JPS5847087A - Hydrocarbon conversion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the kilning of solid, sulfur-containing materials in a manner that achieves reduced emissions of sulfur oxides to the atmosphere.

According to one particular embodiment, the invention comprises the catalytic cracking of a sulfur-containing hydrocarbon feedstock by a method that achieves a reduction in the amount of sulfur oxides released from a regeneration zone of a hydrocarbon catalytic cracking unit. .

Typically, catalytic cranking of hydrocarbons occurs in a reaction zone under hydrocarbon cranking conditions to produce at least one hydrocarbon raw material. f and deposits carbonaceous material (coke) on the catalyst.

Additionally, some of the sulfur already present in the feedstock hydrocarbons, such as part of the coke, is deposited on the catalyst. In an FCC reactor, approximately 50% of the sulfur in the feedstock
It has been reported that when H2 is converted to H2S, 40% remains in the liquid product and about 4-10 H2 is deposited on the catalyst. These violets are feedstock type, hydrocarbon recirculation rate, water vapor), IJ tubing rate, catalyst type,
The reaction varies depending on the temperature of the 8 chickens.

Sulfur-containing coke deposits tend to deactivate Clara Kink catalysts. The Clara Kink catalyst is continuously regenerated to a low coke content, typically less than about 0.4% by weight, by combustion with an oxygen-containing gas in a regeneration zone, thus facilitating the reaction. It works satisfactorily when recirculated into the vessel. In the regeneration zone, at least a part of the sulfur deposited on the catalyst is oxidized together with carbon and hydrogen, changing the form of sulfur oxides (S02 and S03, hereinafter referred to as rsOXJ) to substantial amounts of Co2, Co2 and t(io
Considerable research and research efforts have been directed toward reducing sulfur oxide emissions from these various gas streams, including those from the regenerator flue of FCC systems.

Although he tried his best, the results were not as desirable.

A number of metal-based compounds have been proposed as substances for absorbing sulfur oxides in FCC equipment (and other desulfurization applications), and as cranking catalysts and [inert materials (1ner)].
ts) Support force of each or, including particles of J; proposed as a support for active metal reactants. Proposed metallic anti-5
Much of the body loses its effectiveness when subjected to repeated circulation. Thus,
When oxides of metals from group 1 of the periodic table are impregnated onto FCC catalysts or various supports, the activity of metals from group 1 decreases rapidly under the influence of circulation conditions. When combined with catalyst particles and exposed to high temperature e.g.
Less effective in reducing OX release. The inclusion of significant amounts of chromium on the alumina support to improve SOX adsorption results in undesirable coke and gas formation.

Accordingly, it is an object of the present invention to provide improved compositions and methods for reducing sulfur oxide emissions.

An additional object of the present invention is to provide improved compositions and methods for reducing sulfur oxide emissions from the regeneration zone of a hydrocarbon catalytic cracking unit.

Another object of the invention is to provide an improved hydrocarbon conversion catalyst. These and other objects of the invention will be apparent from the following description and examples.

In one general aspect, the invention provides sulfur oxidation, at least a portion of which is sulfur trioxide, by burning a solid, sulfur-containing material by contacting it with gaseous oxygen in a combustion zone under combustion conditions. combustion products including combustion products. The improved method of the present invention comprises this contacting of an effective amount, preferably a major amount by weight, of a loose entity containing at least one metal-containing spinel, preferably an alkaline earth metal-containing spinel. reducing the amount of sulfur oxides released from the combustion zone (compared to combustion in the substantial absence of loose entities). In another embodiment, the improved method of the present invention provides this contacting with an effective amount, preferably a major amount by weight, of at least 1 m of alkaline earth metal-containing spinel and a minor amount combined with the spinel. In particular, in the presence of a loose entity containing at least one rare earth metal component of 3 - "f" (compared to combustion in the substantial absence of a loose entity) from the smoldering zone. This includes reducing the amount of sulfur oxides released.

According to another aspect, the invention includes a conversion process carried out in at least one chemical reaction zone and at least one regeneration zone, preferably in the substantial absence of additional free hydrogen, In the zone, the yellow-containing hydrocarbon feedstock is contacted with the particulate material to form at least one hydrocarbon product and a sulfur-containing carbonaceous material deposited on the particulate material, and in the regeneration zone, the sulfur-containing carbonaceous material is deposited on the solid particles. Combustion of the sulfur-containing carbon-based material by contacting at least a portion of the deposited sulfur-containing carbon-based material with gaseous oxygen, and combustion products containing sulfur oxides, at least a portion of which is sulfur trioxide. Manufacture things.

The improvements of the present invention include (B) an effective amount of solid particles capable of promoting the desired hydrocarbon chemical conversion under raw hydrocarbon conversion conditions; of the apparatus, i.e. at least about 50% by weight, of at least one gold-containing spinel, preferably an alkaline earth metal-containing spinel. Where the loose entity comprises an alkaline earth metal-containing spinel, such loose entity further comprises a fraction of at least one rare earth metal, preferably cerium, combined with the spinel. In embodiments, the loose entities also include a small amount of a catalytically effective amount of at least one species of crystalline aluminosilicone effective to promote hydrocarbon conversion, such as cranking, under hydrocarbon conversion conditions. It also contains acid salts.The loose presence is sufficient to reduce the number of sulfur oxides in the regeneration zone effluent when used in a reaction zone-regeneration zone system as described in the Exist in quantity.

In one preferred embodiment, the particulate material, preferably loose, further comprises at least one additional species capable of promoting the oxidation of sulfur dioxide to sulfur trioxide under conditions in the regeneration zone. Includes metals, such as Group I platinum group metals.

Preferred platinum group metals are palladium and platinum, preferably platinum.

Preferred relative amounts of solid particles and loose entities are about 80-99 parts and about 1-20 parts, respectively.

The catalyst system is particularly effective for catalytic cranking of lower boiling products of hydrocarbon feedstocks. The catalyst system preferably also has improved carbon monoxide oxidation catalytic activity stability.

The improved process of the present invention can be used in any conventional reactor-regenerator system, in an ebullating catalyst bed system, for reaction N and
It can be advantageously used with catalysts placed in systems such as those involving continuous transport or circulation of the catalyst between regeneration zones. Circulating catalyst systems are preferred. Typical circulating catalyst bed systems are conventional moving bed and fluidized bed reactor-regenerator systems. Although both of these circulating bed yarns are commonly used in hydrocarbon conversion, such as hydrocarbon cranking, fluidized catalyst bed reactor-regenerator systems are preferred.

The catalyst system used according to a particular embodiment of the invention is 2
It consists of a mixture of said particles of species types.

Although the solid particles and discrete entities useful in the present invention can be used as a physical mixture of separate particles, in one embodiment, the discrete entities are combined as part of the solid particles. That is, discrete entities, e.g.
Metal-containing spinel, preferably at least one powerful p.
of calcined microspheres containing a metal component are combined with the solid particles, preferably in a separate and distinct phase, for example during the production of the solid particles, and the presence of the solid particles and loose particles useful in the present invention. form a combined particle that functions as both objects. One preferred method for providing a bonded particle is to calcine the loose entities prior to incorporating them into the bonded particles.

