JPH01500108A - Method for producing spinel composition containing alkaline earth metal aluminum - Google Patents

Abstract

A process for the production of an alkaline earth metal, aluminum-containing spinel composition comprises: (a) combining (1) an acidic, aluminum-containing composition in which the aluminum is present in a positively charged species, and (2) a basic, alkaline earth metal-containing composition to form a mixture; and (b) calcining the mixture to form the alkaline earth metal, aluminum-containing spinel composition. Alkaline earth metal, aluminum-containing spinels having both high surface areas and high attrition resistance, and processes for using spinel compositions, e.g., as sulfur oxide and nitrogen oxide removal agent, are also disclosed.

Description

[Detailed description of the invention] Alkaline earth metal spinel and methods of making and using the same The present invention provides improved alkaline earth metal aluminum spinels and such spinels. The present invention relates to a method of manufacturing pinel and a method of using the same. In particular, the present invention These spinels have both a large surface area and high attrition resistance. Improved methods for producing compositions and reducing sulfur oxide and/or nitrogen oxide atmospheric emissions Related to improved methods of using spinel to reduce

U.S. Pat. Nos. 4.469.589 and 4.472.267, for example, Regarding improvement substances for reducing SOx atmospheric emissions from catalytic cracking units, this These substances include spinel, preferably alkaline earth metal, aluminum-containing spinel. A type of vine that promotes the oxidation of sulfur dioxide to sulfur trioxide under combustion conditions. It may also contain the above metal components. U.S. Patent No. 4,471,070.4.472. 532.4.476245゜4.492,677, 4.492,678.4,4 95,304.4,495,305. and 4,522.937 is also sulfur dioxide Regarding spinel compositions useful for reducing yellow atmospheric emissions and/or 0 U.S. patents to the same assignee as this case relating to a method of manufacturing spinel compositions Unidentified application (agent reference numbers 15256 and 15259 are metal sulfate reduction conditions) and at least one reactive metal component effective to reduce metal sulfates in It relates to the spinel composition it contains. Each of these patents and patent applications is listed here. The contents thereof are hereby incorporated by reference.

Various methods and processes have been proposed for the production of spinel. For example, above References were made to some of the patents and patent applications as well as the patent and other documents discussed therein. stomach.

Additional spinel preparation methods are described in U.S. Patent No. 3.597.365:3.702.8 No. 82.4,256,722; No. 4.400,431.

There is a need for even further improved spinels and spinel compositions, as well as for spinels and spinel compositions. There remains a need for methods of making and using spinel compositions.

A method for making alkaline earth metal aluminum-containing spinel compositions has been discovered.

- In embodiments, the method comprises: (a) (1) aluminum is a positively charged species; (2) an acidic aluminum-containing composition, such as present; and (2) a basic alkaline earth (b) mixing with a metal-containing composition to form a mixture, preferably a gel; Calcining the mixture to form an alkaline earth metal aluminum-containing spinel composition includes doing. an acidic aluminum-containing composition and the basic alkali The earth metal-containing composition is an alkaline earth metal aluminum-containing spinel composition. has a surface area greater than about 50 m"/gm and less than about 2" as defined herein. aluminum-containing spun of alkaline earth metals with an attrition resistance index of consisting of flannel composition. Preferably, the spinel is produced according to the method described above. . In another specific example, the present invention provides (1) a sulfur oxide content in a sulfur oxide-containing gas; and (2) for reducing at least one type of nitrogen oxide in the nitrogen oxide-containing gas. This method is related to the improvement method, and this method consists of a substance comprising the gas and (1) sulfur oxide in the gas. and (2) contact under conditions effective to reduce at least one of the nitrogen oxide components. Including doing. This improvement provides at least a portion of the above substance according to the above method. and/or the use of the spinel described above.

The present method for preparing spinels and spinel compositions provides substantial benefits.

For example, spinel produced by this method has the desirable high surface area and attrition properties. It can also have shock resistance. In addition, the method is relatively easy to implement and manage. For example, it can be used to prepare catalysts for hydrocarbon cracking. oxidized sulfur and/or acid from the preparation process. Feedstock materials can be used that result in a reduction of pollutants such as nitrogenous air emissions.

Spinels and spinel compositions prepared in the present method can be used, for example, in any suitable manner. Vine used in the form of grains of shape and size. These particles can be spray-dried, bill-molded, Tablet molding, extrusion molding, bead molding (e.g. conventional oil drop method), etc. Vine formed by conventional techniques such as. Fluid catalytic cracking unit for spinel-containing powder When the spinel-containing flour is to be used in a 250 microns, more preferably having a diameter in the range of about 20 to 125 microns. is preferable.

The present invention further promotes the oxidation of SOt to SO3 under SOz oxidation conditions. at least one metal component and/or alkaline earth metal in an amount effective to in an amount effective to promote the reduction of alkaline earth metal sulfates under sulfate-reducing conditions. Alkaline earth metals and aluminum containing at least one reducing metal component spinels and spinel compositions. Additional metal components and reducing metal components Alkaline earth metal atomization is conventionally performed using techniques such as impregnation that are well known in the art. Can be included in luminium-containing spinels and spinel compositions. Preferably, add The metal component and the reducible metal component can be added to the spinel of the present invention in a manner discussed in detail below. and spinel compositions.

The spinel structure is based on a cubic close-packed arrangement of oxide ions. Typically, The crystallographic unit cell of the spinel structure contains 32 oxygen atoms. silicic acid mug Regarding nesium spinel, there are 8 Mg atoms and 16 AI atoms in the unit cell. (8 to +gA]204).

The present alkaline earth metal aluminum-containing spinel and subinel compositions contain a first metal (alkaline earth metal) and a second metal (alkaline earth metal) having a valence higher than that of the first metal ( The given alkaline earth metal aluminum of the present invention The atomic ratio of the first metal to the second metal in spinels containing Ni need not match the traditional stoichiometric equation for In one specific example, the The atomic ratio of alkaline earth metal to aluminum in the light spinel is preferably 0 spinels that are at least about 0.17 and more preferably about 0.25. The atomic ratio of alkaline earth metal to aluminum is about 0.17 to 2.5, preferably preferably in the range of about 0.25 to 2.5, more preferably about 0.5 to 1.5. desirable.

A preferred alkaline earth metal is magnesium.

Useful acidic compositions contain aluminum present in positively charged species. this The acidic composition is preferably aqueous and preferably about 1.5 to 5 It has a pH within the range. Aluminum is present in positively charged species and spinel Any suitable singular or plural compound that is useful in the present method of producing a composition. of aluminum components are included in this acidic composition. For example, aluminum , as acid salts such as nitrates, sulfates, formates, or at least partially decoagulated (peb The alumina may exist as a diluted or dispersed alumina. Preferably aluminum is an alkali at least partially decoagulated (bebutified) or dispersed in an acidic composition. Exists as Mina. More preferably, at least the main portion of the aluminum is more preferably Preferably substantially the entire amount is as peptized or dispersed alumina in an acidic composition. exist.

