alkaline earth, aluminum Concerning an improved material for reducing SOx emissions consisting of aluminum-containing spinel Ru. Examples of such metal components include non-IB metals, group B metals, and 1VB metals. Genus, %■A 2! ! Metals, No. IBm metals, No. A, Group metals, Daijuku Kuroku metals, Examples include rare earth metals, vanadium, iron, tin, antimony and mixtures thereof. It will be done. In specific examples, these features include magnesium and aluminum containing spindles. With such other metal components (e.g., platinum and platinum) using conventional techniques, In addition, these buttocks are impregnated with spinel, which is usually ・Minium b, Iron, chromium, vanadium, manganese, gallium, boron, cobalt and It is disclosed that the mixture may replace all BI5 or ~. parts of aluminum I ion. I'm at 1-. , U.S. Hook Rod 44; ylo7o No. 4.472.532, 4,47 6.245, 4. ' No. 492.677, No. 4.492.678, 4. , 49 The specifications of Nos. 5.304, 4.495.305 and 4.522.937 are also null. Spinel compositions useful for reducing sulfur oxide atmospheric emissions. these ox The name specification of zaf shall apply mutatis mutandis to Invention 1. Good SOx removal and 7/or This shows that the desired oxides have been reduced. Ru.

In one general aspect, the present invention relates to Under oxidizing conditions, metals with higher valences, secondary to oxidation H- and H-2 are effective for promoting the oxidation of sulfur dioxide to sulfur trioxide. A small amount of a third metal other than the metal (tomo-i component, and the first metal sulfuric acid in the secondary lid) The first salt effective to promote the reduction of the first metal salt in the salt-reducing layer ( At least one component of the fourth metal other than the second and third gold ingots is stored in the warehouse, but the third gold If the fourth metal is a rare earth metal or vanadium, at least -6 all-pole-containing spinel, preferably containing no such bipolarity as a major component. It is called ROS J! ; bar, l-dium , Rare Earth Metal Names 1"Nel Composition is a U.S. patent application S assigned to TLT, 8. (mouth al l’4”, 1 (A, ttorr+ey 1)ockct Nn 15 256) and was disclosed in J6, the details of which are the present invention←τoi℃ Mutatis mutatis mutandis -1-, 7,... In another embodiment, the invention is based on the main carbon f. 1. To the hydrogen converter H, “(encouraging the hydrocarbon converter l”) 4 Ruko J’s new arrival!,,tJ,: .

Solidity of body particles and subordinate members @T2'f-? 18, above) ( Intensely mix the ``'i1 iscrit body (#1 scattering\]J'') formed by cutting O8. 1.1. Catalyst system 6-・Hmm. , the main enemy's ROS i, j is an example of hydrocarbons Contact cracking with a tactile spoon 4t 'Ryoyu 6; 14. The analogy is the reaction region of hydrocarbon contact. Improved effective τ() for the release of associated sulfur oxides in the Or the headline again. , present in Ros; the first, -second and fourth metal chambers are The third and fourth metal components are carbonized/'carboxylated, e.g. substantially in the cranking method. It is better to be different so as not to cast a harmful influence on the public.

In yet another embodiment, the present invention provides; l) the oxidation of sulfur oxide-poor gases; At least one of sulfur-containing and (nitrogen oxide-containing scum containing 21 oxides), Alternatively, there is a method of reducing both the gases by fi + the sulfur oxide content of the gas and ( 2) Contact with a substance under conditions that reduce at least one of the nitrogen oxide content of the gas The sexual characteristic is to prostrate. The substance used is the RO8 first reviewed above. Ru.

Furthermore, in another embodiment, the present invention provides a method for converting sulfur-containing hydrocarbon feedstocks. The present invention relates to an improved hydrocarbon conversion, preferably claraging process, for the production of hydrocarbons. This person The method can facilitate the conversion of fi+ feedstocks into feedstock hydrocarbon conversion conditions. contacting the solid particles in at least one reaction zone and at least one type of carbonization; generation of hydrogen products and inactivation of sulfur-containing carbonaceous materials onto solid particles. (2) deposit-containing particles in an oxygen-containing gaseous medium and a small amount of carbonaceous deposit material; solid particulate hydrocarbons by burning at least a portion in at least one regeneration zone; to regenerate at least a portion of the conversion catalyst activity and to regenerate at least a portion of the conversion catalyst activity and ) and/or forming a regenerated waste gas containing 9 elements of oxide, and (3) step (1 ) and (2) are repeated periodically. The improvements of the present invention are as follows: The first RO8 is intimately mixed and has a different chemical composition from the secondary violet solid particles. It is characterized by using a discrete body comprising: such discreet It is effective in reducing sulfur oxides and/or nitrogen oxides in exhaust gas. Exist on rent.

In one embodiment, the discrete body also has a sub-catalytically effective carbonization The hydrogen conversion analogy is a small amount effective to promote cracking in hydrocarbon conversion conditions. Contains at least one type of crystalline substance.

The preferred relative amounts of solid particles and discrete bodies are about 80 to about 99 parts by weight, respectively. and about 1 to about 20 parts by weight. This catalyst system is designed to improve the performance of hydrocarbon feedstocks and reduce Particularly useful for catalytic cranking of boiling point products. The uninvented catalyst system was also improved. It also has excellent carbon monoxide oxidation catalytic activity and stability.

In another embodiment, R,OS is (ordinary B.

E, 1', by law) approximately 25 m2/1m, ~ approximately 600 m2/Jiml, More preferably about 40 m2/1 m, ~400 m2/pmo, even more preferably Preferably, it has a surface area of about 50 m2/l1 m, ~ about s o o m2/m2. Ru. These relatively high surface areas allow sulfur oxides and/or nitrogen oxides to escape into the atmosphere. It has been found that this gives an improved reduction in

The present invention allows the catalyst (solid particles and discrete bodies) to be transferred to any conventional reactor - regeneration 4. In the system, the catalyst is continuously transported between the boiling a'ps medium bed system, the reaction zone and the regeneration zone. Alternatively, it can be handled and used advantageously in a circulating system.

Circulating catalyst systems are preferred. Circulating catalyst bed systems are typically used in conventional moving wood and fluidized bed reactions. It is a regenerator-regenerator system. Both of these circulating bed systems are used for hydrocarbon conversion, e.g. Fluidized catalyst bed reactor-regenerators commonly used in packing operations are preferred.