The morphology, ie, particle size, of the catalyst particles of the invention, both solid particles and loose entities, as well as bound particles, is not critical to the invention and will vary depending on, for example, the type of reaction-regeneration system used. Such catalyst particles can be used in conventional processes to form buildings, cakes, extrudates, powders,
It can be formed into any desired form, such as granules, globules, etc. For fluidized catalyst bed systems, it is preferred that the predominant amount by weight of the catalyst particles have a circumferential diameter of from about 10 microns to about 250 microns, and preferably from about 20 microns to about 150 microns.

Solid particles can promote desired hydrocarbon conversion. Solid particles also have a different composition (
In other words, it is characterized by having a chemical composition). In one compact embodiment, the solid particles (or the solid particle portion of the bonded particles described above) are substantially free of metal-containing spinels, such as alkaline earth metal-containing spinels.

In one aspect of the invention, the loose entities preferably include at least one metal-containing spinel, preferably an alkaline earth metal-containing spinel, and preferably a small amount of catalytically effective leaves for hydrocarbon conversion. Contains at least one crystalline aluminosilicate capable of promoting hydrocarbon conversion under conditions. Such a bulk alkaline earth metal present contains a small amount of at least one rare earth component, preferably a cerium fraction, combined with the spinel. In another aspect of the invention, discrete entities are solid entities in which they are present as separate and distinct particles and/or in the form of a single, preferably substantially homogeneous, combined particle. Conditions in which the particles and/or solid particles and/or one or more other types of solid particles (i.e., those having a different composition than the solid particles and loose entities present), e.g. contains a small amount of at least one additional metal, such as a platinum group metal, capable of promoting the oxidation of sulfur dioxide to sulfur trioxide. For example, an effective amount of at least one sulfur oxide oxidation catalyst component supported on a support, e.g. one or more inorganic oxides, e.g.
A metal or metal compound selected from groups VIB, VIA and III and mixtures thereof may be included together with the solid particles and the discrete entities and/or the solid particles may be included in the discrete entities. May be included above. As mentioned above, the sulfur oxide oxidizing component may be associated with, for example deposited on, the spinel component of the present discrete entity.

The composition of the solid particles useful in this invention is not critical, provided that such particles can promote the desired hydrocarbon conversion.

Particles with widely varying compositions are typically used as catalysts in such cliff hydrogen conversion processes, but the particular f+lJ g is selected depending on the chemical conversion of the desired type of hydrocarbon, e.g. .

By definition, solid particles suitable for use in the present invention include at least one natural or synthetic material capable of promoting the chemical transformation of a desired hydrocarbon. For example, when the desired hydrocarbon conversion involves one or more of hydrocarbon cracking, disproportionation reactions, isomerization, polymerization, alkylation, and dealkylation, such suitable materials include montmorillonite, Acid-treated natural clays such as kaolin and bentonite clays, natural or synthetic amorphous materials such as amorphous silica-alumina, silica-magnesia and silica-zirconia composite materials; optionally zeolite molecular sieves This includes crystalline aluminosilicates called . In certain cases, for example in hydrocarbon cranking and disproportionation reactions, the solid particles will preferably include crystalline aluminosilicate to enhance catalytic activity.

Methods for producing such solid particles and bound solid particles-discrete entity particles are conventional and well known in the art. Some of these methods are described in U.S. Pat. 140, 253 and U.S. Reissue Patent No. 2 7. It is described in detail in No.639.

Compositions of solid particles particularly useful in the present invention include, for example, a porous matrix containing an amorphous material that may or may not itself be capable of promoting hydrocarbon conversion, in an amount effective to promote the desired hydrocarbon conversion. For example, it is blended in an amount effective as a catalyst. Included in such matrix materials are clays and silicas.
Amorphous compositions such as alumina, magnesia, zirconia, mixtures thereof, and the like. The crystalline aluminosilicate is preferably incorporated into the matrix material in an amount of about 1 to 751 N, preferably about 2 to 50 N, of the total solid particles. The preparation of crystalline aluminosilicate-amorphous matrix catalyst materials is described in the above-identified patents. Catalytically active crystalline aluminosilicates formed during and/or as part of a process for producing solid particles, discrete entities and/or casings or bonded particles are within the scope of the present invention. enter. The solid particles are preferably deposited on the catalytic amorphous IJ lux material. Although substantially free of additional rare earth metal components, such as cerium, such rare earth metal components may be combined with the crystalline aluminosilicate component of the solid particles.

As noted, the loose entities utilized in the present invention preferably include a predominant amount of at least one metal-containing spinel, preferably an alkaline earth metal-containing spinel. In another aspect, the present discrete entity comprises a small amount of at least one additional metal, such as a platinum group metal component, capable of promoting the total oxidation of sulfur dioxide.

The spinel-type structure is based on a cubic close-packed arrangement of oxide ions; typically, the crystallographic unit cell of the spinel-type structure contains 32 oxygen molecules, with +( (there are two peranions in it) are occupied by divalent metal ions, and + (in which π2
peranions) are occupied by trivalent gold ions.

This typical spinel structure or its variants are type M”
Mg”04 (e.g. FeCr toa, ZnAe
tO4 and many other mixed metal oxides of type M'2M'04 (9I
For example, TIZnz04 and SnCog04) and type M 2MA04 (e.g. Na2M0O
4 and Ag5M004). This structure is X [Yz) 04
It is symbolized as , where [ ] confines the ion in the gap of the regular tetrahedron. An important form of the glaze is the reverse spinel 4-shaped structure Y [XY] 04, where half of the X ions are located in the gaps of the regular tetrahedron, and the X ions are together with the remaining 5 and half of the X ions. It is inside the gap of the regular octahedron. The inverted spinel type structure is the “metal-containing spinel (metal-containing 5-pir; +,
, el) are included within the scope of the expression J.

This inverted spinel structure occurs when the X ion strongly prefers octahedral coordination than the X ion. all M
ll'M2 1104 is, for example, Zn (ZnTl)0
4J: UK reverse spinel type, also MIIM2
Many of IIIO4 are also Fe” (Co■Fe■)04
s NjMz04g peml (FeHFe”)04
Yes, there are also many compounds with distorted spinel-type structures in which only a small portion of the X ions are in regular tetrahedral loci, such as Fe(NiFe)04 and Fe(NiFe)04. This occurs when the preference of X and X ions for octahedral and tetrahedral loci does not change significantly.

Further details regarding spinel-type structures can be found in the references listed below. %Modern ASpeCtS
of ■organic chemistry 'J(
,i,Emeleus and A,G,5har,pe
(1973), p. 57-58 and 512-513.
:%5truCtural Inorganic Ch
emistry' 3rd edition (1962) A, 1;', W
ells, p130.487-J190.503 and 526; and 'Advanced Inorgan
ic Chemistry'g 3rd edition.

F-A, Cotton and Q, Wi 1kinso
(1972), p, 5d-55° Metal-containing spinels include the following:

MnA1204-FeA1 *Oa, CoAl! o
4-NjAl 204-ZnA'204-MgT
lMg04 , Feh1gFe04 a FeT I
Fe04-ZnSnZn04-GaMgGa0a,
InMgIn04* BeLI 2F 4 , SLI
204, MoLI 1104-8aMg 204
a MgA 1204- CLIA l t04 s
(LIA 160g) -ZnKz (CN)4
- CdK2 (CN)4- HgKt (CN)4
, ZnTj 204゜FeVxO< e MgCr
2o46 MnCr 204, FeCr 204
a CoCr 20a -NjCJ 204, Zn
Cr2O4-CdCr z04, MnCrzS4.
Zn(J2S4-CdCr2S4, l T IM
n 204 a MnFe 204 * FeFe 2
04. COR's+04.