The bebutyzable alumina useful in the present invention has a lower content in propanoic acid. at least partially in the presence of an aqueous solution of at least one monobasic acid having a strong anion. Examples of such basic acids, including those that are partially pebutylated or dispersed, include formic acid. , acetic acid, propanoic acid, HNOs, HCl, citric acid, chino, g and tri Mention may be made of chloroacetic acid as well as mixtures thereof. What is “Veptinization” or “Dispersion”? , is meant to provide a substantially homogeneous, aggregate-free solution or sol.

The acidic composition is preferably made of bebutyzable (dispersible) alumina, e.g. boehmite etc. and/or such alumina precursors, water and one or more veptides. forming agent, such as one or more of the above acids, to form bevated alumina. It is prepared by The veptidizing agent or agents are preferably selected so as to have no substantially deleterious effect on the process or product.

"Such alumina precursors" are Aluminums that occur or behave in substantially the same manner as bebutizable (dispersible) alumina means a minium component. Preferred bevating agents include formic acid, -basic mineral acids, etc. Examples include HNOs, MCI, etc. and mixtures thereof. Environmental, performance and other considerations Accordingly, formic acid is more preferred for use in the aluminum-containing acidic compositions of the present invention. Delicious.

Useful basic alkaline earth metal-containing compositions are characterized in that the basic composition is The mixture is preferably selected such that a gel is formed when mixed with the umium-containing composition. Ru.

- In specific embodiments, the basic composition is e.g. an aqueous group and the alkaline earth metal component is Soluble or insoluble in aqueous media. any suitable alkali or alkalis Earth metal components may be used in the preparation of the basic composition or may be present in the basic composition. Examples of suitable alkaline earth metal components that may be present and used in preparing the basic composition include oxides, oxide precursors, nitrates, sulfates, formates, acetates, acetates, tylacetonates, phosphates, halides, carbonates, sulfonates, oxalates etc., as well as mixtures thereof. Preferred alkaline earth metal components include oxides, selected from oxide precursors and mixtures thereof.

The basic composition comprises alkaline earth metal oxides and/or precursors of such oxides. It can be prepared by mixing with water. "Oxide precursors" are useful salts. Substantially the same state as the alkaline earth metal oxide in the basic alkaline earth metal-containing composition. means an alkaline earth metal component that occurs and acts in a similar manner. As such a precursor In particular, mention may be made of alkaline earth metal hydroxides. Magnesium oxide is the base If used in a sexual composition, the material may exceed about 25 m''/gm. surface area preferably greater than about 50 m2/gm (square meters per duram) (as measured by standard B, E, T, method) ), the use of magnesia with such a large surface area and thus high reactivity can result in improved results. It has been found that this gives an increased amount of spinel formation.

of the aluminum component in the acidic composition and of the alkaline earth metal component in the basic composition. The amounts of the specific aluminum and alkaline earth metals used are, respectively, e.g. It varies widely depending on the genus composition and the type of processing equipment used. These compositions If the product is aqueous, the acidic composition should be about 1-50% by weight calculated as alumina. of aluminum and the basic composition is about 1 to 50% aluminum, calculated as oxide. Acidic and basic compositions used, preferably containing % alkaline earth metals The relative proportions of the substances depend on the desired chemical composition of the product spinel composition, e.g. Depends on the earth metal to aluminum atomic ratio.

The relative proportions of acidic and basic compositions are may be selected to provide a single composition. - In embodiments, the spinel composition is preferably Preferably free magnesia, more preferably about 0.1 to 30% by weight free magnesia. Contains. The inclusion of such free magnesia is an improvement for species consisting of It has been found that this method provides the effect of removing sulfur oxide and/or nitrogen oxide.

The mixture preferably formed in step (a) of the method is preferably a base. It is gender. If the mixture is preferably aqueous, the ph of the mixture is greater than 7, more preferably in the range 7 to 10.5, even more preferably 8 to 9. It is preferable that it is in the range of 5. The basicity of the mixture must be determined after the mixture is formed. It is prepared by adding an acid or base as necessary. Preferably, acidic Acidity of aluminum-containing compositions and basicity of basic alkaline earth metal-containing compositions are appropriately selected so that the mixture has the desired degree of basicity, e.g. the desired pH. .

Step (a) of the method comprises preparing an alkaline earth metal aluminum-containing mixture, preferably a gel The process is carried out under conditions, such as temperature, pressure and time, which are effective to form a polyurethane.

These conditions may include, for example, the equipment used, the specific raw material components used and the can vary widely depending on the degree of gelation involved. In many cases, ambient temperature and pressure will permit. give acceptable results. The time allowed to form the gel is approximately 0.1 to 24 It can be a range of hours or more. Various ingredients mixed in step (a) may be added in any suitable order, eg, in any convenient order. For example, acidic compositions may be added to the basic composition, or vice versa. These compositions are available in a single volume. You can also add them to the container together. Also, other materials containing additional and reactive metals, e.g. The compositions may be added separately or together with the acidic and/or basic compositions. step( During a) stirring is provided. Additionally, the gel is more easily transferred to the next processing step. Water or another liquid may be added to make it boil.

Preferably the dried mixture is calcined to form an alkaline earth metal containing aluminium. Generate spinel. Drying and baking can be done at the same time. However, drying From the temperature at which hydration water is removed from the spinel precursor mixture or gel Preferably, it is carried out at a low temperature. Thus, this drying process takes about 500 "lower than" F, preferably about 230-450" F, more preferably about 250-4 Vine in flowing air at a temperature of 50'F.

Drying of the mixture can be carried out, for example, by spray drying, drum drying, flash drying, tunnel drying. Single or multiple drying temperatures can be achieved in various ways by drying, etc. A portion of the phase is selected to be removed. Drying time is critical to the invention. rather than over a relatively wide range sufficient to provide the desired dry product.

Drying times ranging from about 0.2 to 24 hours or more can be advantageously used.

Traditionally used to produce catalyst particles suitable for use in fluidized bed reactors. Any spray drying equipment may be used in the practice of this invention.

A suitable firing temperature for the mixture or dry mixture is about 1000-1800'F. range. However, it is even more preferred that the firing temperature be between about 1o50 and 1600'F. improved spinel formation when maintained in the range of 1150-1400'F. It was found that this occurs. Calcination of the gel can range from about 0.5 to 24 hours or more. within a range of about 1 to 10 hours, more preferably about 1 to 10 hours. blend The calcination is carried out under suitable conditions, such as inert, reducing or oxidizing conditions. However, oxidizing conditions are preferred.

In one embodiment of the method of the invention, additional metal components and/or reactive metal components as described above may be added. the desired additional metal to the mixture, preferably the gel, formed in step (a). Combined with the spinel composition by impregnation with components and/or reactive metal components. It is closed. The impregnated mixture, preferably a gel, preferably undergoes e.g. dried and fired.

As mentioned above, in certain embodiments of the invention, the alkaline earth metal and Aluminum-containing spinels and spinel compositions also contain at least one additional gold Contains genus components. These additional metal components may be added under sulfur dioxide oxidizing conditions, e.g. At the conditions existing in the catalyst regenerator of the elementary catalytic cracking unit, the concentration of sulfur dioxide Defined as something that can promote oxidation to sulfur oxides. - Increased oxidation of carbon oxides are also obtained by including additional metal components. These additional metal components are Preferably, IB, ITB, IVB, VIA, VIB, ■A, and ■groups of the periodic table, Rare earth metals, niobium, tantalum, vanadium, tin, antimony and mixtures thereof and which are useful in accordance with one or more embodiments of the present invention. vine is included in the oil composition. A more preferred additional metal component for use is rare earth gold. selected from the group consisting of the genus and mixtures thereof. A particularly preferred additional metal component is cerium It is um.