The solid particles and discrete bodies useful in the present invention are separated particles. In one embodiment, the disc may be used as a physical mixture of the discs. The reeet bodies are assembled as part of the solid particles. That is, for example, the fired For example, a discrete body consisting of microspheres can be combined with solid particles during the packaging of solid particles. Both solid particles and discrete bodies are useful in inventions. form a combination of particles. In this embodiment, the discrete bodies are Preferably, the phases are separated and differentiated at the intragranular pressure. This combination grain One preferred method for providing a particle is to combine discrete bodies and use intraparticle pressure induction. It must be fired before being poured.

Non-inventive particles, such as solid particles and discrete bodies as well as combined particle forms That is, the particle size is not essential for the present invention (for example, depending on the type i of the reaction-regeneration system used). It's okay to be different. Such particles can be of any desired shape, e.g. pills, cakes, extrudates, powders. The end, condyle, sphere, etc. may be formed using conventional methods. For example, the final particle is a solid foot bed. In one case designed for use, the particles are at least about [101 in. The smallest possible dimension and the largest dimension up to about a hand inch or 1 inch (2,5z) or more It was first formed in the 14th child. Approximately 0.06 inch to approximately CL25 inch (c L76~&4,), preferably about 003 inches~IECL15 inches (176 In a fixed bed or transferred #1 bed operation, spherical particles with a diameter of Shihashi is useful. For fluidized bed systems, the main proportion of particles is about 10 mF. lon to about 250 microns, more preferably about 20 microns to about 150 microns Preferably, it has a diameter.

The solid particles are capable of promoting the desired hydrocarbon conversion. "hydrocarbon "Conversion" means conversion of one or more feed materials or reactants and/or one or more products, i.e. Where the conversion product is substantially hydrocarbon in nature, e.g. It is made of hydrogen. Solid particles also have a different composition (i.e. chemical composition). In one preferred embodiment wherein the solid particles (i.e., the solid particle portion of the combined particles) are substantially RO8 There is no.

The composition of solid particles useful in the present invention is such that such particles promote the desired hydrocarbon conversion. It doesn't matter how far you can go. Solid particles with widely varying compositions Commonly used and selected gender compositions as catalysts in such hydrocarbon feedstock processes The examples vary depending on the type of hydrocarbon chemical conversion desired. In other words, it is used in non-invention. Solid particles suitable for It includes at least -d natural or synthetic substances. For example, if the desired hydrocarbon conversion hydrocarbon cracking (preferably a substantial amount of added free molecular water) Absence'T:), disproportionation reaction, isomerization reaction, hydrocracking, reforming reaction, In cases involving one or more of dehydrocyclization, polymerization, alkylation and dealkylation , such suitable materials include acid-treated natural clays such as montmorillonite, carbonate, etc. olin and bentonite clays, natural or synthetic amorphous materials such as aluminum silica, silica-alumina, silica-magnesia and silica-zirconia complex Combination is an example of a crystalline substance called zeolite or molecular sieve. aluminosilicate, 5APO, TAPO% MeAPO, LZ-210, Examples include LZ-10. Some of these crystalline materials are described in U.S. Pat. 10.440, 4.44Q, 871, 4.500,651 and 4.50& No. 023, each specification, and each FI All III book of these patents is single phase.

In some cases, for example in hydrocarbon cranking and disproportionation reactions, solid particles are preferred. Preferably, such a crystalline material is included in order to increase the catalytic activity. the Solid particles such as This is a known method. For example, crystalline aluminosilicate compositions contain alkali metals. From silicates and alkali metal aluminates to alkali at initial concentrations. Can be made to contain metals.

Sodium is used for hydrocarbon conversion reactions such as hydrocarbon cracking and disproportionation reactions. tend to reduce the catalytic activity of the composition. Therefore, crystalline aluminosilica Most or all of the sodium in the Others such as aluminum ions or rare earth element ions associated with minosilicate It will be released in FY8 with Metal Canaon. This is done by treating crystalline aluminosilicate with acid or alkali. By contacting with a hydrogen ion source such as a hydrogen precursor such as an ammonium compound can be achieved.

These operations are based on the US' FHf 14Q, 25!1 specification and reissue%#f27 , No. 639.

Particularly useful solid particle compositions in the present invention are those in which the crystalline material achieves the desired hydrocarbon conversion. A catalytically effective amount of carbon dioxide is itself effective to promote the conversion of such hydrocarbons. Porous matrices of amorphous materials that may or may not promote elementary conversion. This is what has been introduced into the box. Crete is an example of such a matrix material. - and alumina, silica, silica-alumina, magnesia, zirconia, this Examples include amorphous compositions such as mixtures of. Crystalline substances are matrix Preferably from about 1 to about 75 weight itX of total solid particles in the material, more preferably from about 2 to Preferably, the content is within about 50% violet.

The preparation of crystalline-amorphous matrix catalysts is described in the above patents. . Hedron particles, discrete bodies during ha and/or as part of the manufacturing method and/or or as part of a process for producing solid particles, discrete bodies and/or combined particles. The catalytically active crystalline materials produced are within the scope of the invention. solid particles are preferred Preferably, a rare earth metal such as seri is added to the amorphous matrix material of the catalyst. Although it is preferable that there is no substance or substance, such fabric gold-stripe composition is preferable. The fraction may be accompanied by a crystalline material of times jl+ particles.

The solid particles useful in the catalytic hydrocarbon cracking embodiments of the present invention are hydrocarbon cranking under the conditions existing in the hydrocarbon cracking conditions. Any conventional catalyst that can be promoted. Similarly, the contact of such solid particles Media activity is restored under the conditions existing in the regeneration zone. Typical of these common catalysts Examples include amorphous silica-alumina and about 8 angstroms. at least one crystalline aluminosilicate having a diameter of about 15 angstroms; and mixtures thereof. Uninvented hydrocarbon crackin' The solid particles and/or discrete bodies used in embodiment 2 of the invention are crystalline. When containing aluminosilicate, the crystalline aluminosilicate is An example of a ubiquitous stimulant may include rare earth gold M% and cerium.