N l li'e 2o411 Cupe 1Io4
e ZnFe 204 @ CdFe 204 @ M
gC0204@TlCo204e C0C01104-
ZnCo2O4-5nCo204- COCO2Sn
-CucO2s4 * GeNI 204 a
NjN' 2 Sa a ZnGa t04 *
WAgz04* and zBSn204 - The metal-containing snails useful in the present invention contain a first metal and a second metal having an atomic fifl higher than the valence (oxidation state) of the first metal. The first and second metals may be the same metal or different metals. In other words, the same metal may exist in two or more different oxidation states in a given spinel; The atomic ratios of the metals do not have to match this classical theoretical formula for spinel. In one biological embodiment, the atomic ratio of first metal to second metal in the metal-containing spinels useful in the invention is at least about 0.17, preferably at least about 0.25. .

If the first metal is a monovalent metal, the atomic ratio of the first metal to the second metal is preferably at least 0.34, more preferably at least about 0.5.

The light and heavy metal-containing spinels for use in Invention 1 are alkaline earth metal spinels, particularly magnesium aluminate spinels. Lithium-containing spinels, which can be manufactured using conventional techniques, are also suitable for use. In the case of magnesium aluminate spinel, 8 Mg atoms and 16 M atoms are placed respectively in a single cell (8
MgAezO4 Other alkaline earth ions such as calcium, strontium, barium and mixtures thereof can be used to replace all or part of the magnesium.

Similarly, other pentavalent metal ions such as iron, chromium, vanadium, manganese, aluminum, cobalt, and mixtures thereof can be used in place of all or part of the aluminum ions. If the spinel contains a divalent metal (e.g. aluminum), the atomic ratio of divalent to trivalent metal in Subineno C is preferably in the range of about 0.17 to about 1.0; Preferably from about 0.25 to about 0.75, even more preferably from about 0.35 to about 0.
65, and even more preferably from about 0.45 to about 0.65, and even more preferably from about 0.45 to about 0.65.
It is 55.

Metal-containing spinels useful in the present invention can be derived from conventional and well-known sources. For example, these spinels are naturally occurring or manufactured using techniques well known in the field.
Therefore, a detailed description of such techniques was not included here. However, a brief description of the method of manufacturing the most preferred spinel, namely magnesium aluminate spinel, is disclosed below. Certain of the techniques described, such as drying and calcination, are applicable to other metal-containing spinels.

Magnesium aluminate spinels suitable for use in the present invention can be made, for example, by the method disclosed in US Pat. No. 2,992,191. Spinel can be polyformed by reacting a water-soluble magnesium inorganic salt and a water-soluble aluminum salt in which aluminum is present as an anion in an aqueous medium.

Suitable salts include strongly acidic magnesium salts, such as chlorides, nitrates or sulfates, and water-soluble alkali metal aluminates. When the magnesium salt and aluminate salt are dissolved in an aqueous medium, the cisvinel precursor is precipitated by neutralization of the aluminate acid with the acidic magnesium salt. It is preferred not to use excess acid salts or aluminates, thus avoiding precipitation of excess magnesium or alumina. Preferably, the precipitate is washed free of foreign rice ions before further processing.

Magnesium aluminate spinel is obtained by drying and firing. Drying and baking occur simultaneously. However, it is inconvenient to carry out the drying below the temperature at which water of hydration is removed from the spinel precursor. Thus, the drying is carried out at a temperature of less than about 260°C (500″F), preferably from about 104°C (220°F) to about 262°C.
(450”F). The preferred firing temperature is about 450”F.
27°C (800°F) to approximately 1093°C (20'0Of
f) Illustrated by a temperature range of V or above.

Calcination of the spinel precursor is carried out for a time of at least about half an hour, preferably for a time ranging from about 1 hour to about 10 hours.

Another method of making magnesium aluminate 2V flannel useful in the present invention is disclosed in U.S. Pat. No. 3,791,992. This method reduces the alkali metal content by mixing a solution of a soluble salt of divalent magnesium with a solution of an alkali metal dispersed in aluminium, separating and washing the resulting precipitate, and replacing the washed precipitate with an ammonium compound solution. , followed by washing, drying and baking steps. Generally, as noted above, metal-containing spinels useful in the present invention can be manufactured by methods conventional and well known in the art.

The composition, which is based on metallic spinel, is chosen because it has zero particles which can be formed using conventional methods into particles having any desired morphology, e.g. buildings, cakes, extrudates, powders, granules, globules, etc. The size of the final loose entity depends on the intended environment in which it is to be used, e.g. a fixed catalyst bed or a circulating catalyst bed reaction system, or as separate particles or in a mass of combined particles. As part of the vine.

Substantially non-intrusive proportions of other well-known refractory materials, such as inorganic oxides such as silica, zirconia, doria, etc., may be included in the discrete entities of the present invention. Free magnesia and/or alumina (ie, different from alkaline earth metal-containing spinel) can also be included in a loose entity, for example using conventional techniques. For example, the loose entity may contain about 0.1-25% by weight of free magnesia (calculated as MgO). In effect, "do not get in the way (n
□n-n-1interferrin J refers to amounts of other materials that do not have a substantial adverse effect on the catalyst system or hydrocarbon conversion process of the present invention. The inclusion of materials such as silica, zirconia, doria, etc. in the loose plugs of the present invention appears to serve to improve one or more of the functions of the loose entities.

Lithium-containing spinels useful in the present invention, such as lithium aluminate spinels, are preferably combined with a small amount of at least one rare earth metal component.

Cerium or other suitable rare earths or mixtures of rare earths can be combined with the spinel using any conventional technique or combination of techniques well known in the art, such as impregnation, coprecipitation, ion exchange, etc., with impregnation being preferred. . The impregnation is carried out in a solution of a subinel-earth, preferably an aqueous solution, such as a cerium ion+4 (preferably Ce, Ce- or a mixture thereof) or a mixture of rare earth cations containing a substantial amount (for example at least 40%) of a cerium ion. This is done by contacting the solution. Water-soluble sources of rare earths include nitrates and chlorides.

Included are solutions with rare earth concentrations ranging from 3 to 30%. Preferably about 0.05 calculated as elemental metal
-25% (1 concentration) of rare earth, more preferably about 0.1 to 15% rare earth, and even more preferably about 1.0 to 15% rare earth on the particles. Added.

It may not be necessary to wash the spinel after adding certain soluble rare earth salts (eg nitrates or acetates).

After impregnation with rare earth salts, the spinel can be dried and calcined to decompose the salts and form oxides in the case of nitrates or acetates.

Alternatively, the spinel, for example in the form of loose particles, could be fed into a hydrocarbon conversion, e.g. cracking unit, along with rare earths in salt form. In this case, the rare earth salt having a thermally decomposable anion is decomposed into an oxide in the reactor and can be used for combination with SOX in the regenerator.