Additional metallic component(s) present in the final spinel and spinel composition The amount of spinel is often small compared to the amount of spinel, preferably the final spinel and and spinel compositions containing a small amount, more preferably up to about 25% by weight (element containing at least one additional metal component (calculated as metal); The amount of additional metal added depends, for example, on the degree of sulfur dioxide oxidation desired and the A more preferred embodiment will depend on the effectiveness of the additional metal component to promote oxidation. When the additional metal component is a rare earth metal component, the preferred dish for this additional metal component is is about 1 to 20% by weight of the spinel or spinel composition as a whole, more preferably about in the range 2-15% by weight (calculated as elemental rare earth metals).

The additional metal component is at least partially an oxide with the spinel or spinel composition. , sulfides, halides, etc., or in the elemental state. good Preferably, at least a portion of the additional metal component is present as an oxide.

One or more additional metal components may be present in the present spinel or spinel composition and spinel composition. Incorporation in any suitable manner such as by impregnation of the spinel composition at any stage in the preparation of the product It can be done. Various ways to incorporate these components into the present spinel compositions include: It is conventional and well known in the industry. However, preferably The additional metal component(s) may be included using one embodiment of the method of the present invention. It will be done. That is, at least one of useful acidic and basic compositions or step (a) The separate additional composition mixed with the first and second compositions is a spinel composition. contains an effective amount of at least one additional metal component. Both contain an additional metal compound. Preferably, the additional metal compound is a basic alkali. present with a lithium metal-containing composition. More preferably the additional metal compound is a base oxide, even more preferably ceric oxide, which is present as a solid with the composition. It is mu.

Preferably, the present spinels and spinel compositions contain at least one reactive metal component. of alkaline earth metal sulfate reducing conditions, such as the reaction of a hydrocarbon catalytic cracking unit. Facilitates the reduction of alkaline earth metal sulfates under the conditions present in the reaction zone. Contains in an amount effective for. More preferably, one or more reactive metal components and the additional metal component(s) under the nitrogen oxide reducing conditions, e.g. hydrocarbon catalytic fraction. Facilitates the reduction of nitrogen oxides in the conditions present in the catalyst regeneration zone of the decomposition unit. present in an effective amount. The reducing metal component is preferably iron, nickel , titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molyb a metal selected from the group consisting of den, antimony, vanadium, and mixtures thereof; It is an ingredient. In a preferred embodiment, both the additional and reactive metal components are present. The reactive metal component(s) is a separate metal from the additional metal component(s). It is preferable that More preferably, the reducing metal is iron, nickel, cobalt. selected from the group consisting of carbon dioxide, manganese, tin, vanadium, and mixtures thereof. Special For good results, the reactive metal component is a vanadium compound.

The specific amounts of reducing metal components included in the spinel compositions are as follows: They can vary widely as long as they are valid as described. Preferably a reducible metal The ingredients range from about o,ooi to 10% by weight of the spinel composition (calculated as elemental metals). present in amounts ranging from Excess amounts of reducing metal components are especially important for hydrocarbon conversion applications. be avoided in order to reduce the risk of having a substantial adverse effect on the main process. is preferred, if a vanadium component is included as a reducing metal component. is about 0.05 to 7% by weight, more preferably about 0.1% by weight, calculated as elemental metal. Vanadium is present in an amount of ~5% by weight, even more preferably about 0.2-2% by weight. Preferably.

The one or more reducing metal components are present in the present spinel or spinel composition and spinel combination. In any suitable manner, such as by impregnation of the spinel composition, at any stage in the preparation of the composition. can be entered. Various ways to incorporate these components into the present spinel compositions is conventional and well known in the industry. However, preferably The reactive metal component(s) obtained using one embodiment of the preparation method of the present invention may be I can't stand it. That is, at least one of useful acidic and basic compositions or stages ( The separate additional composition mixed with the first and second compositions in a) is a spinel composition. in an amount sufficient such that the composition contains an effective amount of at least one reactive metal component. Contains at least one reactive metal compound.

If the reactive metal component is one or more vanadium components, in the above method The vanadium compounds used are water-soluble vanadium compounds, i.e. calculated as elemental metals. water-soluble vanadium such that at least about 1% by weight of vanadium is dissolved in water; Preferably, it is a umium-containing species (entity; for example, a compound, a complex, etc.), More preferably, the vanadium compound used has a temperature range of 18-22°C and It is water soluble throughout the pH range of 2-11.

To obtain favorable water solubility, the vanadium compound is treated with at least one complexing agent. A wide variety of complexing agents are used, preferably in the form of vanadium complex salts. Ru.

The main criterion for selecting one or more complexing agents is that the selected The purpose is to provide a "water soluble" vanadium compound. Of course, the singular or plural complex The generating agent must have no substantial adverse effect on the process or the product spinel composition. stomach.

Preferred complexing agents for use in the present invention have from 2 to about 12 complexing agents per molecule. Dicarboxylic acids containing carbon atoms, such as oxalic acid, malonic acid, succinic acid, geltanic acid, Malene derivative Niacetylacetonate: Acetylacetonate derivative: Ethylene Useful in the method selected from the group consisting of diaminetetraacetic acid and mixtures thereof Vanadium in water-soluble vanadium compounds is found to be in the +4 oxidation state. If the vanadium is reduced to the +4 oxidation state, the +4 acid vanadium above the oxidation state and an amount effective to reduce the vanadium to the +4 oxidation state Preferably, it is mixed with one or more complexing agents present in the compound. Such a banner If sium reduction is desired, the complexing agent should be present in a concentration of 2 to about 12, more preferably 2 to about 12 complexing agents per molecule. preferably selected from the group consisting of dicarboxylic acids containing from 2 to about 8 carbon atoms. is preferable. Even more preferred complexing agents for use in the present invention are acids, malonic acid, succinic acid, geltanic acid, maleic acid, phthalic acid, tetralic acid, and selected from the group consisting of mixtures thereof. Specific examples of specific complexing agents include the listed complexes. to form a generating agent and/or to form a preferred water-soluble vanadium compound. These compounds, including precursors and derivatives thereof, which function in the same manner as complexing agents. .

Excellent results when the vanadium complexing agent used in the present invention is oxalic acid is obtained.

The specific amount of complexing agent to be used in the present invention is as described herein. The amount used is not critical as long as it is sufficient to act as a The particular type of complexing agent or complexing agents being used, the water-soluble vanadium to be formed. Depends on the chemical composition of the compound and the oxidation state of vanadium in the materials fed to the process. exist and change. - In specific examples, the number of molecular weights of the complexing agent used is Preferably in the range of about 0.5 to 10, more preferably about 1 to 6 per atomic weight of um. It is in.