As mentioned above, the RO8 of the present flash is preferably present in effective amounts, preferably the primary violet first metal and the primary violet metal. a type of spinel, preferably containing an alkaline earth metal; Sulfur trioxide of sulfur dioxide under sulfur dioxide oxidation conditions of spinel and secondary violet at least some component of a different third metal effective to promote oxidation to The first metal-containing term in the secondary storage is effective for promoting the reduction of first metal sulfuric acid under the original conditions. It comprises at least a part of a different fourth metal. Another good case. In terms of this aspect, RO8 of this defense promotes the reduction of nitrogen oxides under nitrogen oxide reduction conditions. a third metal component and a fourth metal component in amounts effective to promote

The spinel structure is based on a cubic close-packed arrangement of oxide ions. Typically, the spine The crystallographic unit cell of the structure contains 32 oxygen atoms and has tetrahedral holes (their - of the grains (there are two per anion) are occupied by divalent metal ions, and eight Half of the holes in the facepiece (of which there are two per anion) are filled by trivalent metal ions. occupied.

This typical spinel structure I formation or its variant is type MIIM2III04 Many other mixed metal oxides (e.g., FeCr2O4, SnAl20 a and Co IICO2■Oa), type VIIO MM　2　a　(e.g., T　S　n　20　a and S　n　CO2 0a), and those with type MIM1'''04 (e.g., Na2Nfo04 and Ag2Mob4). This structure is often written as XCY2〕04. The parentheses with squares in the formula surround the ions in the four darknesses of the octahedron. Ru. An interesting variant is the inverted spinel structure Y (XY:104), and in this structure is in the tetrahedral gap between the X ion and the other half of the X ion. Both are in octahedral darkness. The inverted subi-ru'cl # structure is the "golden" used in the ceremony. Spinel containing the genus is included within the scope of the term. This inverted spine The structure has a strong preference for the octahedral top rather than the X ion or the X ion. The craftsman lives. All Δ(r″M2T104 is inverted. For example, 5n (SnTi) 04, and many M, n M2Ill o4, for example Fe (Co　Fe　)04, NiAl2O4, Fe■(FeHFe■)04■　■ ■ and Fe(NiFe)04. Also, only a part of the X ion is a tetrahedral site. There are also many compounds that have a threaded spinel structure. This is for X and Y It occurs when the preferences of both ions for octahedral and tetrahedral sites are not significantly different.

Furthermore, details about the spinel structure are described in the following documents, which are sometimes Applies mutatis mutandis: “Modern Aspectsof Inorganic C hemistry”, H, 1, Emeius and A.

G. 5harpe, (1973), pp. 57-58 and 512-513. ;”5structural Inorganic Cbemistry” , 3rd edition, (1962) A, F, WellSfi, pp, 130.48 7-490.503 and 526; and “Advanced Inorganic "Chemistry", 3rd edition, P, A, Cotton and G.

Wilkinson, (1972), pp, 54-55° Spinel in Gold As for the following: MnA, I　Os　FeA, I204, CoA l 2 (Ja, NiAl2O,, ZnA1204, λtgT 1Mg04 , FeM, gFeO4, FeTiFe04, Zn5nZn04, GaMgGa0 4.1nλ1. glno4, BeLi2F4, Mo L I204, S nMg 20 a, MgAl2O3, CuAl204, (1, i A l s Os ), ZnX2(CN)a, CaX2(CN)4, )4gl(2( (ki) 4, Z n, T r 204, FeV2O4, AigCr20. , MnC r2O,, YeCr204, CoCrO, NiCrO, ZnCr2O4, C dCr2O,, MnCr S, ZnCr S, CdCr S, TiMn2 04. M　n　F　e　204, FeFe2O4, CoFe2O4, NiFe 2O,,Cu　F　e　20　a, ZnFe, 04, CdFe2O4, MgCo 2O4, Tr　CO20a, coCo204, ZnCo2O4, Sn　CO 204, coCo2S4, CuCo254, GeNi204, N I N I 2 S4, ZnGa204, WAg204, and Zn5n204゜In the present invention A metal-containing spinel that is useful as a metal-containing spinel is It contains a second metal that has a valence (oxidation state). The first and second metals are the same. - Can be metal or different metals. In other words, the same metal can be made of two or more different types. Spinel may be present in other oxidized states. As above, any given speed The atomic ratio of the first metal to the second metal in the spinel is determined by the classical chemistry of such spinels. There is no comfort in matching the stoichiometric formula.

In one embodiment, the gold maple-containing spinels useful in the present invention include The atomic ratio of genus to second union is at least about α17, preferably at least about (125 It is.

If the first metal is a monovalent metal, the atomic ratio of the first metal to the second is favorable. or less (both about cL34, more preferably at least about 0.5).

Preferred all-pole spinels for use in the present invention are alkaline earth metals. Magnesium (first metal) and aluminum (ferric gold) pA) Contains spinel. Other alkaline earth gold maple ions are calcium, Rontium, barium and their mixtures contain all or part of the magnesium ions. You may take charge of the department.

Similarly, other metal ions such as iron, chromium, vanadium, manganese, and gallium Cobalt, boron, cobalt, Group 1B metals, Group 1V metals, Group 1A metals, platinum group metals Daughter-in-law, 孭子bi4i'Ff4. Te, Nb, Ta, Sc, Zn , Y 1 \l', ), , to 8, Tl, l (e, IJ, T1 (and If the mixture thereof contains all or part of the ryaminium ion, preferably t=< is A part of 4 in the V miniudo ion may be substituted. Spinel plays two metal songs (e.g. in spinel if it contains metals (e.g. aluminum) and iovalent metals (e.g. aluminum). The atomic ratio of two parts one to five curved metal is about f117--about 25, more preferably 4) 0.25 □ - about 2 [), more preferably a range of about 0.35 to about 1.5 1, books, etc., [power smell' (-The 5-person metal attack is a record! The usual l -] Well-known source 6. can get. Example: Spinel of 4 and 1 is natural H 8 in O・) or Zhou: jdJ's fk1 hoJke, condolence(・'(synthesized r1 heart 9. However, with such technical details, I'm not good at playing strings. RO8 is in danger A useful method for writing and writing poems is ``Y, country about it m5erialb (Attoyn eyI)ocketm 1536'7), the specification of which is Applies mutatis mutandis to ``!'ru.

Other well-known substances with non-interfering proportions in F'J include silica, Zirconia, Doria, etc. No 8! Oxides may be included in the non-inventive RO8 . Actual negative Efi) "non-tDi harm" means uninvented RO8's punishment depending on the case. 1. “Noe, there is no fire in the catalytic system or hydrocarbon conversion process, the 6th sound of Shaya. Taste the delicate substance that cannot touch you. , silica, silica-alumina, zirconia A, the dyes into the uninvented RO8 of substances such as Doria are the ~・-'' of these RO3. -Improved functions of filters and filters. Lumina (i.e., apart from alkaline metal-containing subine, ru) 4. ,,.