Concentration of rare earth metals, e.g. cerium, calculated as metal in spinel-containing loose entities; about 1 to 25 divisions of total loose entities, more preferably about 2 to 15 i
Particularly good results are obtained using a range of quantities.

The discrete entities of the present invention are preferably capable of promoting the desired hydrocarbon conversion in even smaller amounts, at least 1
Contains seeds of crystalline aluminosilicate. Typical aluminosilicates are as described above. Preferably such aluminosilicates contain about 1-30% by weight, more preferably about 1-10% by weight of loose entities. The presence of such aluminosilicates in the present entities serves to increase the overall catalytic activity of the solid particle-discrete entity mixture to promote the desired hydrocarbon conversion.

As mentioned above, in one preferred embodiment, the particulate material useful in the present invention, such as the loose entities used in the present invention, also contains at least one metal, such as a platinum group metal, component. These additional metal component combustion conditions are defined as being capable of promoting the oxidation of carbon dioxide to carbon dioxide, such as those present in a catalyst regenerator.

Containing at least one additional metal component-
Increased carbon monoxide oxidation is also achieved. These metal components are found in elements 1B and IIB of the periodic table.

selected from the group consisting of Group IVB, IVB, VIIA and III, rare earth metals, vanadium, iron, tin and antimony and mixtures thereof, in any suitable manner in the particulate material useful in the present invention, e.g. Can be included. Additional metals, e.g. platinum group metals such as platinum, may be present in particulate matter, e.g. It can exist. In general, the total platinum group metal content present in the final loose entity is small compared to the amount of spinel; platinum group metal content is calculated on an elemental basis relative to the weight of the light or heavy loose entity. and about 0.0
5 p to about 1 part, more preferably about 0.05 to 1.0
00pu, and even more preferably about 0.0pu. S~500
Contains p1m. Separate entities weigh approximately 50-20
Excellent results have been obtained when containing at least one platinum group metal component of 0pIII, especially about 50 to 90p.

The other additional metal converts at least a portion, preferably a major portion, of the sulfur dioxide present to sulfur trioxide under combustion conditions, such as those present in the catalyst regeneration zone of a hydrocarbon catalyst cranking device. It is incorporated into the particulate material in an amount effective to promote oxidation. Preferably, the loose entities of the invention contain a small amount (calculated as elemental metal) of at least one additional metal component. Of course, the additional metals used may vary, for example, to the extent of the desired oxidation of sulfur dioxide! and the effect of additional metal components that promote such oxidation.

Instead of being included in discrete entities, one or more additional metal acid components may be included in all or some of the above solid particles and/or in the solid particles of the present invention or in discrete entities. For example, separate particles consisting of at least one additional metal component and a porous inorganic oxide support, such as platinum-supported alumina to promote the oxidation of sulfur dioxide, can be incorporated into particles of a type other than solid. Can be included in particles and discrete entities.

Additional metals, such as platinum group metal components, may be added by any suitable method, such as by impregnating the spinel at any stage of its manufacture and after or before firing of the spinel-based composition. , can be combined with spinel-based compositions. As mentioned above, various methods of incorporating additional metal components into particulate materials are common and well known in the art. One preferred method of adding platinum group metal to the spinel involves using a water-soluble compound of the platinum group metal to impregnate the spinel.

For example, platinum can be added to the spinel by mixing the spinel with an aqueous solution of chloroplatinic acid. Other water-soluble compounds of platinum can also be used as impregnating solutions, such as ammonium chloroplatinate and cyclized platinum.

Inorganic and organic solid compounds of platinum group metals are useful in incorporating platinum group gold components into the discrete entities of this invention. Preference is given to platinum group metal compounds, such as chloroplatinic acid and palladium chloride.

For example, if it is desired to use the solid particles alone for hydrocarbon conversion, or if it is desired to recover the discrete entities for other uses or for platinum group metal recovery, It is desirable to be able to separate things. This can conveniently be achieved by manufacturing the second solid particles in such a way that the second solid particles have a different size from the first solid particles.

Separation of the first and second solid particles can be readily accomplished by screening or other subdivision means.

As mentioned above, the solid particles and loose entities useful in the present invention include aggregate systems of bound particles that function as both solid particles and loose entities, e.g., to promote hydrocarbon conversion. Such bound particles can be produced by any suitable method, some of which are conventional and known in the art.

Although the present invention is useful in many hydrocarbon chemical conversions, the catalysts of the present invention, mixtures containing solid particles and loose entities, and methods are suitable for catalytic cranking of hydrocarbons and the regeneration of catalysts thus used. of particular applicability in systems. Such catalytic hydrocarbon cracking converts heavier or higher-boiling hydrocarbons into gasoline and other hydrocarbons. lll low-boiling components such as hexane, hexene, pentane, pentene, butane, butylene, propane, propylene, ethane,
Includes conversion, or cranking, to ethylene, methane and mixtures thereof. Depending on the case, the substantially hydrocarbon feedstock may be e.g. petroleum, mineral oil, tar sand oil,
Contains gas oil fractions derived from coal etc. As such, the feedstock may consist of a mixture of straight-run fractions, ie raw gas oils. Such soot oil fractions may vary from approximately 204 to 537"C (400 to 1000"C).
Boils in the 'F) range. Other substantially hydrocarbon feedstocks, such as petroleum oils, mineral oils, tar sand oils, other high boiling point or heavy fractions such as rock oil, can be cracked using the catalyst and method of the present invention. Such essentially hydrocarbon feedstocks often contain small amounts of impurities, such as sulfur, nitrogen, etc. In one aspect, the invention involves converting a hydrocarbon feedstock containing sulfur and/or sulfur chemically combined with molecules of the hydrocarbon feedstock. In the present invention, the amount of sulfur in such a hydrocarbon feedstock is about 0.01 to 5%, preferably about 0.1% based on the total feedstock.
It is particularly useful when the range is .about.3-wt.

Hydrocarbon cranking conditions are well known and vary from about 451 to 1100°C (850 to 11 (IQoF)).
, fEl shi<napproximately 482~565℃ (900~105℃
0°F). Other reaction conditions are usually about 7
．． 03 to 9/crIa (100 psia), a catalyst to oil ratio of about 1 to 2 to about 25 to 1, preferably about 3 to 1 to about 15 to 1, and a weight per hour space velocity of about 3 to about 60 ( WH8V)-. These hydrocarbon cracking profiles vary, for example, depending on the feedstock and solid particle size or combined particles in use and the desired product.

Historically, catalytic hydrocarbon cranking yarns include a regeneration zone to restore the catalytic activity of solid particles or bound particles of catalyst that have already been used to promote hydrocarbon cranking. Carbonaceous, especially sulfur-containing, carbonaceous deposits from the reaction zone are regenerated under conditions that restore or maintain the activity of the catalyst by removing at least some of the carbonaceous material from the catalyst particles, i.e. by smoldering. Upon contact with a free oxygen-containing gas in the zone, when the carbonaceous deposit material contains sulfur, at least one sulfur-containing combustion product is produced in the regeneration zone and then leaves the zone with the regenerator flue gas. be able to. The conditions under which such free oxygen-containing gas contact occurs may vary, for example, within normal ranges. The temperature in the catalytic regeneration zone of a hydrocarbon cranking system varies from about 482 to 815°C (900 to 1 soo"ir), preferably about 593 to 732°C (11 (JO to 135°F)
+), and more preferably about 593-704°C (11
00-1300'F). Other conditions within this regeneration zone are, for example, 7.03Kg/(I4.(100
psia) and an average catalyst contact time within the range of about 3 to 120 minutes, preferably about 3 to 75 minutes.