Products prepared by the method of the invention have unique structural or textural properties, such as exhibiting area and attrition resistance and compared to products prepared by conventional methods. For example, it is used as a sulfur oxide and/or nitrogen oxide removal material in fluid catalytic cracking operations. The layer exhibits excellent properties.

The present method of preparation preferably produces a product with a weight of more than about 50 gm, more preferably 70 m2/gm, even more preferably 90 m2/gm or more, and about less than 2, more preferably less than about 1.5, even more preferably less than about 1.3 Alkaline earth metal aluminum containing attrition resistance index (API) Manufactures spinel.

The API for cracking or decomposition catalysts is the catalytic It was found that it gives a reasonable correlation to the attrition of the medium. API high The higher the expected attrition loss of the catalyst.

API is measured as follows. Powder material being tested (greater than 20 microns) grain size) is placed in the attrition stage. This attrition student The starting step is to place a predetermined amount of powder in a hollow, long tube, and blow the powder into three high-speed air jets. The fines (particles less than 20 microns) associated with exposure to jets are It is separated through the core separation section and collected in the chimple. Weight per unit line Volume loss is measured hourly for 5 hours. From these data, in 5 hours The total weight % loss over measured.

The material ARI is a commercially available product sold by Katalistiks, Inc. For the Delta Series 400 cracking catalyst, which is a fluidized hydrocarbon cracking catalyst. Relative slope of the weight % loss versus time plot between 1 hour and 5 hours in comparison. The absolute slope of the plot of 0 wt% loss versus time, defined as will vary somewhat depending on the particular attrition test equipment and conditions. alistiks, Inc. in its sales catalog Delta Series 400 Absolute value of the slope of weight % loss versus time (1 to 5 hours) for cranking catalysts is typically 0.9.

One embodiment of the invention is to remove sulfur oxides and/or nitrogen oxides, such as combustion products. Involves contacting a contained gas with a substance containing the present spinel or spinel composition . As a result of this contact, decreasing concentrations of sulfur oxides and/or nitrogen oxides, e.g. A reduction in sulfur oxide and/or nitrogen oxide emissions from the combustion zone is achieved.

Typical combustion zones include, for example, fluidized bed coal-fired steam boilers and fluidized sand bed waste combustion. In zero coal-fired boiler applications, including roasters, the present spinel and spinel compositions are , in the combustion zone, e.g. in a boiler, where combustion occurs separately or together with sulfur-containing coal. The added composition then leaves the combustion zone with the coal ash and The ash is separated from the ash by sieving, density separation, or other well-known solid separation techniques. − In embodiments, the oxidized sulfur-containing gas is present in one or more gases separate from the composition and the combustion zone. In the zone, contact is made under conditions that reduce the sulfur oxide content in the gas.

These conditions within the contact zone are such that conventional sulfur oxide or nitrogen oxide scavengers cannot be used. It may be one that is typically used in a contact zone. Contains sulfur oxide and/or of the present spinel and spinel compositions used in loads that come into contact with nitrogen oxide-containing gases. The amount preferably covers at least about 50% of the sulfur oxides and/or nitrogen oxides in the gas. The layer is preferably sufficient to reduce the amount by at least 80%. The reduction conditions are based on the composition at least a portion, preferably at least about 50%, more preferably at least about 50% of the sulfur associated with the For example, as reducing conditions, Temperatures in the range of approximately 900 to 1800@F; temperatures in the range of approximately 0 to 100 psig A reducing medium having a pressure ratio of about 1:10, such as hydrogen, hydrocarbon, etc. The continuous sulfur molar ratio can be mentioned.

In yet another example, the present invention provides an improved method for converting sulfur-containing hydrocarbon feedstocks. hydrocarbon conversion, preferably cracking processes. This method ( 1) converting the feedstock under hydrocarbon conversion conditions in at least one reaction zone; producing at least one hydrocarbon product upon contact with the promoting solid particles; Forming a deactivated sulfur-containing carbonaceous material on solid particles: (2) containing the deposit; The powder and the oxygen-containing vaporous medium are attached to the carbon absorbent in at least one regeneration zone. In conditions where at least part of the substance is combusted, more solid particles of the charcoal come into contact with it. regenerates at least a portion of the hydrogen conversion catalyst activity and converts sulfur oxides (e.g. sulfur trioxide) forming a regeneration zone flue gas containing nitrogen oxides; and (3) ) The improvement, which involves periodically repeating steps (1) and (2), This spinel has a chemical composition different from that of the solid particles and is in intimate admixture with the spinel. Containing small amounts of discrete entities (hereinafter referred to as granules) ). These particulates are caused by oxidized sulfur and /or present in an amount sufficient to reduce the amount of nitric oxide.

Preferred relative ratios of solid particles to particulates are about 80-99 parts by weight and about 1 part by weight, respectively. ~20 parts by weight.

The present invention is suitable for use with any conventional reactor-regenerator equipment, effervescent catalyst bed equipment, reaction zone The catalyst is handled in equipment that continuously transports or circulates the catalyst between the It is advantageously used with catalysts (solid particles and granules) that Circulation type equipment is preferable. Typical examples of circulating catalyst bed equipment are conventional moving bed and fluidized bed reactors - regeneration. equipment. Both of these circulation methods are used for hydrocarbon conversion, for example, hydrocarbon cracking. Fluidized bed reactor-regenerator equipment is particularly preferred. Delicious.

Solid particles and granules are used as physical mixtures of separate particles - specific examples In this case, the particulates are incorporated as part of solid particles. That is, for example, RO3 Granules consisting of growing microspheres are mixed with solid particles during the production of solid particles, for example, to form solid particles. form a coalesced particle that functions as both a particle and a granule. In this specific example, the grain The particles are preferably separate phases of the coalesced particles. One to provide coalesced particles A preferred method is to calcinate the granules prior to incorporating them into the coalesced particles. That's true.

The morphology, i.e. the particle size, of the present particles, both solid particles and granules as well as coalesced particles, is are not critical to the invention and depend, for example, on the type of reaction-regeneration equipment used. It exists and changes. These particles can be billed, caked, extruded using conventional methods. Vine shaped into any desired shape such as powder, granules, spheres, etc.6 For example, if the final particles are intended to be used as a fixed bed, the particles are preferably or a minimum dimension of at least about 0.01 inch and about 0.5 inch to 1 inch or more. is formed into grains having a maximum dimension of up to Especially for fixed bed or moving bed operations 0.03 to 0.25 inch, preferably about 0.03 to 0.15 inch. For fluidization systems, where spherical particles with a diameter of 1/2 inch are often useful, Preferably, the majority of the particles are about 10 to 250 microns, more preferably The thickness is approximately 20 to 150 microns.

The solid particles promote the desired hydrocarbon conversion. What does “hydrocarbon conversion” mean here? , one or more of the feed materials or reagents and/or one or more of the products or conversion products are chemical reactions that are hydrocarbon in nature, e.g. consisting primarily of carbon and hydrogen. It means response or transformation. Solid particles also have a different composition (i.e. chemical composition). In one preferred embodiment, The solid particles (or the solid particle portion of the above-mentioned combined particles) are substantially free of the present spinel.