Using Nuritsu's technique, it is possible to use [+za, 3'): l (even if it includes 1 in the OS).Example. In one embodiment, the OS is about 11% to about 301% free polymer. It is effective to include gnesia (84 g (') and division by) 1, such as f, The free magnesia contains ROH, this oxide, /' or nitrogen oxide, gas 4'1' 5 + 3rd metal composition to improve effectiveness and effectiveness. The minute and fourth 'tNS components can be any suitable combination of techniques i, :, : or techniques poor J. l) For example; soaking 1. Ha 1me, Ionda's chivalrous 41゛ public spirit J's Senshijutsu' bowl 1 1＼・te、−、bee・°;ni imidjigusa wo stone, 9. [Go] also, second metal and second metal The four-metal component may be an integral part of the spinel or may be separate from the spinel. Even if they are in the same phase (e.g. on Subineh) or both are Yes. These metal phrases ij:, lh: i-low (・('''different-'=>ta i2 go According to the handler, the lower one with Spinel was met in the 1171 order of Jihui 4' , ノ, ト ＆ Then, it is preferable to combine the whole range of components of spinel together with spinel. 5. Impregnation is performed by dipping the spinel into a solution of tertiary and quaternary metal salts (which is in contact with water-soluble metals). It is done by touching.

The third metal component is 1, 2, 3, oxidized, N, K-g, 1.・Triacid of sulfur dioxide Promote oxidation to sulfur - (Rununi is young and should be avoided from y minutes. Preferably Group 1H metals, Group nB metals, Group VIA metals, rare earth metals , platinum group metals, and mixtures thereof. Yo More preferred are rare earth metals, platinum group metals, and mixtures thereof. The third metal Excellent results were obtained with cerium and/or platinum, with cerium being the most I will give you a good result.

The fourth metal component is the first metal (e.g. magnesium) fiR salt reducing conditions, e.g. carbonization under the conditions prevailing in the typical reaction zone of a hydrogen fluid catalytic cracking unit. Selected from ingredients effective in promoting the reduction of metal sulfur salts. The quaternary metal component is preferred. < is iron, nickel, titanium, chromium, manganese, cobalt, kermanium , tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof. It is a metal component selected from the group consisting of: More preferably, the fourth metal is iron or nickel. selected from kel, cobalt, man i7, tin, vanadium and mixtures thereof .

The specific extenuating amounts of the tertiary and quaternary metal components included in RO8 are as follows: may vary widely as long as it remains effective. Preferably, the third metal component is elemental It is present in about α001 to about 20'N1% of RO8 in terms of metal, and The tetrametallic component is approximately α001 to approximately 10’1 ftX of RO8 in terms of elemental metals. Exists in negative. In particular, in hydrocarbon transfer applications, there is a substantial negative impact on the dominant method. Avoid tertiary and/or quaternary metal components in Violet to reduce the risk of It is preferable to Preferably RO8 is about [1,1 to about 2] calculated as elemental metal. 0 heavy view%, more preferably about α05 to about 20 heavy view%, even more preferably about 2 to Contains about 15 times 1iX of rare earth metal. Of course, platinum metals are used in RO8. If so, a greatly reduced concentration (eg 1 part per million) is used. vanadium If it is included as a quaternary metal component, it is equivalent to vanadium as an elemental metal. from about α05 to about 7% by weight, more preferably from about α1 to about 5″: 1iffifX, Even more preferably it is present in an amount of about α2 to about 2 times tX.

Certain soluble tertiary and quaternary metal salts (e.g. nitrates or acetates) are added. It is not necessary to wash the spinel after washing. After impregnation with tertiary and quaternary metal salts, spin Drying and calcining the flannel to decompose the salts, forming oxides in the case of nitrates and acetates. can do. Alternatively, the spinel analogy is in the form of discrete particles. A hydrocarbon conversion analogy can be to lay down the light metal in the form of a salt into a cracking unit. . In this case, the tertiary and quaternary gold J1% salts with thermally decomposable anions are unit It can be oxidized and decomposed within the trap.

The discrete bodies of the present invention further facilitate the production of desired hydrocarbon feedstocks in accordance with the present invention. The crystallized material may contain at least -m of crystallized material. Typical isocrystalline substances are the above That's right. Such crystalline VJ bonds are about 1% to about 30% of the discrete bond, For example, f11~about’+o! - may occupy mX. Such crystalline @ quality present invention The presence of solid particles in the discrete body promotes the desired hydrocarbon conversion. - Acts to increase the overall catalytic activity of the discrete body mixture.

Preferably, the third and fourth metal components are substantially uniformly disposed in or on the RO8. It's good to be able to do it.

Among the rare earth metals useful in this invention are lanthanum or the lanthanide series (element cycle? Includes metals (Table 4) and mixtures thereof. The preferred rare earth metal is lanthanum, praseodymium, lanthanum, and mixtures thereof; Cerium is more preferred.

As mentioned above, the solid particles and discrete bodies useful in the present invention are solid particles and functions, such as promoting hydrocarbon conversion, and functions as a discrete body. It can be used as a set of combined particles that provide both. That kind of combination The particles may be loaded in any suitable manner, some of which are conventional. This is a commonly used and well-known item.

The present invention is useful with many hydrocarbon feedstocks, or the catalysts of the present invention are solid particles and Mixtures comprising discrete bodies and hydrocarbon conversion processes allow oxidative regeneration of the catalyst. It is particularly useful in systems used for catalytic cracking of hydrocarbons. such contact coal The hydrochloride cracker has a lower boiling point component than the other one. Other lower boiling components such as hexane, hexene, pentane, pentene, butane , butylene, propane, propylene, ethane, ethylene, methane and mixtures thereof. This includes converting or cranking into a compound. Often essentially a source of hydrocarbons. The raw materials are obtained from petroleum, shale oil, tar sands oil, coal, etc. It comprises a gas oil fraction. Such raw materials can be processed in straight runs, e.g. barges. It may consist of a mixture of gas oil. Such gas oil distillate Boiling primarily in the range of about 400'F to about 1000'F (240° to 568°C) do. Other substantially hydrocarbon feedstocks, such as naphtha, high boiling petroleum or Oil fractions, petroleum residues, shale oil, tar sand oil, coal, etc. cracked using catalysts and methods. Such essentially hydrocarbon feedstocks are What about other elements of the seven subordinate children, such as sulfur? Contains oxygen, oxygen, etc. one In one aspect, the present invention provides chemical bonding with molecules of sulfur and/or hydrocarbon feedstock. This involves transferring sulfur-containing hydrocarbon feedstocks. The present invention The sulfur storage in a high quality hydrocarbon feedstock is about 1 lO1 to about 51% of the total feedstock, preferably It is particularly useful when it is in the range of about α1 to [rare]31tX.