Sufficient oxygen is preferably present to completely combust the carbon and hydrogen of the carbonaceous deposit material to, for example, carbon dioxide and water. The amount of carbonaceous material deposited on the catalyst in the reaction zone is preferably about 0.005 to 15% by weight of the catalyst.
H, more preferably about 0.1 to 5 H. The amount of carbonaceous material deposited on the catalyst in the reaction zone is preferably between about 0.005 and 15% based on the weight of the catalyst, more preferably about 0.
．． It ranges from 1 to 10 inches. The amount of sulfur, if any, contained in the carbonaceous deposit I material varies, for example, depending on the amount of sulfur in the hydrocarbon feedstock. This deposit material is approximately 0
．． Contains 0.01 to 10 - or more by weight sulfur. At least a portion of the regenerated catalyst is optionally returned to the hydrocarbon cracking reaction zone.

The solid particles useful in the catalytic hydrocarbon cracking embodiment of the present invention may be any conventional catalyst capable of promoting hydrocarbon cranking under the conditions present in the reaction zone, ie, hydrocarbon racking conditions. Typical of these common catalysts are amorphous silica-alumina and about 8
A containing at least one crystalline aluminosilicon, acid salt, and mixtures thereof having an al pore diameter of A to 15. 1 When the solid particles and/or loose entities to be used in the hydrocarbon cranking embodiment of the present invention contain crystalline aluminosilicate, the crystalline aluminosilicate groups are combined with small amounts of conventional metal promoters, such as rare earth metals. In particular, it can contain cerium.

As previously noted, one aspect of the present invention is to contact solid, sulfur-containing materials in a combustion zone under combustion conditions to
producing a combustion product containing at least one glaze of sulfur oxides, at least a portion of which is sulfur trioxide. Reduction of sulfur oxide emissions from the combustion zone can be achieved by carrying out this contact in the presence of a loose entity containing at least one alkaline earth metal spinel and at least one rare earth metal component.

Typical solids combustion zones include, for example, fluidized bed coal-fired steam boilers and fluidized bed waste combustors. The loose entities of the present invention have sufficient strength to withstand conditions in such combustion zones. In coal burner boiler applications, the loose material is added separately to the combustion zone, e.g. the boiler, along with the sulfur-containing coal;
Smoking occurs here and at least some sulfur trioxide is formed. The loose entities leave the combustion zone along with the coal ash and are separated from the ash by, for example, screening, density separation or other well known solids separation techniques. The flue gas leaving the combustion zone has a reduced amount of sulfur oxides compared to, for example, combustion in the absence of loose entities. The loose entities from the combustion zone are then dissociated from the loose entities, such as at least a portion of the sulfur combined with the loose entities, e.g. in the form of H2S, and removed for subsequent processing, e.g. sulfur recovery. For example, contact with 17H2 in a reducing environment under such conditions. After removing the sulfur, the loose material is recycled to the combustion zone, such as a boiler.

Conditions in the boiler are those typically used in fluidized bed coal-fired boilers. The amount of loose entities used will reduce the sulfur oxide emissions in the boiler flue gas by at least about 50%, and preferably by at least about 8%.
It takes only a few minutes of light to reduce the amount by 0%. Conditions within the reduction zone are characterized by a low amount of sulfur combined with loose entities (and some
Preferably about 50%, more preferably at least 80%
are the four things that are removed. For example, reducing conditions are approximately 4
82-982℃ (9[] 0-18000F) No'N circumference approximately 0.98-7.03 Ky/crl (14-1
00 psia) and a H2 to bound sulfur molar ratio in the range of about 1 to 1°.

In fluidized sand bed waste combustion applications, for example, it acts as a heat sink. The fluidized sand is combined with loose material and circulated from the combustion zone to the reduction zone. A reduction in sulfur oxide emissions from combustion is thus achieved.

Conditions in the combustion zone may be those typically used in fluidized sand bed waste combustors. The amount of loose entities used is sufficient to reduce the sulfur oxide emissions in the combustion-like flue gas, preferably by about 50 degrees, more preferably by about 80 degrees. Conditions in the reduction zone are 1 for coal-fired boiler applications.
This is the one disclosed above and Mr. Pi.

By presenting some specific implementation aspects of the invention:
The following examples are presented to further illustrate the invention without limiting it.

Example 1 This example demonstrates the preparation of bulk entities useful in the present invention.

3.20 Kf (7,051 b) of sodium aluminate (298 wt. US NazO and 44.85 wt.% Ag)
2o, and analysis) was made into as much solution as possible by stirring with a total of 1 gallon of deionized water, and this was made into a solution of 25.4
The mixture was filtered through the furnace cloth using a crn (10 inch) defner funnel. The Pi solution was diluted to 8t with deionized water.

3.61 Ky (7,95 lb) Mg(NOx) *
Dissolve 6H20 in 1 gallon of water and add 166-concentrated HNO
3 was added.

The solution was diluted to 8t with deionized water.

521 of the two final solutions in a long rubber lined drum.
simultaneously from biuret in deionized water. The mixture was stirred vigorously during the addition. Addition of the No. 2 solution took 36 minutes. 2760 ml of sodium aluminate solution was added during this period.

pHi was maintained at Z5 from 7.0. After addition of all the magnesium nitrate-containing solutions, a PHk of 8.5 was achieved by adding sodium aluminate solution. After this, 1080v of aluminic acid solution remained, so it was discarded.

The mixture was kept overnight and then passed through a plate-frame filter. The cake was washed in the press with 110 gallons of deionized water. The cake was reslurried with 10 gallons of deionized water. 269 Mg(NOx)*6Hz O
A solution of 'ir 200- in deionized water was added to the slurry. The slurry was filtered and washed as before. After repeated slurrying, filtering and washing, the cake was dried in a forced air drying oven at about 121°C (250'F).

The dried product was then milled in a thermomill, first passing through a 1,27 mm (-0,050 inch) sieve;
Next, the part from 0 to 60 mesh is again this time 0.254
Hammer milled on a 0.010 inch sieve. The desired fine material was passed through a 60-menshi sieve. The product thus obtained, a magnesium aluminate spinel precursor, was then transferred to a 59 mm diameter quartz tube where it was heated at 482° C. (900° F.) for about 3 hours in a fluidized state at about 106°C per hour.
By firing at an air flow rate of t, aluminium or magnesium subineno-1 is formed, and the nine-1 nucleus is approximately 0.4
It was found to have a magnesium to aluminum valence of 8.

The resulting magnesium aluminate spinel particles were sieved to produce final particles having a diameter of less than 100 microns.

Examples except that the final magnesium aluminate subinel particles were impregnated with a total chloroplatinic acid aqueous solution using conventional techniques.''
1 was repeated. When the resulting particles were dried and fired, they contained about 100 pu of platinum, defined as elemental platinum, based on the weight of the total platinum-containing particles. The platinum was substantially distributed over the spinel-containing particles.