The composition of solid particles useful in the present invention is such that such particles achieve the desired hydrocarbon conversion. The present invention is useful in the conversion of many hydrocarbons. However, the present catalyst and hydrocarbon conversion method have oxidative regeneration properties of the catalyst. These Catalysts are generally Y zeolite, LZ-210, ZSM-5 and molded products of the above. It contains components for decomposing zeolite. Many of these hydrocarbon catalytic cracking is a heavy or higher boiling component such as gasoline, hexane, hexene, pentane, or pentane. Butane, butylene, propane, propylene, ethane, ethylene, methane, and and other lower boiling components such as mixtures thereof. often, practically Typically, hydrocarbon feedstocks include petroleum, shale oil, tar sands oil, coal, etc. It consists of gaseous oil fractions derived from etc. Such feedstocks are straight distillates, e.g. barges. It may consist of a mixture of gaseous oils. Such gaseous oil fractions are often boils primarily in the range of about 400-100°F. Other substantial hydrocarbon feedstocks , such as naphtha, high-boiling or heavy distillates of petroleum, petroleum residues, shale oil, tar Rusand oil, coal etc. and mixtures thereof can also be separated using the catalyst and method of the present invention. It is understood. These essentially hydrocarbon feedstocks contain small amounts of other elements, such as sulfur, Contains nitrogen, oxygen, etc. - In one aspect, the present invention provides sulfur and/or hydrocarbon converting a hydrocarbon feedstock containing sulfur chemically bound to the feedstock molecules; It depends. The amount of sulfur in these hydrocarbon feedstocks is preferably about 0.01 to 5% by weight of the total feedstock. The present invention is particularly useful, preferably in the range of about 0.1 to 3% by weight.

Hydrocarbon cracking conditions are well known and often range from about 850 to 1100 and other reaction conditions including a temperature in the range of about 900-1050"F, preferably about 900-1050"F. The pressure is typically up to about 100 psig, preferably about 1:2 to 25:1. or a catalyst-to-oil ratio of 3 to 1 to 15 to 1 and a weight hourly space velocity (W H3V) is included. These hydrocarbon decomposition conditions are, for example, as well as the solid or coalescing particles, the reactor-regenerator equipment used, e.g. will vary depending on the moving bed catalytic cracking equipment and the desired product or products. Good morning.

In addition, hydrocarbon catalytic cracking equipment uses solid particles of catalyst to promote hydrocarbon cracking. Alternatively, it may include a regeneration zone to restore the catalytic activity of the combined particles. from the reaction zone Carbonaceous, especially sulfur-containing, carbonaceous deposits catalyst particles absorb free oxygen in the regeneration zone. removing or burning the contained gas and at least a portion of the carbonaceous material from the catalyst particles; The contact can be carried out under conditions that restore or maintain the activity of the catalyst.

When the carbonaceous deposit contains sulfur, at least one kind of sulfur is added in the regeneration zone. Containing combustion products are generated. The conditions for such free oxygen-containing gas contact are , for example, varies over a conventional range. In the catalyst regeneration zone of hydrocarbon cracking equipment. The temperature is about 900-1500°F, preferably about 1100-1350°F.

More preferably within the playback band, often in the range of about 1100 to 13oO°F. Other conditions include, for example, pressures up to about 100 psig and Average catalyst contact times in the range of minutes are included. Examples of carbon and hydrogen as adhering substances For example, there is sufficient oxygen in the regeneration zone for complete combustion to carbon dioxide and water. is preferably present. The amount of carbonaceous material deposited on the catalyst in the reaction zone is Preferably from about 0.005 to 15% by weight of the catalyst, more preferably from about 0.1 to 10% by weight of the catalyst. The amount is in the range of %. If the carbonaceous deposit contains sulfur, the amount depending on the amount of sulfur in the hydrocarbon feedstock. This attached substance weighs approximately 0.01 to 10 Contains a large amount of sulfur.

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

The following examples present various specific embodiments of the methods and compositions of the present invention. Rather, it is shown to further illustrate the invention rather than to limit it.

Plate” - Oiyu Lλ These examples illustrate the complexation of oxalic acid with vanadium materials.

An aqueous solution containing vanadium was treated with 2 molecular weight oxalic acid dihydrate (HzCt04. 2HtO) and 1 molecular weight (7) NH, VO3t in the required amount of water at 40'C. It was prepared by dissolving it. A green solution containing water-soluble vanadium compounds is produced. did. The green solution is probably in the +4 oxidation state when one molecular weight of oxalic acid is added. Takumi turned blue due to the formation of water-soluble vanadium compounds containing vanadium An aqueous solution containing vanadium is mixed with 2 molecular weight oxalic acid dihydrate and 1 molecular weight pentaacid. prepared by dissolving vanadium chloride in the required amount of water at 40-50°C. Manufactured. The final solution has a deep blue color, which is the +5 acid of vanadium in the +5 oxidation state. Reduction to vanadium state and water-soluble vanadium compound HzVO (C204) It suggested the formation of z.

[ This example shows a magnesia-enriched, magnesium, aluminum compound according to the preparation method of the invention. 2 illustrates the formation of a spinel composition containing Ni.

A gel-containing water slurry having a pH of 9.15 was added to 68 g at ambient temperature. water, 2.76 kg of formic acid, 3°91 g of pseudoboehmite alumina on a solid basis, and By mixing 3.1 Kg of magnesia with a surface area of 96 m”7 g Formed. Spray dry the slurry and spray dry product at 1350″F. It was fired in an air atmosphere for 2 hours. This substance contains magnesium and aluminum. spinel and magnesia (17% of the total weight as determined by X-ray diffraction) free magnesia), this material had an average particle size of 56 microns, 123 m ”/gm and an attrition resistance index of 1.o8.

Salmon A 85.8 gm of calcined material from Example 3 was first diluted with water to 42 ml of Ce(NOs). ) impregnated with 42 ml of a 60 wt% aqueous solution of As described in Example 2 made from oxalic acid dihydrate and 1.78 gm of vanadium pentoxide. It was impregnated with 25 ml of such aqueous solution. Dry the product overnight at 250''F and then The resulting material was fired at 1325"F for 1.5 hours in air. % cerium (calculated as elemental cerium) and 1% by weight vanadium (calculated as elemental cerium) containing 12.4% free magnesia (by X-ray diffraction) . The physical properties of this substance and the ``sulfur dioxide oxidation and absorption index J (SOAI)'' This is shown in the table presented later.

Salmon 2 42.2 gm of 60% by weight aqueous cerium nitrate solution was diluted to 45 ml with water.

It contains 3.1 gm oxalic acid dihydrate and 0.89 gm vanadium pentoxide. 10 ml of an aqueous solution as described in Example 2 were added. Firing material from Example 3 85. 8 gm was impregnated with the above mixed solution. The product was dried overnight at 250”F and after 1 Bake in air at 325°F for 1.5 hours. The generated material is 10 weight % cerium (calculated as elemental cerium) and 0.5% by weight vanadium (calculated as elemental vanadium) Contains 12.1% free magnesia (by X-ray diffraction). is. Physical properties of this substance and “Sulfur Dioxide Oxidation and Absorption Index J (SOAI)” are shown in the table presented later.