Hydrocarbon cracking is a well-known phenomenon that occurs between about 850'F and about 11 00')'' (4540~599℃), preferred tL<!!about 9oo°F~about 1050' F (4820-566°C). Other reaction beams and pillars are Yingjo 110 Pressure up to 0 psig (7K9!/cyn2G), about 1:2 to about 25:1 , preferably from about 5 to 1 to about 15 to 1 I! I! oil to oil ratio, and about 3 to about 60 1 1 hourly space velocity (WHSV). These hydrocarbon cranking conditions For example, the raw materials and solid particles or combination particles used, and the reactor used. For example, style 1c! or moving bed catalytic cracking system and Pff may vary depending on the product being used. In addition, the hydrocarbon cracking system is carbonized. solid particles or combinations of catalysts previously used to promote hydrogen cracking; Includes a regeneration zone to restore the catalytic activity of the particles and carbon from the iro reaction zone. carbonaceous matter containing sulfur, and catalyst particles containing deposits containing at least a portion of carbonaceous matter. The catalyst activity is restored or maintained by removing the material from the catalyst plate and burning it. contact with free oxygen-containing scum in the regeneration zone under conditions. Carbonaceous deposits contain sulfur If the sulfur-containing combustion products contain is generated, and the area is QQed along with the regeneration 6 exhaust gas. Such free oxygen containing gases The conditions under which contact is made may vary over a normal range, for example. hydrocarbon crankin Temperatures in the catalyst regeneration zone of gas systems often range from about 900°F to about 1500'F ( 4820 to 816°C), preferably below 1100 to about 1350"F (595' to 732°C), more preferably about 1100 below to about 16006F (5850 to 704 ℃). Other conditions within the neck area include, for example, approximately 100 Pressure at psig (7 to 9/cm2G) t, average 5 within the range of about 3 minutes to about 75 minutes Includes medium contact time, etc. An example of burning carbon and hydrogen with negative carbon and hydrogen as the starting material is There is sufficient oxygen in the regenerated Wt region to burn even carbon dioxide and water. Toto is preferred. In the reaction zone, a drop of carbon7ifi material is deposited on the catalyst. is preferably from about αOOS to about 15% of the catalyst, more preferably from about a1 to about io n amount%. When sulfur is contained in carbonaceous deposits, it means carbonization. Varies depending on the amount of sulfur in the hydrogen feedstock. This deposited material is about 101 to about 10 weight tX Contains more than sulfur.

At least some of the regenerated catalyst is often returned to the hydrocarbon cracking reaction zone. .

One embodiment of the present invention provides a sulfur oxide and/or nitrogen oxide-containing gas such as fuel contacting the product with a ROS of the invention. As a result of this contact, the concentration decreased. degree of sulfur oxide and/or nitrogen oxide, for example sulfur oxide and/or nitrogen oxide from the combustion area. A reduced emission of nitric oxide is achieved.

Typical fuel areas include, for example, fluidized rock backfired steam boilers and sand bed waste combustion. Including pottery etc. In coal-fired boiler applications, the ROS of the present invention The combustion chamber used in this example is added to the boiler separately or together with sulfur and government-owned coal. . The ROS of the present invention is then evaporated into the combustion zone together with the coal ash, for example by sieving from the ash. It can be divided into parts a-f by caustic separation or other known solid separation techniques.

In one embodiment, the sulfur-containing gas is combined with the ROS of the present invention in one or more regions. For example, under conditions that reduce the sulfur oxide content of the gas in a region other than the combustion region. be contacted. In any case, the exhaust gases leaving the combustion zone/contact zone may e.g. ■ Decreased sulfur oxide and/or has nitrogen oxide. ROS from the combustion area or contact area are subject to reduction. For example, reducing media such as hydrogen, hydrocarbons, etc. and at least the ROS-associated For example, sulfur is omitted in the form of hydrogen sulfide and further processed, so the fake is sulfur L. This is referred to in Article Y+, which is excluded and considered for collection purposes. ROS after sulfur recovery is burned (sen area) Alternatively, () may be circulated to the contact area.

Conditions within such contact areas may be reduced by using ysn sulfur oxide or nitrogen oxide scavengers. It should be used specifically in the contact area where the device is located. Sulfur oxide...mentioned and/or nitrogen oxide-containing gases. Preferably, the sulfur oxide and/or nitrogen oxide content of the gas is at least about 50×1. The amount of blood is at least 80x reduced. Reduction conditions are RO8K Preferably at least about 50 pieces, more preferably at least about 50 pieces Such that approximately 80X of sulfur is removed. For example, the reduction condition is about 900 Lower ~ iJ1800"F (4820~982℃) IIJ ambient temperature, about 14~1 Pressure in the range of 00 psig (1-7 kg 7 cm2G) and about 1 to about Examples of reducing media in the range of 10 include water spores, hydrocarbons, and other sulfur molar ratios. It will be done.

The following examples illustrate some specific embodiments of the compositions and methods of the invention. It is given to better illustrate the invention without limiting it further.

Examples 1-14 A series of magnesium and aluminum containing spinel compositions were prepared as follows. .

Spinel particles containing magnesium and aluminum are prepared using conventional coprecipitation/calcination techniques. The obtained subiod was 1 o o m2/ha, (one duram). 1,000 kametor), l] Rijin Kii Mendan and 0.77 magnesium-added aluminum The child had a high IQ ratio. The average plate diameter of these spinel particles is approximately 65 microns per girth. De-da-da.

Fourteen sections of these spinel particles were conventionally impregnated with an aqueous solution of each metal. /The following 14 compositions were prepared by subjecting them to the calcination technique.

Example 7 10X manganese If the blue spinel particles contain two metals, the spinel particles are made of both metals. impregnated at the same time.

Impregnation/calcination of each a1 part of the spinel particles is carried out on the surface 8 of the spinel or depending on the size of the particles. did not substantially change the

Examples 15-28 A commercially available crystal with approximately the same particle size distribution as the spinel-containing particles of Examples 1-14 Solid particles of crystalline aluminosilicate hydrocarbon cracking catalyst were added to the top of Examples 1-14. Each of the final products and 175 heavily decorated spinel-containing particles (disc IJ-1 body) and A mixture of 98.25 parts by weight of solid particles was obtained. of solid particles Catalytic activity used in industrial fluidized bed catalytic cranking (discrete bodies and K prior to bonding) ).