Example 3 Example 1 was used except that the calcined monomagnesium aluminate spinel was impregnated with cerium.

For cerium impregnation, 177 ml (0,391b) of cerium carbonate'i1820- was slurried in water and 350 ml of cerium carbonate was slurried in water.
- Dissolve 1.70 Kg (3,75 lb) of calcined magnesium aluminate spinel in the carbonate salt by mixing slowly with 70% nitric acid and place in a Pyrex tray, using rubber gloves. Impregnated with cicerium solution by hand stirring 3, after completion of impregnation, the mixture is 1
Equilibrated overnight.

The impregnated product was dried under IR light and finally at 127°C.
(260'F) oven overnight. dry product vi
-482°C (9°C) for 3 hours in a 59tan diameter quartz reactor
Calcined in a fluidized bed at an air flow rate of about 83 t/hr at 00°F. The obtained magnesium aldimate aluminum particles were sieved to produce final particles having a diameter of less than 100 microns, these final particles having a total content of 5% by weight of cerium, calculated as elemental cerium. was.

Example 4 Contains about 6 weight percent crystalline aluminosilicate, about 54 weight percent amorphous silica-alumina, and 40 weight percent alpha alumina, and about the same size as the final particles from Example 1. By combining an amount of solid particles of a commercially available hydrocarbon cranking catalyst with the final particles of Example 1, a loose entity of 51i and 95iki%
A mixture consisting of solid particles was obtained. The catalytic activity of the solid particles was equilibrated (prior to binding with loose entities) by using the same particles in a commercial fluidized bed catalytic cranking operation.

The mixture of solid particles and final particles was charged to a conventional fluidized bed catalytic cranking unit (FCCM) and used to crank the petroleum derived gas oil fraction, combined fresh feed and recycle stream. The new gas oil fraction is approximately 204 ~
It boils in the range 400-1000'F and is substantially hydrocarbon in nature, containing small amounts of sulfur and nitrogen as impurities. Typical hydrocarbon cranking and catalyst regeneration conditions are used in the reaction zone and regeneration zone, respectively, with a weight ratio of catalyst particles to total (fresh and recycled) hydrocarbon feed entering the reaction zone of about 6:1. Other conditions in the reaction zone are temperature °C (p) 499 (930) pressure
Kg/rda(psia) 1.05 (15)
WH8V 15 These conditions are 204℃ (400'F) for gas oil feedstock.
This resulted in a conversion of approximately 70 volumes to a product boiling below.

The catalyst particles from the reaction zone contained about 0.8% by weight carbonaceous deposit material that was at least partially combusted in the regeneration zone. This carbonaceous material also contained a small amount of sulfur, which produced SOZ under combustion conditions formed in the regeneration zone. The amount of oxygen in the regeneration zone is the amount theoretically necessary to completely burn out this deposit. heated to. The conditions during the regeneration zone are as follows.

Warm black 5℃C'F) 593(
11oO) Pressure Kg/ctda (psia)
15 Average Catalyst Residence Time, Minutes After 60 hours, the catalyst was shown to be still effective in promoting hydrocarbon cracking in the reaction zone and to reduce sulfur (as oxidized sulfur) from the flue gas in the regeneration zone. , a reduced release (compared to the treatment in the absence of the final aluminium-replaced magnesium spinel-containing particles) was obtained.

Example 5 The sister example 4 was repeated except that the platinum-containing particles of Example 2 were used in place of the magnesium aluminate spinel particles of Example 1. After a period of time, the catalyst remained effective in promoting hydrocarbon cracking in the reaction zone and oxidation of carbon monoxide and sulfur dioxide in the regeneration zone. Additionally, sulfur (as sulfur oxides) from the regeneration zone flue gas
A reduced release of (compared to treatment in the substantial absence of platinum-gold particles) was obtained.

Example 6 Example 4 was repeated except that the cerium-containing particles of Example 3 were substituted for the particles of Example 1.

Over time, the catalyst showed that it was still effective in promoting hydrocarbon cracking in the reaction zone, and of sulfur (as sulfur oxides) from the flue gas in the regeneration zone (final magnesium aluminate). A reduced release was obtained (compared to treatment in the absence of spinel-containing particles).

Example 7 RR magnesium aluminate spinel particles, platinum-containing particles, and cerium-containing particles each contain about 7% by weight of a crystalline aluminosilicate known to be catalytically active in promoting hydrocarbon cranking. Examples 1, 2, and 3 were repeated except that The crystalline aluminosilicate was incorporated into the particles using conventional, well-known techniques. Platinum, and particularly cerium, components are included in the particles such that substantial amounts, e.g., greater than about 50%, of the platinum and cerium are associated with the magnesium aluminate spinel of the particles rather than with the crystalline aluminosilicate. Ta. Cerium combined with crystalline aluminosilicate was substantially less effective at reducing SOX emissions than, for example, monocerium deposited on the magnesium aluminate spinel portion of the particles.

Example 8 The magnesium aluminate produced in Example 7 was prepared in Example 1.
Example 4 was repeated six times, except that particles were used instead.

After time in a hydrocarbon cranking operation, these catalyst mixtures were shown to be effective in promoting hydrocarbon cranking, resulting in reduced sulfur emissions from the regeneration zone. In particular, the crystalline aluminosilicate present in the loose entity improves hydrocarbon cranking in the reaction zone over that which occurs in yarns with the loose entity containing substantially no zeolitic components. It was discovered that

Example 9 A mass of bound particles is produced as follows.

Magnesium aluminate spinel solution was added to form an aqueous slurry of a magnesium aluminate spinel precursor (prepared as in Example 1) such that the spinel concentration, calculated as MgAlzO4, was about 9N. Manufactured a fragmented entity with a main body.

Known to be effective for promoting hydrocarbon cracking. By adding sufficient crystalline aluminosilicate to the slurry, the final magnesium aluminate spinel-based loose entity is reduced to about 10% of such crystalline aluminosilicate on a dry basis. Contains salt. This slurry is stirred for about 1 hour to ensure uniformity and then the loose Entity 1 is removed by spray drying at a temperature below that required to eliminate a substantial portion of the water of hydration. Manufactured. These loose entities were fired in an electric Matsufuru furnace using a programmed timer that increased the temperature from 149°C (300'F) to 566°C (1051°F) per hour and held this temperature for 6 hours. . The loose entities were impregnated with platinum and cerium as in Examples 2 and 3. The final loose mass had a total content of about 7 molar mass of cerium and about 100 molar mass of platinum, calculated as 9 molar mass of elemental cerium. The main parts of cerium and platinum are crystals,
was associated with spinel rather than with aluminosilicate.

Essentially all of the calcined loose entities had a largest dimension of less than about 200 micron.

Discarded loose objects larger than 60 microns.

adelphia qua diluted with equal weight of water
The solid particle-conjugate material was separated by adding 6000 parts by weight of rzCompany-O%El grade sodium silicate solution to 3000 parts of dilute (density -1,234) HgSO4.These 2N After thoroughly mixing the solution of ?, 1200 parts by weight of A12(' 5O4)
! A solution containing 1 18H20 was added. Sufficient crystalline aluminosilicates known to be effective in promoting hydrocarbon cranking are added to the mixture so that the final solid particle binder material is approximately 10% such crystalline on a dry basis. The resulting mixed food containing aluminosilicate was left to dell. The resulting 9 quarts of bait was cut into approximately 1.91 on (3/4") cubes and covered with concentrated NH4OHk diluted with an equal volume of water. This material' was left overnight and had a final pH of 11.
It had This substance was then washed by irrigating with water to eliminate Na and SO4 ions.