Fifty-two In a continuous experiment, 11.5 kg of formic acid, 20.6 kg of pseudo-boehmite on a solid basis Toalumina, a 16.4Kg mag with a surface area of 9.6m”7g on a solid basis Contains an aqueous gel containing nesia and 5.65 kg of ground cerium oxide on a solid basis. A slurry (8% solids by weight) was prepared. Spray dry the slurry and spray dry The product was calcined at 1350°F for 2 hours in an air atmosphere. 20 of fired substances Impregnating 0gm part with 4.6gm NH, VO3 and 9.9gm oxalic acid dihydrate did. Dry the impregnated product at 250°F and store the dried product at 1325°F. The mixture was baked in an air atmosphere for 2 hours. This magnesium and aluminum containing spine 1% by weight cerium (calculated as elemental cerium) and 1% by weight vanadium (calculated as elemental cerium). (calculated as elementary vanadium) and 13.3% free magnesia (by X-ray diffraction) Contained. The physical properties and (SOAI) of this material are shown in the table presented below.

Takumi 1 Example 6 was repeated except that the magnesia used to prepare the slurry was 36 It had a surface area of m27grn. Spinel composition containing magnesium and aluminum The spinel contains less magnesium and aluminum than the corresponding composition of Example 6. It only included This is a more preferred highly reactive magnesia, i.e. about 50 m'' One of the main advantages of using magnesia, which has a surface area greater than /gm Demonstrate.

Takumi 1 The aqueous gel-containing slurry was mixed with 19 g of water, 700 gm of formic acid, and 979 gm of dry pseudo-boehmite alumina of 775. 2 gm (dry basis) of magnesia and 844 gm of Ce(NOs)s6HJ It was prepared by mixing a 60% by weight aqueous solution of. Spray dry this slurry The dried product was then calcined at 1325°F for 2 hours in an ambient atmosphere. firing 98.2 gm of product was mixed with 1.78 gm of vanadium pentoxide and 6.17 gm of sulfur. It was impregnated with an aqueous solution 83+I11 containing uric acid dihydrate.

Dry the impregnated product overnight at 250'F and dry the dried product at 1325'F. It was baked for 2 hours. The produced magnesium and aluminum-containing spinel composition is um, vanadium and 15.4% free magnesia (by X-ray diffraction). , the physical properties of this substance and (S.

AI) is shown in the table presented later.

Takumi Dan The aqueous gel-containing slurry was mixed with 19 kg of water, 700 gm of formic acid, and 979 gm (dry weight). Standard) pseudo-boehmite alumina, with a surface area of 96 m”/gm, 775.2 gm (dry basis) of magnesia, and 36.6 gm of vanadium pentoxide and 123 By mixing 436 ml of an aqueous solution containing gm of oxalic acid dihydrate. Prepared. This slurry was spray dried and the dried product was exposed to 1325''F. The mixture was baked in an air atmosphere for 2 hours. 87.7 gm of this calcined product was added to 71 m of water. With a 60 wt% aqueous solution of 42.2 gm of Ce(NOs)s・6H*0 diluted to 1. Impregnated. Dry the impregnated product at 250°F for 3 hours and dry the product at 1325°C. Baked for 1.5 hours in an air atmosphere at °F. Generated magnesium, aluminum The spinel composition contains cerium, vanadium and 10.7 wt.% free mag. (by X-ray diffraction). The physical properties of this material and (SOAI) This is shown in the table presented later.

Acid, 979 gm (dry basis) pseudo-boehmite alumina, 98 m27 gm surface 775.2 gm (dry basis*) of magnesia, 844 gm (lDce (No,)s・6)1.00) 60% by weight aqueous solution and 36.6gm of pentoxide bar Mix 436ml of an aqueous solution containing sodium and 123gm of oxalic acid dihydrate. It was prepared by combining. This slurry was spray dried and the dried product was Fired in air at 25@F for 2 hours. Generated magnesium, aluminum The spinel composition contains cerium, vanadium and about 8.3% by weight free mag. The physical properties of this material and (SOAI), including (by X-ray diffraction) The superficial aqueous gel-containing slurry presented later was prepared by adding 56 g of water, 2.56 kg of formic acid, 3.36kg (dry weight basis) pseudo-boehmite alumina, 0.95kg Ce0a (Dry weight basis) Containing 14.1 kg of aqueous pulverized slurry, 96 m”/gm table with an area of 2.9 kg (dry basis) of magnesia and 124.6 gm of pentaacid. 1100 ml of an aqueous solution containing vanadium chloride and 370 gm of oxalic acid dihydrate. It was prepared by mixing the liquids. Spray dry this slurry and dry product was fired. The produced magnesium, aluminum-containing spinel composition is cerium , vanadium and about 15% by weight free magnesia (by X-ray diffraction). child The physical properties of the material and (SO, AI) are shown in the table presented below.

Salmon top An example of this is the production of spinel compositions in which the aluminum raw material is present in anionic form. This exemplifies yet another method.

By dissolving 9Kg of Mg(NOs)z・6H20 in 16g of water Solution (A) was prepared and mixed with 48 g of water.

The second solution (B) was mixed with 7.8 kg of sodium aluminate aqueous solution (41% by weight sodium mate), 0.73 g of 50 wt% aqueous NaOH solution and 13.3 K It was prepared by mixing g of water. Mixing solution (B) with solution (A) under high shear was added gradually to form a gel. After completion of addition, 1.86Kg of 60% nitric acid Aqueous cerium solution was added to the gel and the resulting mixture was stirred for 30 minutes. Enjoy the gel and washed with 25 ml of water per solid duram. The produced filter cake is 11 % solids by weight. This material was mixed with enough water to give a total solids content of 10% by weight. The slurry was slurried and fed to a wheel atomizer-spray dryer.

After spray drying, the microsphere powder is washed with 20 ml of water per solid unit duram and rinsed. The purified powder was dried at 2200F and then dried at 1350@F for 2 hours in ambient air. Fired. A 60 gm portion of fired material was combined with 1.07 gm of vanadium pentoxide and 3.1 gm of vanadium pentoxide. 7 gm of oxalic acid dihydrate. This impregnated raw The composition was dried overnight at 250°F and incubated at 1325°F for 2 hours in an atmospheric atmosphere. Baked for a while. The produced magnesium, aluminum-containing spinel composition is cerium and vanadium but no free magnesia (by X-ray diffraction) , the physical properties and (SOAI) of this composition are shown in the table presented below.

From examples, surface area, average grain, attrition resistance The final child size of John index 5 OAI participation month 2 "Namori - animal" / Dannie Mi Kron” Ninoe U3 123 56 1.08 - 4 113 62 1.21 17.25 106 58 0.42 15.7 6 196 56 0.26 12.18 103 49 1, 08 19.6 9 107 49 0.77 18.910 167 53 1.02 17. 111 1 05 53 1.07 10.612 164 56 3.94 19.6*Sulfur dioxide oxidation and absorption index in the presence of a given composition of Pick up sulfur trioxide produced by oxidation of sulfur dioxide in 15 minutes at temperature Defined as the percentage of magnesium in the composition that participates in gas The flow rate was 16l60-17O/min and the gas was 0.32 mole% dioxide Contains sulfur and 2.0 mole% oxygen, with the balance being nitrogen. 5OAI is For example, if a given composition is It is a measure of the ability to connect with The higher the 5OAI, the greater the composition's ability to bind sulfur oxides. In good condition.