The ability of each blend to continue to remove sulfur oxides over a period of time I met. This study was retrospective as follows. Process 1 is to extract sulfur oxides from regeneration 4 exhaust gas. This included an initial determination of the blend's ability to remove Process 1 is the size of the construction strip. The flow MJ that is known to give results that can be correlated to the results obtained in the diameter of The experiment was carried out at a J-bed catalytic cracking pilot plant. Raw materials for step 1 and The conditions were as follows: Raw material: Mid-continent castor oil containing about 2x tX Reactor temperature: 1, 1000″F (538°C) Pressure generator temperature: 1280′ F (693°C) Stripper temperature - 930 below (499°C) Pressure --- 11115 psia, (t1 kJ!/cyrr2k) Approximate catalyst regeneration time -m-30 minutes Catalyst to oil weight ratio ------6 Weight per hour wall speed---10 Steam as inert storage in the reactor, 3 mol%.

Step 2 of the test process is the type of aging that occurs in industrial fluidized bed catalytic cranking. including continuous and accelerated aging in a fluidized bed reactor to combat JIiI1 Met. The raw materials and conditions used in step 2 were as follows: Raw material: Mid-continent gas oil containing 21% sulfur Reactor temperature: -1--, 1150'F (621°C) Reactor pressure: -1-1s psig (11kg/cm2G) reaction p8 medium/oil 1 weight ratio--15 N friend hourly space velocity---m-α8 Nyuuki IM degree -,,-,-------, 1350'F (732℃) Regenerator pressure ---15psig (t11K97'α2G) Catalyst regenerator feeding time -3 0 minutes Bed generator combustion air flow ratio, -, -20 bond air/hontokoichi daily cycle number □１１ Step 3 of the test procedure is to determine how much sulfur oxide is present in the blend during aging in step 2. including repeating step 1 periodically to determine whether the removing activity is lost; Met.

The amount of total sulfur oxide released with the exhaust gas from regeneration using the blend is used as a basis for evaluating the blend's ability (i.e., activity) to remove various sulfur oxides. It was done.

Test results for these blends were as follows: These data apply to the present invention. The compositions according to the invention, compositions 12 and 13, have substantial initial oxidized sulfur removal activity. It clearly shows that.

For example, the initial sulfur oxide removal activity of Composition 12 (5X tin, 15X cerium) was t for composition 1 (5X cerium) or composition 11 (10X tin). Ru. Composition "411J13 (1X iron/10X cerium) is composition 2 (10% cerium) ) or composition 6 (10X iron) with increased initial sulfur oxide removal activity. do. In addition, the stability of the sulfur oxide scavenging activity of Composition 13, i.e., the acid The ability of Composition 2 to retain sulfur removal activity is increased compared to that of Composition 2.

Samples of initial and aged compositions 12 and 13 were placed in the contact cranking pilot plate described above. Samples were taken from the reaction zone and Takao zone of the sample and analyzed for sulfur content. these The sulfur content of the samples was significantly lower than that of other materials, such as those of compositions 1.2 and 3. won. In this way, the Subiyoru-containing discrete pieces of Compositions 12 and 16 reacted. It appears to have a reduced sulfur content. compositions 12 and 13 with increased kinetics of sulfur oxidation 'a removal in the regeneration zone. Gives power to the driving side.

For each of Compositions 12 and 13, the Tests were conducted to determine the ability to reduce the nitrogen oxide (NOX) content of exhaust gases. That is, , a sample of each of these blends was subjected to the steps of the test procedures set forth in Examples 15-28 above ( 2) was used to perform 22 reaction/Hyo cycles. After this aging, top up the blend. The nitrogen oxide content of the regeneration zone flue gas was tested according to the test procedure described above. It was measured. These test results show that compositions 12 and 16 according to the invention It has been shown that it does indeed provide a reduction in nitrogen oxide emissions from the gas.

Although the present invention has been described with respect to each specific example and embodiment, the invention is not limited thereto. (which may be practiced without fail within the scope of the claims listed below) It should be marked as ``1''.

November 8, 1988 Yoshi, Commissioner of the Patent Office 1) Takeshi Moon person who makes corrections Relationship to the incident: Patent applicant 〒103 Address: Oil and Fat Industry Hall, 3-13-11 Nihonbashi, Chuo-ku, Tokyo Telephone: 273-64 No. 36 Date of notification of amendment order: November 1, 1986 Target of amendment Translation of the specification and claims (1 copy each) Power of attorney and bubble translation (1 copy each) Contents of the amendment as shown in the attached sheet International search report of the translation of the letter of claim 8 and the scope of claims (no change in content) ANNEX To 4rE INTERNAτ:CNAL 5EARC! (RE PCRT ON [Co., Ltd.] / Founder: Bhattacharya, Alakananda Ame1no pre 8f1 Country 21104 Maryland, Mario Tutsville, Tompuso United States 210 45 Maryland, Columbia, Hourglass Switzerland 9240

Claims (1)

[Claims] 1. a first metal and a second metal having a valence higher than that of the first metal; a second metal effective to promote the oxidation of sulfur dioxide to sulfur trioxide under oxidizing conditions; at least one component of a third metal other than the first and second metals, and a dependent amount of the first metal sulfate effective to promote reduction of the first metal sulfate under the first metal sulfate reducing conditions. , at least a fourth metal other than the second and third metals also contains one component, provided that if said third metal is a rare earth metal, said fourth metal is a set comprising at least one metal-containing spinel other than vanadium. A product. 2. The spinel has an area of about 25 m2/gm. ~about 600m2/gm. The composition according to claim 1, having a surface area in the range of . 3. 3. A composition according to claim 2, wherein said composition comprises a major weight proportion of said spinel. 4. The third metal is a Group IB metal, a Group IIB metal, a Group VIA metal, or a rare earth metal. metals of the platinum group, platinum group metals, and mixtures thereof, and the fourth metal is selected from the group consisting of The group consisting of sumas, molybdenum, antimony, vanadium and mixtures thereof The composition according to claim 1, which is selected from the group consisting of: 5. The composition of claim 1, wherein at least one of the third metal component and the fourth metal component is introduced into the composition by impregnation. 6. 2. The composition of claim 1, wherein said spinel comprises an alkaline earth metal-containing spinel and wherein the atomic ratio of said first metal to second metal is at least about α17. 7. The third metal component and the fourth metal component reduce nitric oxide under nitrogen oxide reducing conditions. 2. The composition of claim 1, wherein the composition is present in an amount effective to promote the reduction of the element. 8. 5. The composition of claim 4, wherein said third metal is selected from the group consisting of rare earth metals, platinum group metals, and mixtures thereof. 9. 5. The composition of claim 4, wherein said fourth gold surface is selected from the group consisting of iron, nickel, cobalt, manganese, tin, vanadium, and mixtures thereof. 10. The fourth metal is iron, nickel, cobalt, manganese, tin, vanadium and 9. The composition of claim 8, wherein the composition is selected from the group consisting of: and mixtures thereof. 11. A third metal component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental third metal, and the vanadium component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental quaternary metal. A composition according to claim 1, wherein the composition is present in an amount of 10% by weight. 12. 5. The composition of claim 4, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 13. 10. The composition of claim 9, wherein the spinel is an alkaline earth metal-containing spinel and the atomic ratio of the first metal to the second metal is at least about 0.17. 14. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 5. A composition according to claim 4, wherein the molecular weight is at least about 0.25. 15. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 10. The composition of claim 9, which has a molecular weight of at least about 0.25. 16. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 11. The composition of claim 10, which has a molecular weight of at least about 0.25. 17. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. The composition according to claim 4, comprising: 18. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. The composition according to claim 9, comprising: 19. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. The composition according to claim 10, comprising: 20. Claim 10, wherein said third metal is selected from the group consisting of cerium, platinum, and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, vanadium, and mixtures thereof. Compositions as described. 21. (1) Oxidation of the sulfur oxide content of the sulfur oxide-containing gas and oxidation of the nitrogen oxide-containing gas. (2) contact with a substance under conditions that oxidize at least one of the sulfur oxide content and (2) the nitrogen oxide content of the gas, and the substance has a first metal and a valence higher than that of the first metal; at least one component of a third metal other than the first and second metals that is effective to promote the oxidation of sulfur dioxide to sulfur trioxide under sulfur dioxide oxidizing conditions; , and a corresponding amount of at least one component of a fourth metal other than the first, second and third metals effective to promote the reduction of the first metal sulfate under the first metal sulfate reducing conditions. provided that when said third metal is a rare earth metal, said fourth metal comprises at least one metal-containing spinel other than vanadium. 22. The spinel has an area of about 25 m2/gm. ~about 600m2/gm. 22. The method of claim 21, having a surface area in the range of . 23. 23. The method of claim 22, wherein said composition comprises a predominant weight percentage of said spinel. 24. the third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, rare earth metals, platinum group metals and mixtures thereof; and the fourth metal is iron, nickel, titanium. 22. The method of claim 21, wherein the metal is selected from the group consisting of chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium, and mixtures thereof. 25. At least one of the third metal component and the fourth metal component is included in the composition. 22. The method of claim 21, wherein the method is introduced by immersion. 26. 22. The method of claim 21, wherein the spinel comprises an alkaline earth metal-containing spinel and the atomic ratio of the first metal to the second metal is at least about 0.17. 27. 22. The method of claim 21, wherein said third metal component and said fourth metal component are present in amounts effective to promote reduction of nitrogen oxides under nitrogen oxide reduction conditions. 28. Is the third metal a group consisting of rare earth metals, platinum group metals, and mixtures thereof? 25. The method according to claim 24, wherein the method is selected from: 29. The fourth metal is iron, nickel, cobalt, manganese, tin, vanadium and and mixtures thereof. 30. 25. The method of claim 24, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 31. 25. The method of claim 24, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 32. 30. The method of claim 29, wherein the spinel comprises an alkaline earth metal-containing spinel and the atomic ratio of the first metal to the second metal is at least about 0.17. 33. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 25. The method of claim 24, wherein the amount is at least about 0.25. 54. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 30. The method of claim 29, wherein the 0.25 is at least about 0.25. 35. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 31. The method of claim 30, wherein the oscillation rate is at least about 0.25. 36. The material further contains about 0.1% to about 30% by weight of free magnet as MgO. 35. The method of claim 34, comprising shea. 37. The material further contains about 0.1% to about 30% by weight of free magnet as MgO. 30. The method of claim 29, comprising shea. 38. The material further contains about 0.1% to about 30% by weight of free magnet as MgO. 31. The method of claim 30, comprising shea. 39. A third metal component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental third metal, and the vanadium component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental quaternary metal. 22. A method as claimed in claim 21, wherein the compound is present in an amount of 10% by weight. 40. 31. The third metal is selected from the group consisting of cerium, platinum and mixtures thereof, and the fourth metal is selected from the group consisting of iron, nickel, vanadium and mixtures thereof. Method. 41. Capable of promoting hydrocarbon conversion under major hydrocarbon conversion conditions. a second metal having a different chemical composition than the first metal and a valence higher than the valence of the first metal; at least one component of a third metal other than the first and second metals that is effective for promoting the oxidation of sulfur dioxide to sulfur trioxide under the sulfur dioxide oxidation conditions of and at least one constituent of a fourth metal other than the first, second and third metals effective to promote the reduction of the first metal sulfate under the first metal sulfate reducing conditions. However, if the third metal is a rare earth metal, the fourth metal is a banana. A composition comprising intimately admixed discrete bodies of spinel containing at least one metal other than dium. 42. The hydrocarbon conversion is substantially the same as that of hydrocarbon conversion in the absence of added molecular hydrogen. racking, at least one of the solid particles and the discrete body is Contains crystalline aluminosilicate, which is effective in promoting hydrohydride cracking, and and a predominant weight percentage of the solid particles range from about 10 microns to about 250 microns. 