Thoroughly kneading 500 parts (on a dry weight basis) of the washed no-hydrodel and 80 parts (on a dry weight basis) of the remaining calcined loose material and 10.000 parts by weight with stirring;
Grind and mix. The resulting slurry was dried in a 17+i spray dryer. This dryer uses approximately 1.41 to 97 crly (20 ps) to disperse the slurry into the drying chamber.
It was equipped with a two-fluid nozzle system using air. The drying gas, or flue gas from the in-line burner, enters the drying chamber at approximately 399°C (7500F') and
Remove from the chamber at temperatures ranging from ~157°C (305-315° FI). °This drying gas is led to the top of the drying chamber, while
Sura +) Dispersed upward from near the bottom of the second chamber. The material to be dried by this method t1 was exposed to both a countercurrent flow (during its rise from the nozzle system) and a cocurrent flow (during its descent by gravity) to the downward drying gas flow. The resulting dried particles were calcined in a manner similar to the calcining of the loose entities described above for spinel purple organisms. The resulting combined particles were sieved to obtain particles of suitable size for use in a fluidized catalyst bed reaction zone-regenerator hydrocarbon cranking system. Example 10 Example 4 was repeated except that the loose entities and catalyst particles used in Example 4 were replaced with the bonded particles produced in Example 9. After time, these bound particles were shown to be still effective in promoting hydrocarbon cranking in the reaction zone and reducing the amount of sulfur in the regeneration zone flue gas released into the atmosphere. .

Example 11 Ll (NOJ, 3HzOk PwIt (NOa
) Example 1 was repeated except that 2.6120 was used; the final lithium aluminate spinel particles had a diameter of less than 100 microns. obtained n
The valence of lithium ions to aluminum ions in the yx spinel was approximately 2.

Example 12 The final particles of Example 11 were impregnated with chloroplatinic acid using conventional techniques. When the obtained spinel-containing particles were dried and calcined, they contained approximately 100 g of platinum based on Njl of the total platinum-containing particles, calculated as elemental platinum (g1). The platinum was substantially uniformly dispersed over the spinel-containing particles.

Example 13 The final particles of Example 11 were impregnated with an aqueous cerium nitrate solution using conventional techniques. When the obtained spinel-containing particles were completely dried and calcined, they contained about 10% of cerium, calculated as elemental cerium.
child.

Examples 14-16 Example 4 was repeated three times, except that the final particles of Example 1 were replaced with the spinel-containing particles obtained in each of Examples 11, 12, and 13. A reduced emission of sulfur (as sulfur oxides) from the flue gas was obtained.

Examples 17-21 Using conventional techniques, particles containing diameters less than 100 microns of the following pyrotechnical spinel materials were prepared.

Example Spinel 17 FeAl20a.

18 Mn1%1204 19 MfCg04 20 Fe! Tj04- 21' MfFe204 Examples 22-26 Example 4 was repeated five more times, except that the final particles of Example 1 were replaced with spinel-containing particles obtained in each of Examples 17, 18, 19, 20, and 21. . In each case, reduced emissions of sulfur (as sulfur oxides) from the flue gas of the regeneration zone were obtained.

Examples 27 and 28 These examples demonstrate the surprising benefits of the present invention.

Particle formulations were prepared for testing. The formulation is as follows.

o Formulation A - SeIJ prepared as in Example 1
Magnesium-impregnated magnesium aluminate spinel final particles 5
% heavy leaf and 95% by weight of a conventional zeolite-containing hydrocarbon cranking catalyst equilibrated in a commercial fluidized bed catalytic cracking operation.

○ Formulation B - 5 weight calculated as elemental cerium -
The cerium-impregnated alumina particles contain 50% cerium and have particle sizes ranging from 25 to 100 microns.
1% and 95% of the same conventional zeolite-containing catalyst as that used to make Formulation A. Cerium-alumina particles are known to have good initial sulfur oxide removal activity when used in fluidized catalyst cranking operations.

Both formulations were tested to determine their ability to continue removing sulfur oxides over extended periods of time. The test procedure is as follows. Step 1 includes an initial determination of the activity of the formulation to remove sulfur oxides from the regenerator flue gas.

Step 1 was carried out in a fluidized bed catalytic cranking pilot plant known to give results that correlate with those obtained in industrial scale equipment. The raw materials and conditions for Step 1 are as follows.

○Feedstock - Mid-continent gas oil containing 2.0 wt% sulfur ○Reactor temperature - 499°C (930°F) ○Regeneration i@IN
F -593℃ (1100'F) ○ Stripper temperature -
499°C (930°F) O pressure - 1,05 Ky/cJ (
15 psia) Approximate catalyst regeneration time - 30 minutes 0 Approximate stripping time - 10 minutes Approximate reaction time - 1 minute Steam as inert in the reactor, 6 mol.

Step 2 of the test procedure involved continuous and accelerated aging in a fluidized bed reactor that mimics the type of aging that occurs in commercial fluidized bed catalytic cracking operations.

The raw materials and conditions used in Step 2 are as follows.

○Feedstock - Gulf of Mexico coast gas oil containing sulfur related to 2,0x ○Reactor @ -499°C (930°F') ○Reactor pressure car 1.05 h/al (15 psia) ○Reactor retention Time - 1 minute ○ Reaction catalyst/oil weight ratio - 6 0 Stripping temperature - 499°C (930"F) ○ Regenerator temperature - 593°C (1100°F') O Regeneration group pressure car 1
．． 05 Kf/Ct/l (15 psia) ○ Catalyst regenerator retention time - 30 0 Regenerator combustion air flow ratio - 9,08 Kg (20 l b)
Air 10.454 Kg (1 lb) Coke Step 3 of this test procedure is to determine whether the activity of the formulation in removing sulfur oxides during the aging of Step 2 has been demonstrated.1 Repeating Step 1 periodically. It contained.

The amount of sulfur oxides released with the flue gas from regeneration using the formulations was used as the basis for determining the ability (ie, activity) of such formulations to remove total sulfur oxides.

The test results for formulations A and B according to the above procedure were as follows.

0 100 1002
93 43 4 89 18 818 (1) One day of aging under Step 2 conditions is more severe than the aging that would occur in a commercial FCC operation. Therefore, there is no direct one-to-one correlation between aging in these two types of aging modes.

These results indicate that the cerium-magnenium aruninate spinel particles in Formulation A are the same as the cerium-aluminum f
It is very clearly shown that it retains its sulfur oxide removal activity much longer than particles.

Relatively rapid loss of sulfur removal activity has been one of the major problems with prior art attempts to reduce sulfur oxide emissions, such as with cerium-supported alumina particles. Accordingly, these results show that the present invention provides substantial and surprising advantages in reducing sulfur oxides from combustion zones, such as regeneration zones of fluidized bed hydrocarbon catalytic cranking units.