The present spinel compositions (Examples 3-6 and 8-11) have high surface area and good attrition properties. It also has low API and low API resistance. It has a high surface area but compared to about 2 Strips prepared by methods outside the scope of the invention that exhibit only low attrition resistance Contrast with the Pinel composition (Example 12).

Present spinel composition 4, 5.6.8.9.10. and 11 SOA I values for each set. The composition is useful as an oxidized sulfur remover, e.g. in a catalytic cracking unit. show.

i1 Lord Nuyu A composition equivalent to the final composition from each of Examples 4, 5, 6.8, 9.10 and 11 was prepared. Conventional crystalline aluminosilicate-containing fluid catalytic cracking catalysts as separate particles. Together, the total composition/catalyst system contained approximately 1% by weight of the composition. this Each promotes cracking of gas oil feedstock containing approximately 0.7% by weight sulfur. It was used in industrial fluid catalytic cracking equipment for this purpose. After a period of time, each effective in promoting the desired hydrocarbon cracking and in the catalyst regeneration zone of the equipment. Reduce the amount of sulfur oxides and nitrogen oxides emitted from the area in the absence of the above compositions. It was effective in reducing the amount of sulfur oxide and nitrogen oxide released.

The present invention provides improved spinel compositions, methods of preparing spinel compositions, and such spinel compositions. The spinel composition of the present invention provides a method for using spinel with high surface area and increased It also has attrition resistance that makes it suitable for use in catalysts circulating in catalytic cracking equipment, for example. This makes their use as sulfur oxide/nitric oxide inhibitors particularly attractive. Honsu The method for preparing pinel compositions is relatively easy to perform and manage and provides very useful products. give a product. In addition, by appropriately selecting raw materials, this preparation method Yellow/Nitrogen oxides are reduced or not produced at all. 9 Examples of the present invention that can be implemented and specific examples have been described, but the present invention is not limited to them, and It is to be understood that the invention may be practiced in various ways within the scope of the following claims.

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Claims (83)