42. The composition according to claim 41, having a diameter. 43. the discrete body contains a predominant weight proportion of the spinel; flannel is about 25m2/gm. ~about 600m2/gm. 42. The composition of claim 41, having a surface area of . 44. the third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group IVA metals, rare earth metals, platinum group metals and mixtures thereof, and the fourth metal is iron, nickel, 42. The composition of claim 41 selected from the group consisting of titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof. 45. At least one of the third metal component and the fourth metal component is 42. A composition according to claim 41, which is introduced into a matrix by impregnation. 46. 42. The composition of claim 41, wherein said spinel comprises an alkaline earth metal-containing spinel and wherein the atomic ratio of said first metal to said second metal is at least about 0.17. 47. 42. The composition of claim 41, wherein said third metal component and said fourth metal component are present in amounts effective to promote reduction of nitrogen oxides under nitrogen oxide reduction conditions. 48. Is the third metal a group consisting of rare earth metals, platinum group metals, and mixtures thereof? 45. The composition according to claim 44, selected from: 49. The fourth metal is iron, nickel, cobalt, manganese, tin, vanadium and and mixtures thereof. 50. The fourth metal is iron, nickel, cobalt, manganese, tin, vanadium and 49. The composition of claim 48, wherein the composition is selected from the group consisting of: and mixtures thereof. 51. 45. The composition of claim 44, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 52. 50. The composition of claim 49, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 53. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 45. The composition of claim 44, wherein the molecular weight is at least about 0.25. 54. The spinel contains magnesium as the first metal and aluminum as the second metal. containing aluminum, and the atomic ratio of sium to aluminum in the spinel is low. 50. The composition of claim 49, wherein the molecular weight is at least about 0.25. 55. The spinel contains magnesium as the first metal and aluminum as the second metal. containing aluminum, and the atomic ratio of magnesium to aluminum in the spinel is low. 51. The composition of claim 50, wherein the composition is at least about 0.25. 56. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. 45. The composition according to claim 44. 57. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. 50. The composition according to claim 49, comprising: 58. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. 51. The composition according to claim 50, comprising: 59. A third metal component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental third metal, and the vanadium component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental quaternary metal. 42. A composition according to claim 41, wherein the composition is present in an amount of 10% by weight. 60. Claim 50, wherein said third metal is selected from the group consisting of cerium, platinum and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, vanadium and mixtures thereof. Compositions as described. 61. A hydrogen conversion method for converting a sulfur-containing hydrocarbon feedstock, the method comprising: (1) contacting the feedstock in at least one reaction zone with solid particles capable of promoting conversion of the feedstock under hydrocarbon conversion conditions to produce at least one hydrocarbon product and to inert the sulfur-containing carbonaceous material. to form on the solid particles. (2) exposing the sediment-containing particles to an oxygen-containing atmosphere; the solid medium and at least a portion of the carbonaceous deposit material in at least one regeneration zone; combusting the solid particles to regenerate at least a portion of the hydrocarbon conversion catalyst activity of the solid particles and form a regeneration zone exhaust gas containing sulfur oxides and/or nitrogen oxides; and (3) a method comprising periodically repeating steps (1) and (2), in intimate admixture with said solid particles, having a chemical composition different from that of said solid particles in a subsequent quantity; a metal and a second metal having a valence higher than that of the first metal; Promotes the oxidation of sulfur dioxide to sulfur trioxide under oxidizing conditions. at least one constituent of a third metal other than said first and second metals that is effective for of at least a fourth metal other than said first, second and third metals effective to promote the reduction of the first metal sulfate under the first metal sulfate reducing conditions. one However, if the third metal is a rare earth metal, the fourth metal is other than vanadium, and the discrete body contains sulfur oxides and/or nitrogen oxides in the waste gas. at least one metal-containing substance present in sufficient amount to reduce A method characterized by using a discrete body made of spinel. 62. The hydrocarbon conversion is substantially the same as that of hydrocarbon conversion in the absence of added molecular hydrogen. racking, at least one of the solid particles and the discrete body is Contains crystalline aluminosilicate, which is effective in promoting hydrohydride cracking, and and a predominant weight percentage of the solid particles range from about 10 microns to about 250 microns. 62. The method of claim 61, wherein the third and fourth metal components do not have a substantially deleterious effect on the hydrocarbon cracking. 63. the discrete body contains a predominant weight proportion of the spinel; flannel is about 25m2/gm. ~about 600m2/gm. 62. The method of claim 61, having a surface area of . 64. The third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group IVA metals, rare earth metals, platinum group metals, and mixtures thereof, and the fourth metal is iron, nickel, titanium, Chromium, manganese, cobalt, germanium, tin, vinyl The group consisting of sumas, molybdenum, antimony, vanadium and mixtures thereof 62. The method of claim 61, selected from: 65. At least one of the third metal component and the fourth metal component is included in the composition. 62. The method of claim 61, wherein the method is introduced by immersion. 66. 62. The method of claim 61, wherein the spinel is an alkaline earth metal-containing spinel and the atomic ratio of the first metal to the second metal is at least about 0.17. 67. the third metal component and the fourth metal component are present in combination in an amount effective to promote the reduction of nitroxides under nitrogen oxide reduction conditions; and 62. The method of claim 61, wherein the nitrogen oxide is present in an amount sufficient to reduce the amount of nitrogen oxides in the exhaust gas. 68. Is the third metal a group consisting of rare earth metals, platinum group metals, and mixtures thereof? 65. The method of claim 64, wherein the method is selected from: 69. The fourth metal is iron, nickel, cobalt, manganese, tin, vanadium and 65. The method of claim 64, wherein the method is selected from the group consisting of: 70. The fourth metal is iron, nickel, cobalt, manganese, tin, vanadium and and mixtures thereof. 71. 65. The method of claim 64, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 72. 70. The method of claim 69, wherein the spinel comprises an alkaline earth metal-containing spinel, and the atomic ratio of the first metal to the second metal is at least about 0.17. 73. The spinel contains magnesium as the first metal and aluminum as the second metal. aluminum, and the atomic ratio of magnesium to aluminum in the spinel is low. 65. The method of claim 64, wherein the amount is at least about 0.25. 74. The spinel contains magnesium as the first metal and aluminum as the second metal. and the atomic ratio of magnesium to aluminum in the spinel is low. 70. The method of claim 69, wherein the 0.25 is at least about 0.25. 75. The spinel contains magnesium as the first metal and aluminum as the second metal. mineral content, and the atomic ratio of magnesium to aluminum in the spinel is low. 71. The method of claim 70, wherein the amount is at least about 0.25. 76. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. 65. The method according to claim 64, comprising: 77. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. 69. The method according to claim 69, comprising: 78. It further contains about 0.1 to about 30% by weight of free magnesia, calculated as MgO. 71. The method according to claim 70, comprising: 79. The third metal component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental third metal, and the vanadium component is present in an amount ranging from about 0.001 to about 20 weight percent, calculated as elemental quaternary metal. 62. The method of claim 61, wherein the amount is 10% by weight. 80. Claim 70, wherein said third metal is selected from the group consisting of cerium, platinum and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, vanadium and mixtures thereof. Method described.