Although the invention has been described with respect to various specific examples and implementations, it will be understood that the invention is not limited thereto and may be practiced in many ways within the scope of the claims.

Priority claim September 14, 1981■United States (US)■
301678 0 Inventor John A. Zietsker 2352 Homewood Clydetilas 6043 0 Illinois, USA

Claims (1)

[Scope of Claims] (f) A hydrocarbon conversion process in which a sulfur-containing hydrocarbon feedstock is reacted with at least one solid particle capable of promoting the conversion of the feedstock PI:'T: (2) forming at least one hydrocarbon product: and deactivated sulfur-containing carbonaceous material on the solid particles, thus forming deposit-containing particles; The deposit-containing particles are treated with an oxygen-containing vaporous medium at least once
regenerating at least a portion of the hydrocarbon conversion catalytic activity of the solid particles by contacting at least a portion of the carbonaceous deposit under combustion conditions in a regeneration zone containing sulfur trioxide; forming a regenerated flue gas, and (3
) A hydrocarbon conversion method for converting a sulfur-containing hydrocarbon feedstock comprising repeating steps (1) and (2) in all cycles, the method comprising: and at least one metal-containing spinel containing a first metal and a second metal having a valence higher than the valence of the metal, and the atomic ratio of the first metal to the second metal in the spinel is at least about 0.17, and the loose entities reduce the amount of sulfur oxides in the flue gas. A method of improvement consisting of being present in an amount sufficient to reduce the 2. The method of claim C1), wherein the discrete entity comprises at least one alkaline earth metal-containing spinel and at least one rare earth metal component associated with the spinel. (3) the conversion includes hydrocarbon cracking in the substantial absence of added molecular hydrogen, the solid particles and loose entities are flowable, and the reaction zone and the regeneration zone are A method as claimed in claim (1), in which the method rotates between (4) the transfer includes hydrocarbon cranking in the substantial absence of added molecular hydrogen, and the solid particles and loose entities are flowable between the reaction zone and the regeneration zone; The method of claim 2, as claimed in the appended claims. (5) The discrete entity has a mass of at least about 70
t% of the spinel, and the spinel contains about 25
tr? The method of claim 3, wherein the solid particles and/or the loose entities have a surface area of from about 600 m"/l to about 600 m"/f. A method according to claim 3, comprising an amount of at least one additional metal component capable of promoting the conversion of sulfur dioxide to sulfur trioxide under the conditions of step (2). 7.) The method of claim 6, wherein said additional metal component is at least one platinum group metal component. 8. At least one of said solid particles and loose entities further comprises a small amount of catalyst. 4. The method of claim 4, further comprising an amount of at least one additional metal component capable of promoting the conversion of sulfur dioxide to sulfur trioxide under the conditions of step (2). (9) The method of claim (8), wherein the additional metal component is at least one platinum group metal component. The atomic ratio of the second metal to the second metal is at least about 0.2.
3) Method described in section 3). αυ The method of claim tA00), wherein the spinel contains magnesium and aluminum, and the atomic ratio of magnesium to aluminum in the spinel ranges from about 0.25 to about 0.75. . a21 The spinel of claim 4, wherein the spinel contains magnesium and aluminum, and the atomic ratio of magnesium to aluminum in the spinel ranges from about 0.35 to about 0.65. Method. aJ The loose entities weigh at least about 90 -
3. The method according to claim 3, wherein the spinel comprises: 0荀 The method of claim 121, wherein the loose entity contains at least about 90% by weight of the spinel. 1. The rare earth metal component contains cerium. The method of claim 2, wherein the rare earth metal component of α is a cerium fraction and is present in an amount from about 1% to about 25% by weight of the bulk entity. The method described: αD solid, sulfur-containing material by contacting the solid, sulfur-containing material with gaseous oxygen in a combustion zone under combustion conditions to produce combustion products comprising at least one sulfur oxide. A method of burning a substance, comprising reducing the amount of sulfur oxides released from the combustion zone by carrying out the contacting in the presence of loose particles containing a major amount of metal-containing spinel, the method comprising: and the metal-containing spinel contains a first metal and a second metal having a valence higher than the valence of the second metal, and the metal-containing spinel contains a first metal and a second metal having a valence higher than that of the second metal, and The atomic ratio of is at least about 0
．． The improvement method is 17. QS Combustion of a solid, sulfur-containing material by contacting the solid, sulfur-containing material with gaseous oxygen in a burn zone under combustion conditions to produce combustion products containing at least one garlic of sulfur oxides. In a method, said contacting is carried out in the presence of loose particles containing a major amount of alkaline earth metal-containing spinel and a minor amount of at least one rare earth metal component, thereby reducing the amount of sulfur oxides released from said combustion zone. wherein the alkaline earth metal-containing spinel contains an alkaline earth metal and a second metal having a valence higher than that of the alkaline earth metal; An improved method wherein the atomic ratio of said alkaline earth metal to said second metal is at least 0.17. a major amount of solid particles capable of promoting the conversion of hydrocarbons under hydrocarbon conditions in an intimate mixture and a minor amount of at least one metal-containing carbonaceous material having a composition different from the solid particles; 1. A composition comprising discrete entities comprising spinel, wherein the spinel contains a first metal and a second metal having a valence higher than the valence of the second metal; The composition wherein the atomic ratio of the first metal and the second metal in the superinel is at least about 0.17. (2G) The composition of claim 01, wherein said discrete entity i comprises at least one alkaline earth metal spinel and at least one rare earth metal component. hydrocarbon cracking in the substantial absence of oxygen, wherein the predominant amount of solid particles by weight is from about 10 microns to about 25 microns.
Claim No. 01 having a circumferential diameter of 0 microns
Compositions as described in Section. (22) The hydrocarbon conversion comprises hydrocarbon cracking in the substantial absence of added molecular oxygen, wherein the predominant amount by weight of the solid particles has a diameter ranging from about 10 microns to about 250 microns. A composition according to claim 00. (2) the loose entities are at least about 70% by weight"
of the spinel, and the spinel is about 2.5 doors/V to about 60 Dw? A composition according to claims Hii;r having a surface area of /y. C'4) the loose entity contains at least about 70 ruq of the spinel, and the spinel has an amount of about 2
The composition of claim 22 having a surface area of from 5 m''/f to about 600 m'/f. The composition according to claim C1'l), comprising at least one additional metal component capable of promoting the conversion of sulfur dioxide to sulfur trioxide in an amount of CO of said solid particles and loose entities. Composition according to claim 22, comprising at least one additional metal component, at least one of which is capable of promoting the conversion of sulfur dioxide to sulfur trioxide in a small, catalytically effective amount. (28) The claimed composition, wherein the additional metal component is at least one platinum group metal component. 6) The composition described in item 6). The spinel is an alkaline earth metal-containing spine. The spinel contains magnesium and aluminum, and the atomic ratio of magnesium to aluminum in the spinel is The composition of claim 01, wherein the spinel contains magnesium and aluminum, and the valence of magnesium to aluminum in the spinel is in the range of about 0.35 to about 0.65. 0.45 to about 0.55, and the rare earth metal component is a cerium component, and is present in a range of about 1 to about 25 parts by weight of the total amount of discrete entities. A composition according to range C4l.