[Claims] 1. (a) (1) acidic aluminum such that aluminum is present in positively charged species; By mixing a composition containing Ni and (2) a composition containing a basic alkaline earth metal, forming a mixture; and (b) Calcinate the mixture to obtain an aluminum-containing spinel composition of an alkaline earth metal. Aluminum-containing spinel composition of alkaline earth metals including forming objects method of manufacturing the product. 2. The method according to claim 1, wherein the alkaline earth metal is magnesium. 3. The patent claims that the acidic composition is aqueous and has a pH in the range of about 1.5-5. The method described in item 2 of the scope of the request. 4. Alumina in which the aluminum in an acidic composition is at least partially peptized A method according to claim 1 existing as 5. Alumina in which the aluminum in an acidic composition is at least partially peptized The method according to claim 3, existing as 6. 4. The method according to claim 3, wherein the basic composition is an aqueous group. 7. At least a portion of the magnesium in the basic composition is magnesium oxide, oxidized exists as a compound selected from the group consisting of magnesium precursors and mixtures thereof; 3. The method of claim 3. 8. At least a portion of the magnesium has a surface area greater than about 25 m2/gm 8. A method according to claim 7, wherein the magnesium oxide is present as magnesium oxide. 9. Claims wherein the magnesium oxide has a surface area greater than about 50 m2/gm The method described in box 8. 10. 2. The method of claim 1, wherein the mixture is basic. 11. 4. The method of claim 3, wherein the mixture is basic. 12. Claims wherein the mixture has a pH within the range of greater than 7 to about 10.5 The method according to paragraph 11. 13. Claim 1, wherein the mixture has a pH within the range of about 8 to about 9.5. The method described in Section 6. 14. the acidic composition is selected from the group consisting of formic acid, monobasic mineral acids and mixtures thereof; 6. The method of claim 5, comprising at least one acid. 15. 15. The method of claim 14, wherein the acidic composition comprises formic acid. 16. Claim 2, wherein the spinel composition contains free magnesia. Method. 17. Patent where the spinel composition contains about 0.1-30% by weight of free magnesia The method according to claim 16. 18. at least one of the acidic and basic compositions or in step (a) the first and The separate additional composition combined with the second composition comprises at least one additional metal compound. The spinel composition converts sulfur dioxide into sulfur trioxide under sulfur dioxide oxidizing conditions. The characteristics include in an amount sufficient to facilitate the oxidation of The method according to claim 1. 19. at least one of the acidic and basic compositions or in step (a) the first and The separate additional composition combined with the second composition comprises at least one additional metal compound. The spinel composition converts sulfur dioxide into sulfur trioxide under sulfur dioxide oxidizing conditions. The characteristics include in an amount sufficient to facilitate the oxidation of The method according to claim 5. 20. at least one of the acidic and basic compositions or in step (a) the first and The separate additional composition combined with the second composition comprises at least one additional metal compound. The spinel composition converts sulfur dioxide into sulfur trioxide under sulfur dioxide oxidizing conditions. The characteristics include in an amount sufficient to facilitate the oxidation of The method according to claim 15. 21. at least one of the acidic and basic compositions or in step (a) the first and The separate additional composition combined with the second composition comprises at least one additional metal compound. The spinel composition converts sulfur dioxide into sulfur trioxide under sulfur dioxide oxidizing conditions. The characteristics include in an amount sufficient to facilitate the oxidation of The method according to claim 16. 22. Claim 18, wherein the additional metal compound is a rare earth metal compound. Method. 23. Claim 20, wherein the additional metal compound is a rare earth metal compound. Method. 24. Claim 22, wherein the rare earth metal compound is a cerium compound. Method. 25. Claim 23, wherein the rare earth metal compound is a cerium compound. Method. 26. Claim 18, wherein the additional metal compound is present in the basic composition the method of. 27. Claim 20, wherein the additional metal compound is present in the basic composition the method of. 28. at least one of the acidic and basic compositions or in step (a) the acidic and basic compositions; A separate additional composition in combination with the basic composition comprises at least one reducible gold composition. The spinel composition is capable of absorbing alkaline compounds under alkaline earth metal sulfate reducing conditions. Sufficient to include in an amount effective to promote the reduction of the lithium metal sulfate. The method of claim 1 comprising in the amount. 29. at least one of the acidic and basic compositions or in step (a) the acidic and basic compositions; A separate additional composition in combination with the basic composition comprises at least one reducible gold composition. Magnesium sulfate in a spinel composition under magnesium sulfate reducing conditions. containing in an amount effective to promote the reduction of The method according to claim 5. 30. at least one of the acidic and basic compositions or in step (a) the acidic and basic compositions; A separate additional composition in combination with the basic composition comprises at least one reducible gold composition. Magnesium sulfate in a spinel composition under magnesium sulfate reducing conditions. containing in an amount effective to promote the reduction of The method according to claim 15. 31. at least one of the acidic and basic compositions or in step (a) the acidic and basic compositions; A separate additional composition in combination with the basic composition comprises at least one reducible gold composition. Magnesium sulfate in a spinel composition under magnesium sulfate reducing conditions. containing in an amount effective to promote the reduction of 17. The method according to claim 16. 32. at least one of the acidic and basic compositions or in step (a) the acidic and basic compositions; A separate additional composition in combination with the basic composition comprises at least one reducible gold composition. Magnesium sulfate in a spinel composition under magnesium sulfate reducing conditions. containing in an amount effective to promote the reduction of 19. The method according to claim 18. 33. at least one of the acidic and basic compositions or in step (a) the acidic and basic compositions; A separate additional composition in combination with the basic composition comprises at least one reducible gold composition. Magnesium sulfate in a spinel composition under magnesium sulfate reducing conditions. containing in an amount effective to promote the reduction of 25. The method according to claim 24. 34. Claim 28, wherein the reducing metal compound is a vanadium compound the method of. 35. Claim 30, wherein the reducing metal compound is a vanadium compound the method of. 36. Claim 32, wherein the reducing metal compound is a vanadium compound the method of. 37. Claim 33, wherein the reducing metal compound is a vanadium compound the method of. 38. Claim 34, wherein the vanadium compound is a water-soluble vanadium compound The method described in section. 39. Claim 35, wherein the reducing metal compound is a water-soluble vanadium compound The method described in section. 40. Claim 36, wherein the reducing metal compound is a water-soluble vanadium compound The method described in section. 41. Claim 37, wherein the reducing metal compound is a water-soluble vanadium compound The method described in section. 42. The vanadium compound is in the form of a vanadium complex salt of at least one complexing agent. 39. The method of claim 38. 43. The vanadium compound is in the form of a vanadium complex salt of at least one complexing agent. 39. The method of claim 39. 44. The vanadium compound is in the form of a vanadium complex salt of at least one complexing agent. 41. The method of claim 40. 45. The vanadium compound is in the form of a vanadium complex salt of at least one complexing agent. 42. The method of claim 41. 46. A dicarboxylic acid, hydroxide, in which the complexing agent has from 2 to about 12 carbon atoms per molecule. Radin, hydrazine derivatives, acetylacetonate, acetylacetonate derivatives Claims selected from the group consisting of ethylenediaminetetraacetic acid and mixtures thereof The method according to item 38. 47. A dicarboxylic acid, hydroxide, in which the complexing agent has from 2 to about 12 carbon atoms per molecule. Radin, hydrazine derivatives, acetylacetonate, acetylacetonate derivatives Claims selected from the group consisting of ethylenediaminetetraacetic acid and mixtures thereof The method according to item 39. 48. A dicarboxylic acid, hydroxide, in which the complexing agent has from 2 to about 12 carbon atoms per molecule. Radin, hydrazine derivatives, acetylacetonate, acetylacetonate derivatives Claims selected from the group consisting of ethylenediaminetetraacetic acid and mixtures thereof The method according to item 40. 49. A dicarboxylic acid, hydroxide, in which the complexing agent has from 2 to about 12 carbon atoms per molecule. Radin, hydrazine derivatives, acetylacetonate, acetylacetonate derivatives Claims selected from the group consisting of ethylenediaminetetraacetic acid and mixtures thereof The method according to item 41. 50. a complexing agent is present in an amount effective to reduce vanadium to the +4 oxidation state; and the complexing agent is a dicarboxylic acid having from 2 to about 12 carbon atoms and mixtures thereof. 42. The method of claim 41, wherein the method is selected from the group consisting of: 51. a complexing agent is present in an amount effective to reduce vanadium to the +4 oxidation state; and the complexing agent is a dicarboxylic acid having from 2 to about 12 carbon atoms and mixtures thereof. 48. The method of claim 47, wherein the method is selected from the group consisting of: 52. a complexing agent is present in an amount effective to reduce vanadium to the +4 oxidation state; and the complexing agent is a dicarboxylic acid having from 2 to about 12 carbon atoms and mixtures thereof. 49. The method of claim 48, wherein the method is selected from the group consisting of: 53. a complexing agent is present in an amount effective to reduce vanadium to the +4 oxidation state; and the complexing agent is a dicarboxylic acid having from 2 to about 12 carbon atoms and mixtures thereof. 50. The method of claim 49, wherein the method is selected from the group consisting of: 54. 47. The method of claim 46, wherein the complexing agent is oxalic acid. 55. 51. The method of claim 50, wherein the complexing agent is oxalic acid. 56. 54. The method of claim 53, wherein the complexing agent is oxalic acid. 57. having a surface area of greater than about 50 m2/gm and an attrition resistance index of less than about 2. Alkaline earth metal aluminum-containing spinel composition. 58. The set according to claim 57, wherein the alkaline earth metal is magnesium. A product. 59. Spinel has a surface area greater than about 70 m2/gm and an attrition resistance of less than about 1.5. 59. The composition of claim 58, having a cation index. 60. Spinel has a surface area greater than about 90 m2/gm and an attrition resistance less than about 1.3. 59. The composition of claim 58, having a cation index. 61. Sulfur dioxide acid with at least one additional metal component associated with the spinel in an amount effective to promote the oxidation of sulfur dioxide to sulfur trioxide under 59. The composition of claim 58 further comprising additional metal components present. 62. At least one reducing metal component that binds to the spinel, including sulfuric acid magnet in an amount effective to promote the reduction of magnesium sulfate under sium-reducing conditions. 59. The composition of claim 58 further comprising a reducing metal component present. 63. At least one reducing metal component that binds to the spinel, including sulfuric acid magnet in an amount effective to promote the reduction of magnesium sulfate under sium-reducing conditions. 62. The composition of claim 61 further comprising a reducing metal component present. 64. 62. The composition of claim 61, wherein the additional component is a rare earth metal component. 65. The set according to claim 62, wherein the reducing metal component is a vanadium component. A product. 66. The additional metal component is a cerium component and the reducing metal component is a vanadium component. 64. The composition of claim 63, wherein the composition is 67. further comprising about 0.1-30% by weight of free magnesia associated with the spinel. A composition according to claim 58. 68. further comprising about 0.1-30% by weight of free magnesia associated with the spinel. A composition according to claim 61. 69. further comprising about 0.1-30% by weight of free magnesia associated with the spinel. A composition according to claim 62. 70. further comprising about 0.1-30% by weight of free magnesia associated with the spinel. A composition according to claim 63. 71. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 1 A method characterized by: 72. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 2 A method characterized by: 73. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas. Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 15 A method characterized by: 74. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 16 A method characterized by: 75. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 18 A method characterized by: 76. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 28 A method characterized by: 77. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 32 A method characterized by: 78. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 56 A method characterized by: 79. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 57 A method characterized by: 80. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 61 A method characterized by: 81. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 62 A method characterized by: 82. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 63 A method characterized by: 83. (1) Oxidized sulfur content of sulfur oxide-containing gas and (2) Oxidation of nitrogen oxide-containing gas In order to reduce at least one of the nitrogen contents, the gas is mixed with a certain substance and (1) the gas Conditions for reducing at least one of the sulfur oxide content of the gas and (2) the nitrogen oxide content of the gas. as at least a portion of said substance. Using a spinel composition produced according to the method of claim 70 A method characterized by: