EP1334165A1 - Desulfuration et nouveaux sorbants permettant cette desulfuration - Google Patents

Desulfuration et nouveaux sorbants permettant cette desulfuration

Info

Publication number
EP1334165A1
EP1334165A1 EP01964246A EP01964246A EP1334165A1 EP 1334165 A1 EP1334165 A1 EP 1334165A1 EP 01964246 A EP01964246 A EP 01964246A EP 01964246 A EP01964246 A EP 01964246A EP 1334165 A1 EP1334165 A1 EP 1334165A1
Authority
EP
European Patent Office
Prior art keywords
sorbent composition
range
process according
component
oxides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01964246A
Other languages
German (de)
English (en)
Other versions
EP1334165A4 (fr
Inventor
Gyanesh P. Khare
Donald R. Engelbert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ConocoPhillips Co
Original Assignee
Conoco Inc
ConocoPhillips Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Conoco Inc, ConocoPhillips Co filed Critical Conoco Inc
Publication of EP1334165A1 publication Critical patent/EP1334165A1/fr
Publication of EP1334165A4 publication Critical patent/EP1334165A4/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/024—Compounds of Zn, Cd, Hg
    • B01J20/0244—Compounds of Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/14—Diatomaceous earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/3289—Coatings involving more than one layer of same or different nature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • This invention relates to a sorbent composition, a process of making a sorbent composition, and to a process of using a sorbent composition for the removal of sulfur from a hydrocarbon-containing fluid.
  • thermally processed gasolines such as, for example, thermally cracked gasoline, visbreaker gasoline, coker gasoline and catalytically cracked gasoline (hereinafter collectively referred to as "cracked-gasoline”) contains, in part, olefins, aromatics, sulfur, and sulfur-containing compounds.
  • Such adverse effect on olefin content is generally due to the severe condition normally employed, such as during hydrodesulfurization, to remove thiophenic compounds (such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkyl benzothiophenes, alkyl dibenzothiophenes and the like) which are some of the most difficult sulfur-containing compounds to be removed from cracked-gasoline, h
  • thiophenic compounds such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkyl benzothiophenes, alkyl dibenzothiophenes and the like
  • Fluidized bed reactors have advantages over fixed bed reactors such as better heat transfer and better pressure drop. Fluidized bed reactors generally use reactants that are particulates. The size of these particulates is generally in the range of about 1 micrometer to about 1000 micrometers. However, the reactants used generally do not have sufficient attrition resistance for all applications.
  • a sorbent composition comprising a promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof.
  • the present invention is based upon our discovery that through the utilization of an attrition-resistance-enhancing component present in an attrition-resistance-enhancing amount in a sorbent composition, there is achieved a novel sorbent composition which permits the ready removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel with a minimal effect on the octane rating of the treated hydrocarbon-containing fluid and where such sorbent composition has an enhanced attrition resistance compared to a sorbent composition that does not contain such attrition-resistance-enhancing component. h one aspect of the present invention there is provided a novel sorbent composition suitable for the desulfurization of a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel.
  • Such novel sorbent composition comprises a support component, a promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof wherein the valance of such promoter component is substantially reduced and such reduced-valence promoter component is present in an amount which is effective in the removal of sulfur from a hydrocarbon- containing fluid, and an attrition-resistance-enhancing component present in an amount which is effective in enhancing the attrition resistance of a sorbent composition of the present invention.
  • a process for the preparation of a novel sorbent composition which comprises: contacting a support component, preferably such support component comprises zinc oxide, silica, and alumina, and an attrition- resistance-enhancing component to form a mixture selected from the group consisting of a wet mix, a dough, a paste, a slurry, and the like; particulating such mixture so as to form a particulate selected from the group consisting of a granulate, an extrudate, a tablet, a sphere, a pellet, a microsphere, and the like; drying such particulate to form a dried particulate; calcining such dried particulate to form a calcined particulate; incorporating a promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof on, in, or with such dried and calcined particulate to form a promoted particulate; drying such promoted particulate to form a dried promoted promoted particulate to form a dried promoted
  • the attrition resistance of the sorbent composition is enhanced by providing an effective concentration of an attrition-resistance-enhancing component.
  • a process for the desulfurization of a hydrocarbon-containing fluid selected from the group consisting of cracked-gasoline, diesel fuel, and the like and combinations thereof which comprises desulfurizing in a desulfurization zone such hydrocarbon-containing fluid with a sorbent composition, separating the desulfurized hydrocarbon-containing fluid and the sulfurized sorbent composition, regenerating at least a portion of the sulfurized sorbent composition to produce a regenerated, desulfurized sorbent composition; activating at least a portion of the regenerated, desulfurized sorbent composition to produce an activated, regenerated, desulfurized sorbent composition; and thereafter returning at least a portion of the activated, regenerated, desulfurized sorbent composition to the desulfurization zone.
  • gasoline denotes a mixture of hydrocarbons boiling in the range of from about 100°F to about 400°F, or any fraction thereof.
  • suitable gasoline include, but are not limited to, hydrocarbon streams in refineries such as naphtha, straight- run naphtha, coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate, isomerate, reformate, and the like and combinations thereof.
  • cracked-gasoline denotes a mixture of hydrocarbons boiling in the range of from about 100°F to about 400°F, or any fraction thereof, that are products from either thermal or catalytic processes that crack larger hydrocarbon molecules into smaller molecules.
  • suitable thermal processes include, but are not limited to, coking, thermal cracking, visbreaking and the like and combinations thereof.
  • suitable catalytic cracking processes include, but are not limited to fluid catalytic cracking, heavy oil cracking, and the like and combinations thereof.
  • suitable cracked-gasoline include, but are not limited to, coker gasoline, thermally cracked gasoline, visbreaker gasoline, fluid catalytically cracked gasoline, heavy oil cracked gasoline, and the like and combinations thereof.
  • the cracked-gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in a process of the present invention.
  • diesel fuel denotes a mixture of hydrocarbons boiling in the range of from about 300°F to about 750°F, or any fraction thereof.
  • suitable diesel fuels include, but are not limited to, light cycle oil, kerosene, jet fuel, straight-run diesel, hydrotreated diesel, and the like and combinations thereof.
  • sulfur denotes sulfur in any form such as elemental sulfur or a sulfur compound normally present in a hydrocarbon-containing fluid such as cracked gasoline or diesel fuel.
  • sulfur which can be present during a process of the present invention, usually contained in a hydrocarbon-containing fluid, include, but are not limited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS 2 ), mercaptans (RSH), organic sulfides (R-S-R), organic disulfides (R-S-S-R), thiophene, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophene, alkyl thiophenes, alkyl benzothiophenes, alkyl dibenzothiophenes, and the like and combinations thereof as well as the heavier molecular weights of same which are normally present in a diesel fuel of the types contemplated for use in a process of the
  • fluid denotes gas, liquid, vapor, and combinations thereof.
  • gaseous denotes that state in which the hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel, is primarily in a gas or vapor phase.
  • Attrition resistance denotes the attrition resistance of a sorbent composition of the present invention measured as the Davison Index.
  • Davison Index refers to a measure of a sorbent's resistance to particle size reduction under controlled conditions of turbulent motion.
  • the Davison Index represents the weight percent of the over 20 micrometer particle size fraction which is reduced to particle sizes of less than 20 micrometers under test conditions.
  • the Davison Index is measured using a Jet cup attrition determination method.
  • the Jet cup attrition determination method involves screening a 5 gram sample of sorbent to remove particles in the 0 to 20 micrometer size range.
  • the particles above 20 micrometers are then subjected to a tangential jet of air at a rate of 21 liters per minute introduced through a 0.0625 inch orifice fixed at the bottom of a specially designed Jet cup (1" ID. X 2" height) for a period of 1 hour.
  • the Davison Index (DI) is calculated as follows: _ ⁇ Weight of 0 to 20 micrometer material formed during test - n . .. . .
  • DI ° _ x 100 x correction factor
  • Correction factor (presently 0.3) is determined by using a known calibration standard to adjust for differences in jet cup dimensions and wear.
  • a sorbent composition of the present invention having an attrition-resistance- enhancing amount of an attrition-resistance-enhancing component has a Davison Index value generally less than about 30.
  • the sorbent composition has a Davison Index value in the range of from about 1 to about 25. More preferably, the sorbent composition has a Davison Index value in the range of from 5 to 20.
  • a sorbent composition of the present invention comprising an attrition-resistance- enhancing component has an enhanced attrition resistance when compared to sorbent compositions which do not have such attrition-resistance-enhancing component.
  • support component denotes any component or combination of components which can be used as a support for a sorbent composition of the present invention to help promote a desulfurization process of the present invention. Examples of a suitable support component include, but are not limited to, zinc oxide and any suitable inorganic and organic carriers and the like and combinations thereof.
  • suitable inorganic carriers include, but are not limited to, silica, silica gel, alumina, diatomaceous earth, expanded perlite, kieselguhr, silica-alumina, titania, zirconia, zinc aluminate, zinc titanate, zinc silicate, magnesium aluminate, magnesium titanate, synthetic zeolites, natural zeolites, and the like and combinations thereof.
  • suitable orgamc carriers include, but are not limited to, activated carbon, coke, charcoal, carbon-containing molecular sieves, and the like and combinations thereof.
  • a preferred support component comprises zinc oxide, silica, and alumina.
  • promoter component denotes any component which can be added to a sorbent composition of the present invention to help promote a desulfurization process of the present invention.
  • suitable promoter components include, but are not limited to, metals, metal oxides, and the like and combinations thereof.
  • metal denotes metal in any form such as elemental metal or a metal- containing compound.
  • metal oxide denotes metal oxide in any form such as a metal oxide or a metal oxide precursor.
  • Attrition-resistance-enhancing component denotes any component which can be added to a sorbent composition of the present invention to enhance the attrition resistance of such sorbent composition compared to a sorbent composition which does not contain such attrition-resistance-enhancing component.
  • suitable attrition-resistance-enhancing component include, but are not limited to, clays, high alumina cements, natural cements, portland cement, calcium aluminate, calcium silicate, talc, and the like and combinations thereof.
  • clay denotes any clay which can be used as an attrition-resistance-enhancing component of a sorbent composition of the present invention.
  • a suitable clay examples include, but are not limited to, bentonite, sodium bentonite, acid-washed bentonite, atapulgite, china clay, kaolinite, montmorillonite, illite, halloysite, hectonite, sepiolite, and the like and combinations thereof.
  • attrition-resistance-enhancing component comprises a clay. More preferably, such attrition-resistance-enhancing component is selected from the group consisting of bentonite, sodium bentonite, acid-washed bentonite, and the like and combinations thereof. Most preferably, such attrition-resistance-enhancing component is bentonite.
  • the promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof may initially be in the form of a metal-containing compound(s) and/or a metal oxide precursor(s). It should be understood that when the promoter component is initially a metal-containing compound(s) and/or a metal oxide precursor(s), a portion of, or all of, such compound(s) and/or precursor(s) may be converted to the corresponding metal or metal oxide of such compound(s) and/or precursor(s) during the inventive process(es) disclosed herein.
  • reduced-valence promoter component denotes that a substantial portion of the valence of such promoter component is reduced, preferably to a value of zero.
  • a novel sorbent composition of the present invention which permits the removal of sulfur from a hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel, without having a significant adverse effect on the olefin content of such treated hydrocarbon-containing fluid, thus avoiding a significant reduction in octane values of such treated hydrocarbon-containing fluid.
  • a novel sorbent composition of the present invention results in a significant reduction of the sulfur content of the treated hydrocarbon-containing fluid.
  • a novel sorbent composition of the present invention has an enhanced attrition resistance when compared to a sorbent composition which does not have such attrition-resistance-enhancing component.
  • the zinc oxide used in the preparation of a sorbent composition of the present invention can be either in a form of zinc oxide such as powdered zinc oxide, or in the form of one or more zinc compounds that are convertible to zinc oxide under the conditions of preparation described herein.
  • suitable zinc compounds include, but are not limited to, zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate, and the like and combinations thereof.
  • the zinc oxide is in the form of powdered zinc oxide.
  • the silica used in the preparation of a sorbent composition of the present invention can be either in the form of silica or in the form of one or more silicon compounds. Any suitable type of silica may be employed in preparing a sorbent composition of the present invention.
  • silica examples include, but are not limited to, diatomite, expanded perlite, silicalite, silica colloid, flame-hydrolyzed silica, hydrolyzed silica, silica gel, precipitated silica and the like and combinations thereof, h addition, silicon compounds that are convertible to silica such as silicic acid, ammonium silicate and the like and combinations thereof can also be employed.
  • the silica is in the form of diatomite or expanded perlite.
  • the alumina used in preparing a sorbent composition of the present invention can be present in the source of silica, can be any suitable commercially available alumina material (including, but not limited to, colloidal alumina solutions, hydrated aluminas, and, generally, those alumina compounds produced by the dehydration of alumina hydrates), or both.
  • the preferred alumina is a hydrated alumina such as, but not limited to, boehmite or pseudoboehmite.
  • the promoter component used in preparing a sorbent composition of the present invention can be any metal, metal oxide, and the like and combinations thereof in any form which is effective in desulfurizing a hydrocarbon-containing fluid according to a process of the present invention.
  • Generally such promoter component is selected from the group consisting of metals, metal oxides, and the like and combinations thereof including compounds which contain such metals and metal oxides.
  • suitable metals include, but are not limited to, cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, vanadium, antimony, and the like and combinations thereof.
  • suitable metal oxides include, but are not limited to, cobalt oxides, nickel oxides, iron oxides, manganese oxides, copper oxides, zinc oxides, molybdenum oxides, tungsten oxides, silver oxides, tin oxides, vanadium oxides, antimony oxides, and the like and combinations thereof.
  • metal-containing compounds which can be used to incorporate the metal of such metal- containing compounds on, in, or with a dried and calcined particulate material to thereby form a dried and calcined promoted particulate material which can then be further dried and calcined, and preferably reduced, to thereby form a sorbent composition of the present invention.
  • the form which such metals can be in include, but are not limited to, metal acetates, metal carbonates, metal nitrates, metal sulfates, metal thiocyanates, and the like and combinations thereof.
  • the promoter component is selected from the group consisting of nickel, cobalt, and the like and combinations thereof. More preferably, the promoter component is nickel, h a preferred method of making process of the present invention, the sorbent composition is promoted with a precursor of a nickel oxide such as nickel nitrate, more preferably nickel nitrate hexahydrate.
  • the zinc oxide will generally be present in a sorbent composition of the present invention in an amount in the range of from about 10 to about 90 weight percent zinc oxide based on the total weight of the sorbent composition, preferably in an amount in the range of from about 15 to about 60 weight percent zinc oxide and, more preferably, in an amount in the range of from 20 to 55 weight percent zinc oxide.
  • the silica will generally be present in a sorbent composition of the present invention in an amount in the range of from about 5 to about 85 weight percent silica based on the total weight of the sorbent composition, preferably in an amount in the range of from about 10 to about 60 weight percent silica and, more preferably, in an amount in the range of from 15 to 55 weight percent silica.
  • the alumina will generally be present in a sorbent composition of the present invention in an amount in the range of from about 0.1 to about 30 weight percent alumina based on the total weight of the sorbent composition, preferably in an amount in the range of from about 1 to about 20 weight percent alumina and, more preferably, in an amount in the range of from 5 to 15 weight percent alumina.
  • the attrition-resistance-enhancing component will generally be present in an attrition-resistance-enhancing amount which is effective in providing a sorbent composition of the present invention having an enhanced attrition resistance compared to a sorbent composition which does not have such attrition-resistance-enhancing component.
  • the attrition-resistance-enhancing component will generally be present in a sorbent composition of the present invention in an amount in the range of from about 1 to about 30 weight percent attrition-resistance-enhancing component based on the total weight of the sorbent composition, preferably in an amount in the range of from about 5 to about 20 weight percent attrition-resistance-enhancing component and, more preferably, in an amount in the range of from 5 to 15 weight percent attrition-resistance- enhancing component.
  • the promoter component will generally be present in a sorbent composition of the present invention in an amount in the range of from about 5 to about 50 weight percent promoter component based on the total weight of the sorbent composition, preferably in an amount in the range of from about 8 to about 45 weight percent promoter component and, more preferably, in an amount in the range of from 10 to 40 weight percent promoter component.
  • the promoter component comprises a combination of metals, metal oxides, and the like, such as a preferred bimetallic promoter component
  • the bimetallic promoter component should comprise a weight ratio of the two metals forming such bimetallic promoter component in the range of from about 20: 1 to about 1 :20.
  • the promoter component is a bimetallic promoter component comprising nickel and cobalt in a weight ratio of about 1:1.
  • the support component is generally prepared by combining the support component, generally comprising zinc oxide and any inorganic or organic carrier, preferably comprising zinc oxide, silica and alumina, and the attrition-resistance-enhancing component together in appropriate proportions by any suitable method or manner which provides for the intimate mixing of such components to thereby provide a substantially homogeneous mixture comprising zinc oxide, any inorganic or organic carrier, and an attrition-resistance- enhancing component, preferably a substantially homogeneous mixture comprising zinc oxide, silica, alumina, and an attrition-resistance-enhancing component.
  • any suitable means for mixing the support component, preferably comprising zinc oxide, silica, and alumina, and the attrition-resistance-enhancing component can be used to achieve the desired dispersion of such components.
  • suitable means for mixing include, but are not limited to, mixing tumblers, stationary shells or troughs, Muller mixers, which are of the batch or continuous type, impact mixers, and the like. It is presently preferred to use a Muller mixer as the means for mixing the support component, preferably comprising zinc oxide, silica, alumina, and the attrition-resistance-enhancing component.
  • the support component generally comprising zinc oxide and any inorganic or organic carrier, preferably comprising zinc oxide, silica and alumina, and the attrition- resistance-enhancing component, preferably comprising a clay, are contacted together by any manner known in the art to provide a resulting mixture which can be in a form selected from the group consisting of a wet mix, a dough, a paste, a slurry and the like.
  • resulting mixture can then be shaped to form a particulate(s) selected from the group consisting of a granulate, an extrudate, a tablet, a sphere, a pellet, a micro-sphere, and the like.
  • the wet mix can be densified, dried under a drying condition as disclosed herein, calcined under a calcining condition as disclosed herein, and thereafter shaped, or particulated, through the granulation of the densified, dried, calcined mix to form granulates.
  • the resulting mixture of the support component generally comprising zinc oxide and any inorganic or organic carrier, preferably comprising zinc oxide, silica and alumina, and the attrition-resistance-enhancing component, preferably comprising a clay
  • the resulting mixture can then be shaped, preferably extruded, to fonn a particulate, preferably cylindrical extrudates having a diameter in the range of from about 1/32 inch to Vz inch and any suitable length, preferably a length in the range of from about 1/8 inch to about 1 inch.
  • the resulting particulates, preferably cylindrical extrudates are then dried under a drying condition as disclosed herein and then calcined under a calcining condition as disclosed herein.
  • the resulting mixture of the support component, preferably comprising zinc oxide, silica and alumina, and the attrition-resistance-enhancing component, preferably comprising a clay is in the form of a slurry and the particulation of such slurry is achieved by spray drying the slurry to form micro-spheres thereof having a size generally in the range of from about 1 micrometer to about 1000 micrometers, preferably in the range of from about 5 micrometers to about 500 micrometers.
  • Such micro-spheres are then subjected to drying under a drying condition as disclosed herein and calcining under a calcining condition as disclosed herein.
  • a dispersant component can be utilized and can be any suitable compound that helps to promote the spray drying ability of the resulting mixture which is preferably in the form of a slurry.
  • these dispersant components are useful in preventing deposition, precipitation, settling, agglomerating, adhering, and caking of solid particles in a fluid medium.
  • suitable dispersant components include, but are not limited to, condensed phosphates, sulfonated polymers, ammonium polyacrylate, sodium polyacrylate, ammonium polymethacrylate, sodium polymethacrylate, poly(methyl methacrylate), poly(acrylic acid, sodium salt), polyacrylamide, and the like and combinations thereof.
  • condensed phosphates refers to any dehydrated phosphate where the H 2 O:P 2 O 5 is less than about 3:1.
  • suitable dispersant components include, but are not limited to, sodium pyrophosphate, sodium metaphosphate, sulfonated styrene maleic anhydride polymer, and the like and combinations thereof.
  • the amount of a dispersant component used is generally in the range of from about 0.01 weight percent dispersant component based on the total weight of the components to about 10 weight percent dispersant component.
  • the amount of a dispersant component used is generally in the range of from about 0.1 weight percent to about 8 weight percent and, more preferably, the amount of a dispersant component used is in the range of from 1 weight percent to 5 weight percent.
  • an acid component can be used.
  • the acid component can be an organic acid or a mineral acid. If the acid component is an organic acid, it is preferred if it is a carboxylic acid. If the acid component is a mineral acid it is preferred if it is a mineral acid selected from the group consisting of nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid, and the like and combinations thereof.
  • the acid is used with water to form a dilute aqueous acid solution.
  • the amount of acid in the acid component is generally in the range of from about 0.01 volume percent based on the total volume of the acid component to about 20 volume percent.
  • the amount of acid is in the range of from about 0.1 volume percent to about 15 volume percent and, more preferably, the amount of acid is in the range of from 1 volume percent to 10 volume percent, h general, the amount of acid component to be used is based on the amount of the dry components. That is, the ratio of all the dry components (in grams) to the acid component (in milliliters) should be less than about 1.75:1. However, it is preferred if this ratio is less than about 1.25:1 and it is more preferred if it is less than about 1:1. These ratios will help to form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray.
  • a support component comprising zinc oxide, silica, and alumina, a dispersant component, and an attrition-resistance-enhancing component comprising a clay can be contacted together in any manner known in the art that will form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray.
  • a support component, a dispersant component, and an attrition-resistance-enhancing component are solids, then they should be contacted in a liquid medium to form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray.
  • Suitable means for contacting these components are known in the art such as, for example, tumblers, stationary shells, troughs, muller mixers, impact mixers, and the like.
  • these components after contacting to form a mixture, are contacted with an acid component as described herein.
  • the dry components and the acid component(s) can be contacted together simultaneously or separately.
  • sorbent material comprising particulates, preferably in the form of micro-spheres, that have a mean particle size in the ranges as disclosed herein.
  • Spray drying is known in the art and is discussed in Perry's Chemical Engineers' Handbook, Sixth Edition, published by McGraw-Hill, hie, at pages 20-54 through 20-58. Additional information can be obtained from the Handbook of Industrial Drying, published by Marcel Dekker. Inc., at pages 243 through 293.
  • the spray-dried sorbent material can then be dried under a drying condition as disclosed herein and then calcined, preferably in an oxidizing atmosphere such as in the presence of oxygen or air, under a calcining condition as disclosed herein to form a calcined, spray-dried sorbent material.
  • the calcination can be conducted under any suitable condition that removes residual water and oxidizes any combustibles.
  • the spray-dried sorbent material has a mean particle size in the range of from about 1 micrometer to about 1000 micrometers, preferably in the range of from about 5 micrometers to about 500 micrometers and, more preferably, in the range of from 10 micrometers to 200 micrometers.
  • mean particle size refers to the size of the particulate material as determined by using a RO-TAP Testing Sieve Shaker, manufactured by W.S. Tyler Inc., of Mentor, Ohio, or other comparable sieves.
  • the material to be measured is placed in the top of a nest of standard eight inch diameter stainless steel frame sieves with a pan on the bottom. The material undergoes sifting for a period of about 10 minutes; thereafter, the material retained on each sieve is weighed. The percent retained on each sieve is calculated by dividing the weight of the material retained on a particular sieve by the weight of the original sample. This information is used to compute the mean particle size.
  • the resulting particulated (preferably spray-dried), dried, and calcined material comprising a support component (generally comprising zinc oxide and any inorganic or organic carrier, preferably comprising zinc oxide, silica, and alumina) and an attrition- resistance-enhancing component (preferably comprising a clay) are then incorporated with a promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof including compounds containing such metals and metal oxides, preferably a nickel oxide compound or a nickel oxide precursor or a bimetallic promoter component comprising a nickel oxide compound, or a nickel oxide precursor, and a cobalt oxide compound or a cobalt oxide precursor.
  • a promoter component selected from the group consisting of metals, metal oxides, and the like and combinations thereof including compounds containing such metals and metal oxides, preferably a nickel oxide compound or a nickel oxide precursor or a bimetallic promoter component comprising a nickel oxide compound, or a nickel oxide precursor, and a cobal
  • the resulting promoted particulates are then subjected to drying under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein to thereby provide dried, calcined, promoted particulates prior to the subjecting of such dried, calcined, promoted particulates to reduction with a reducing agent, preferably hydrogen.
  • the promoter component(s) may be incorporated on, in, or with the particulated (preferably spray-dried), dried, and calcined material comprising a support component and an attrition-resistance-enhancing component by any suitable means or method for incorporating the promoter component(s) on, in, or with, a substrate material, such as the dried and calcined particulates, which results in the formation of a promoted sorbent composition which can then be dried under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein to thereby provide dried, calcined, promoted particulates.
  • the dried, calcined, promoted particulates can then be subjected to reduction with a reducing agent, preferably hydrogen, to thereby provide a sorbent composition of the present invention.
  • a reducing agent preferably hydrogen
  • examples of means or methods for incorporating a promoter component(s) include, but are not limited to, impregnating, soaking, spraying, and the like and combinations thereof.
  • a preferred method of incorporating is impregnating using any standard incipient wetness impregnation technique (i.e., essentially completely filling the pores of a substrate material with a solution of the incorporating elements) for impregnating a substrate, such as the preferred particulated, dried, and calcined material (i.e., particulates) comprising a support component (preferably comprising zinc oxide, silica and alumina) and an attrition-resistance-enhancing component (preferably comprising a clay) prepared according to a process of the present invention, with a promoter component(s).
  • any standard incipient wetness impregnation technique i.e., essentially completely filling the pores of a substrate material with a solution of the incorporating elements
  • a substrate such as the preferred particulated, dried, and calcined material (i.e., particulates) comprising a support component (preferably comprising zinc oxide, silica and alumina) and an attrition-res
  • a preferred method uses an impregnating solution comprising the desirable concentration of a promoter component(s) so as to ultimately provide a promoted particulate(s) which can then be subjected to drying under a drying condition as disclosed herein and calcining under a calcining condition as disclosed herein followed by reduction with a reducing agent such as hydrogen to provide a sorbent composition of the present invention.
  • the impregnating solution can be any aqueous solution and amounts of such solution which suitably provides for the impregnation of the particulates comprising a support component (preferably comprising zinc oxide, silica and alumina) and an attrition-resistance-enhancing component (preferably comprising a clay) prepared according to a process of the present invention to give an amount of promoter component that provides, after reduction with a reducing agent, a reduced promoter component content sufficient to permit the removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel when such fluid is treated in accordance with a process of the present invention.
  • a support component preferably comprising zinc oxide, silica and alumina
  • an attrition-resistance-enhancing component preferably comprising a clay
  • a preferred impregnating solution comprises an aqueous solution formed by dissolving a metal-containing compound, preferably such metal-containing compound is in the form of a metal salt, such as, but not limited to, a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof, in an aqueous solvent comprising water.
  • a metal salt such as, but not limited to, a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof
  • suitable aqueous and nonaqueous solvents include, but are not limited to, water, alcohols, esters, ethers, ketones, and the like and combinations thereof.
  • the weight ratio of promoter component to the aqueous or nonaqueous solvent of such impregnating solution can be in the range of from about 1 : 1 to about 4: 1, preferably, in the range of from 1.5 : 1 to 3 : 1.
  • a promoter component(s) can be added to the spray-dried sorbent material as a component(s) of the original mixture, or can be added after the original mixture has been spray dried, dried, and calcined.
  • the spray-dried sorbent material should be dried again under a drying condition as disclosed herein and then calcined again under a calcining condition as disclosed herein.
  • a prefened impregnating solution is formed by dissolving a metal-containing compound (such as nickel nitrate hexahydrate) in water. It is acceptable to use somewhat of an acidic solution to aid in the dissolution of the metal-containing compound. It is more preferred for the particulates to be impregnated with a nickel component by use of a solution containing nickel nitrate hexahydrate dissolved in water.
  • a metal-containing compound such as nickel nitrate hexahydrate
  • An example method of incorporating a promoter component on, in, or with a material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention, is to impregnate such particulates with a promoter component, initially in the form of a metal-containing compound, which has been melted under a melting condition as described herein.
  • such promoter component is initially in the form of a metal-containing compound such as a metal salt, such as, but not limited to, a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof (such as, but not limited to, nickel nitrate hexahydrate).
  • a metal salt such as, but not limited to, a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof (such as, but not limited to, nickel nitrate hexahydrate).
  • an aqueous or nonaqueous solvent such as water
  • Such melting condition includes a temperature in a range of from the melting point of the promoter component to below the decomposition temperature of the promoter component for a time period and at a pressure that provides for a melted promoter component.
  • decomposition temperature refers to the temperature at which the promoter component is no longer soluble and is no longer suitable for incorporating, preferably impregnating, the promoter component onto the material comprising a support component and an attrition-resistance-enhancing component according to a process of the present invention.
  • the temperature of such melting condition varies depending on the promoter component but such temperature should be such as to provide a melted promoter component.
  • Such temperature is generally in the range of from about 75°F to about 700°F, preferably in the range of from about 85°F to about 300°F, more preferably in the range of from about 95°F to about 280°F and, most preferably, in the range of from 95°F to 250°F.
  • Such melting condition can include a time period generally in the range of from about 1 minute to about 2 hours, preferably in the range of from about 5 minutes to about 1.5 hours and, most preferably, in the range of from 5 minutes to 1 hour.
  • Such melting condition can include a pressure generally in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 150 pounds per square inch absolute (psia), preferably in the range of from about atmospheric to about 100 psia, most preferably about atmospheric, so long as the desired temperature can be maintained.
  • the thus-melted promoter component is then used to incorporate, preferably impregnate, such promoter component onto a material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention.
  • a material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention.
  • the melted promoter component is incorporated, preferably impregnated, onto the material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention, by any manner or method which results in substantially all the surface area of the particulates being contacted with the melted promoter component resulting in distribution of the promoter component.
  • substantially all the surface area of the particulates being contacted with the melted promoter component generally refers to greater than twenty-five percent of the surface area of the particulates, preferably greater than forty percent of the surface area of the particulates, more preferably greater than sixty percent of the surface area of the particulates, and most preferably greater than ninety-five percent of the surface area of the particulates being contacted with the melted promoter component.
  • Another example method of incorporating, preferably impregnating, a melted promoter component onto the material comprising a support component and an attrition- resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention is by mixing a solid promoter component (i.e., an unmelted promoter component) with the particulates by any manner or method which results in a mixture of particulates and solid promoter component.
  • a solid promoter component i.e., an unmelted promoter component
  • the mixture of particulates and solid promoter component is then subjected to a melting condition as described herein, preferably while such mixture is subjected to constant stirring or tumbling, which results in substantially all the surface area of the particulates being contacted with a melted promoter component resulting in distribution of the promoter component.
  • Another example method of incorporating, preferably impregnating, a melted promoter component onto the material comprising a support component and an attrition- resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention is by preheating the particulates under a heating condition as described herein to thereby provide a pre-heated support component (i.e., pre-heated particulates) followed by contact with a solid promoter component (i.e., an unmelted promoter component) which results in a melting of the solid promoter component upon contact with the pre-heated particulates which further results in substantially all the surface area of the particulates being contacted with the melted promoter component.
  • a pre-heated support component i.e., pre-heated particulates
  • a solid promoter component i.e., an unmelted promoter component
  • such pre-heated particulates are under constant stirring or tumbling during contact with the promoter component.
  • Such mixture of particulates and melted promoter component can be further heated near the melting point of the promoter component for a time period in the range of from about 0.5 hour to about 15 hours, preferably in the range of from about 1 hour to about 8 hours and, most preferably, in the range of from 1 hour to 5 hours to further aid in the melting of the promoter component.
  • Such heating condition suitable for pre-heating the material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention, can include a temperature generally in the range of from about 175°F to about 300°F, preferably in the range of from about 185°F to about 280°F and, more preferably, in the range of from 190°F to 260°F.
  • Such heating condition can include a time period generally in the range of from about 1 minute to about 2 hours, preferably in the range of from about 5 minutes to about 1.5 hours and, more preferably, in the range of from 5 minutes to 1 hour.
  • Such heating condition can include a pressure generally in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 150 pounds per square inch absolute (psia), preferably in the range of from about atmospheric to about 100 psia, more preferably about atmospheric, so long as the desired temperature can be maintained.
  • a pressure generally in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 150 pounds per square inch absolute (psia), preferably in the range of from about atmospheric to about 100 psia, more preferably about atmospheric, so long as the desired temperature can be maintained.
  • Another example method of incorporating, preferably impregnating, a melted promoter component onto the material comprising a support component and an attrition- resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention is by subjecting a solid promoter component to a melting condition as described herein to thereby provide a melted promoter component which has become viscous enough to pour.
  • the particulates are then contacted with such melted promoter component by pouring such melted promoter component onto the surface of the particulates by any manner or method(s) which results in substantially all the surface area of the particulates being contacted with the melted promoter component resulting in distribution of the promoter component.
  • such melted promoter component is poured onto the surface of the particulates while such particulates are under constant stirring or tumbling. It can be desirable to pre-heat the material comprising a support component and an attrition- resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention, under a heating condition as described herein before contact with the melted promoter component.
  • solid nickel nitrate hexahydrate is used to incorporate, preferably impregnate, the nickel of such solid nickel nitrate hexahydrate onto the material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention.
  • the nickel of such solid nickel nitrate hexahydrate is incorporated, preferably impregnated, onto the particulates by mixing such solid nickel nitrate hexahydrate with the particulates by any manner or method which results in a mixture of solid nickel nitrate hexahydrate and particulates and then subjecting such mixture, while under constant stirring or tumbling, to a melting condition as described herein with results in substantially all the surface area of the particulates being contacted with melted nickel nitrate hexahydrate resulting in distribution of the nickel nitrate hexahydrate.
  • cobalt nitrate hexahydrate or iron nitrate nonahydrate or manganese nitrate hexahydrate or copper nitrate or zinc nitrate hexahydrate or silver nitrate or the like and combinations thereof can be used in place of nickel nitrate hexahydrate to incorporate, preferably impregnate, the metal of such metal- containing compound(s) onto the particulates in the same above-described manner as for incorporating, preferably impregnating, the nickel of such nickel nitrate hexahydrate.
  • solid nickel nitrate hexahydrate and solid cobalt nitrate hexahydrate are mixed with the particulates and then the resulting mixture, while under constant stirring or tumbling, is subjected to a melting condition as described herein to incorporate, preferably impregnate, the nickel and cobalt onto the particulates.
  • a sorbent composition comprising a bimetallic promoter component comprising nickel and cobalt is formed.
  • the nickel of such solid nickel nitrate hexahydrate is incorporated, preferably impregnated, onto the material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention, by contacting such particulates, which have been pre-heated under a heating condition as described herein, with the solid nickel nitrate hexahydrate while under constant stirring or tumbling.
  • an attrition-resistance-enhancing component preferably particulates comprising zinc oxide, silica, alumina, and a clay
  • Such contacting results in a melting of the solid nickel nitrate hexahydrate upon contact with the pre-heated particulates which results in substantially all the surface area of the pre-heated particulates being contacted with melted nickel nitrate hexahydrate resulting in distribution of the nickel nitrate hexahydrate.
  • cobalt nitrate hexahydrate or iron nitrate nonahydrate or manganese nitrate hexahydrate or copper nitrate or zinc nitrate hexahydrate or silver nitrate or the like and combinations thereof can be used in place of nickel nitrate hexahydrate to incorporate, preferably impregnate, the metal of such metal-containing compound(s) onto the pre-heated particulates in the same above-described manner as for incorporating, preferably impregnating, the nickel of such nickel nitrate hexahydrate.
  • solid nickel nitrate hexahydrate and solid cobalt nitrate hexahydrate can be contacted with the pre-heated particulates while under constant stirring or tumbling to incorporate, preferably impregnate, the nickel and cobalt onto the particulates.
  • a sorbent composition comprising a bimetallic promoter component comprising nickel and cobalt is formed.
  • solid nickel nitrate hexahydrate is subjected to a melting condition to thereby provide a melted nickel nitrate hexahydrate which is viscous enough to pour.
  • the resulting melted nickel nitrate hexahydrate is then used to incorporate, preferably impregnate, the nickel of such melted nickel nitrate hexahydrate onto the material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina, and a clay, prepared according to a process of the present invention, which have been pre-heated under a heating condition as described herein.
  • the nickel of such melted nickel nitrate hexahydrate is incorporated, preferably impregnated, onto the pre-heated particulates by adding such melted nickel nitrate hexahydrate to the pre-heated particulates by pouring such melted nickel nitrate hexahydrate onto the surface of the pre-heated particulates by any manner or method which results in substantially all the surface area of the particulates being contacted with the melted nickel nitrate hexahydrate resulting in distribution of the nickel nitrate hexahydrate.
  • such melted nickel nitrate hexahydrate is poured onto the surface of the pre-heated particulates while such particulates are under constant stirring or tumbling.
  • cobalt nitrate hexahydrate or iron nitrate nonahydrate or manganese nitrate hexahydrate or copper nitrate or zinc nitrate hexahydrate or silver nitrate or the like and combinations thereof can be used in place of nickel nitrate hexahydrate to incorporate, preferably impregnate, the metal of such metal-containing compound(s) onto the pre-heated particulates in the same above-described manner as for incorporating, preferably impregnating, the nickel of such nickel nitrate hexahydrate.
  • melted nickel nitrate hexahydrate and melted cobalt nitrate hexahydrate can be poured onto the surface of the pre-heated particulates while such particulates are under constant stirring or tumbling. After drying and calcining, a sorbent composition comprising a bimetallic promoter component comprising nickel and cobalt is formed.
  • the amount of a promoter component(s) incorporated, preferably impregnated, onto, into, or with the material comprising a support component and an attrition-resistance-enhancing component, preferably particulates comprising zinc oxide, silica, alumina and a clay, prepared according to a process of the present invention is an amount which provides, after the promoted particulate material has been dried under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein, a sorbent composition having an amount of promoter component as disclosed herein.
  • a drying condition can include a temperature in the range of from about 180°F to about 290°F, preferably in the range of from about 190°F to about 280°F and, more preferably, in the range of from 200°F to 270°F.
  • Such drying condition can also include a time period generally in the range of from about 0.5 hour to about 60 hours, preferably in the range of from about 1 hour to about 40 hours and, more preferably, in the range of from 1.5 hours to 20 hours.
  • Such drying condition can also include a pressure generally in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 150 pounds per square inch absolute (psia), preferably in the range of from about atmospheric to about 100 psia, more preferably about atmospheric, so long as the desired temperature can be maintained.
  • a pressure generally in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 150 pounds per square inch absolute (psia), preferably in the range of from about atmospheric to about 100 psia, more preferably about atmospheric, so long as the desired temperature can be maintained.
  • Any drying method(s) known to one skilled in the art such as, for example, air drying, heat drying, vacuum drying, and the like and combinations thereof can be used.
  • a calcining condition as referred to herein, can include a temperature in the range of from about 400°F to about 1800°F, preferably in the range of from about 600°F to about 1600°F and, more preferably,
  • Such calcining condition can also include a time period generally in the range of from about 1 hour to about 60 hours, preferably in the range of from about 2 hours to about 20 hours and, more preferably, in the range of from 3 hours to 15 hours.
  • Such calcining condition can also include a pressure, generally in the range of from about 7 pounds per square inch absolute (psia) to about 750 psia, preferably in the range of from about 7 psia to about 450 psia and, more preferably, in the range of from 7 psia to 150 psia.
  • psia pounds per square inch absolute
  • the desired reduced-valence promoter component sorbent preferably reduced- valence nickel sorbent, is prepared by drying the resulting composition under a drying condition as disclosed herein followed by calcining under a calcining condition as disclosed herein to thereby provide a dried, calcined, promoted particulate(s).
  • the dried, calcined, promoted particulates are thereafter subjected to reduction with a suitable reducing agent, preferably hydrogen, to thereby provide a composition comprising a reduced- valence promoter component, preferably a zero-valence promoter component, with such zero-valence promoter component, preferably zero-valence nickel, being present in an amount sufficient to permit the removal of sulfur from a hydrocarbon- containing fluid such as cracked-gasoline or diesel fuel, according to a process of the present invention.
  • a suitable reducing agent preferably hydrogen
  • a sorbent composition of the present invention comprising a reduced- valence promoter component is a composition that has the ability to react chemically and/or physically with sulfur. It is also preferable that the sorbent composition removes diolefins and other gum-forming compounds from cracked-gasoline.
  • a sorbent composition of the present invention comprising a reduced- valence promoter component comprises a promoter component, preferably comprising nickel, that is in a substantially reduced valence state, preferably a zero valence state.
  • the reduced- valence promoter component is reduced nickel.
  • the amount of reduced- valence promoter component, preferably reduced nickel, in a sorbent composition of the present invention is an amount which will permit the removal of sulfur from a hydrocarbon- containing fluid such as cracked-gasoline or diesel fuel.
  • Such amount of reduced- valence promoter component, preferably reduced nickel, in a sorbent composition of the present invention is generally in the range of from about 5 to about 50 weight percent of the total weight of the sorbent composition.
  • the reduced- valence promoter component, preferably reduced nickel is present in an amount in the range of from about 8 to about 45 weight percent of the total weight of the sorbent composition and, more preferably, in an amount in the range of from 10 to 40 weight percent of the total weight of the sorbent composition.
  • the reduced nickel is present in an amount in the range of from 10 to 40 weight percent reduced nickel based on the total weight of the sorbent composition and the reduced nickel has been substantially reduced to zero valence.
  • zinc oxide is present in an amount in the range of from about 35 to about 50 weight percent zinc oxide based on the total weight of the sorbent composition
  • silica is present in an amount in the range of from about 30 to about 40 weight percent silica based on the total weight of the sorbent composition
  • alumina is present in an amount in the range of from about 6 to about 12 weight percent alumina based on the total weight of the sorbent composition
  • bentonite is present in an amount in the range of from about 2 to about 12 weight percent bentonite based on the total weight of the sorbent composition
  • nickel is present, prior to reduction to zero valence, in an amount in the range of from about 14 to about 30 weight percent nickel based on the total weight of the sorbent composition.
  • a sorbent composition of the present invention which is useful in a process of the present invention can be prepared by a process comprising: (a) contacting a support component, preferably comprising zinc oxide, silica, and alumina, and an attrition-resistance-enhancing component, preferably comprising a clay, so as to form a mixture selected from the group consisting of a wet mix, a dough, a paste, a slurry and the like and combinations thereof; (b) particulating, preferably spray-drying, the mixture to form particulates selected from the group consisting of granulates, extrudates, tablets, pellets, spheres, micro- spheres, and the like and combinations thereof, preferably micro-spheres, where such particulates comprise such support component and such attrition-resistance-enhancing component; (c) drying the particulate under a drying condition as disclosed herein to form a dried particulate;
  • a process of using a novel sorbent composition(s) of the present invention to desulfurize a hydrocarbon-containing fluid comprising cracked-gasoline or diesel fuel to provide a desulfurized hydrocarbon-containing fluid comprising desulfurized cracked-gasoline or desulfurized diesel fuel comprising: (a) desulfurizing, in a desulfurization zone, a hydrocarbon-containing fluid with a sorbent composition of the present invention to thereby provide a desulfurized hydrocarbon-containing fluid and a resulting sulfurized sorbent composition;
  • the desulfurizing of a hydrocarbon-containing fluid is carried out under a set of conditions that includes total pressure, temperature, weight hourly space velocity, and hydrogen flow. These conditions are such that the sorbent composition can desulfurize the hydrocarbon-containing fluid to produce a desulfurized hydrocarbon-containing fluid and a sulfurized sorbent composition.
  • the hydrocarbon-containing fluid preferably cracked-gasoline or diesel fuel
  • the hydrocarbon-containing fluid be in a gas or vapor phase.
  • the total pressure can be in the range of from about 15 pounds per square inch absolute (psia) to about 1500 psia.
  • psia pounds per square inch absolute
  • the total pressure be in a range of from about 50 psia to about 500 psia.
  • the temperature should be sufficient to keep the hydrocarbon-containing fluid in essentially a vapor or gas phase.
  • temperatures can be in the range of from about 100°F to about 1000°F, it is presently preferred that the temperature be in the range of from about 400°F to about 800°F when treating a cracked-gasoline and in the range of from about 500°F to about 900°F when treating a diesel fuel.
  • Weight hourly space velocity is defined as the numerical ratio of the rate at which a hydrocarbon-containing fluid is charged to the desulfurization zone in pounds per hour at standard condition of temperature and pressure (STP) divided by the pounds of sorbent composition contained in the desulfurization zone to which the hydrocarbon- containing fluid is charged, hi the practice of the present invention, such WHSV should be in the range of from about 0.5 hr "1 to about 50 hr "1 , preferably in the range of from about 1 hr "1 to about 20 hr "1 .
  • the desulfurizing (i.e., desulfurization) of a hydrocarbon- containing fluid should be conducted for a time sufficient to effect the removal of sulfur from such hydrocarbon-containing fluid.
  • an agent be employed which interferes with any possible chemical or physical reacting of the olefinic and aromatic compounds in the hydrocarbon-containing fluid which is being treated with a sorbent composition of the present invention.
  • agent is hydrogen.
  • Hydrogen flow in the desulfurization zone is generally such that the mole ratio of hydrogen to hydrocarbon-containing fluid is the range of from about 0.1 to about 10, preferably in the range of from about 0.2 to about 3.
  • the desulfurization zone can be any zone wherein desulfurizing a hydrocarbon- containing fluid such as cracked-gasoline, diesel fuel or the like can take place.
  • the regeneration zone can be any zone wherein regenerating or desulfurizing a sulfurized sorbent composition can take place.
  • the activation zone can be any zone wherein activating, i.e., reducing, a regenerated, desulfurized sorbent composition can take place. Examples of suitable zones are fixed bed reactors, moving bed reactors, fluidized bed reactors, transport reactors, reactor vessels and the like.
  • a diluent such as methane, carbon dioxide, flue gas, nitrogen and the like and combinations thereof can be used.
  • a high purity hydrogen be employed in achieving the desired desulfurization of a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel.
  • a sorbent composition be used having a mean particle size, as described herein, in the range of from about 1 micrometer to about 1000 micrometers.
  • a sorbent composition has a mean particle size in the range of from about 5 micrometers to about 500 micrometers and, more preferably, in the range of from 10 micrometers to 200 micrometers.
  • the sorbent composition should generally have a particulate size in the range of from about 1/32 inch to about l A inch diameter, preferably in the range of from about 1/32 inch to about 1/4 inch diameter.
  • a sorbent composition having a surface area in the range of from about 1 square meter per gram to about 1000 square meters per gram (m /g), preferably in the range of from about 1 m 2 /g to about 800 m 2 /g.
  • the separating of the desulfurized hydrocarbon-containing fluid, preferably gaseous or vaporized desulfurized hydrocarbon-containing fluid, and sulfurized sorbent composition can be accomplished by any manner or method known in the art that can separate a solid from a gas.
  • suitable separating means for separating solids and gases include, but are not limited to, cyclonic devices, settling chambers, impingement devices, filters, and the like and combinations thereof.
  • the desulfurized hydrocarbon-containing fluid preferably desulfurized gaseous cracked-gasoline or desulfurized gaseous diesel fuel, can then be recovered and preferably liquefied. Liquification of such desulfurized hydrocarbon-containing fluid can be accomplished by any manner or method known in the art.
  • the hydrocarbon-containing fluid as described herein preferably gaseous cracked-gasoline or gaseous diesel fuel, suitable as a feed in a process of the present invention is a composition that comprises olefins, aromatics, sulfur, as well as paraffins and naphthenes.
  • the amount of olefins in gaseous cracked-gasoline is generally in the range of from about 10 to about 35 weight percent olefins based on the total weight of the gaseous cracked-gasoline. For diesel fuel there is essentially no olefin content.
  • the amount of aromatics in gaseous cracked-gasoline is generally in the range of from about 20 to about 40 weight percent aromatics based on the total weight of the gaseous cracked-gasoline.
  • the amount of aromatics in gaseous diesel fuel is generally in the range of from about 10 to about 90 weight percent aromatics based on the total weight of the gaseous diesel fuel.
  • the amount of sulfur in the hydrocarbon-containing fluid, preferably cracked-gasoline or diesel fuel, suitable for use in a process of the present invention can be in the range of from about 100 parts per million sulfur by weight of the cracked-gasoline to about 10,000 parts per million sulfur by weight of the cracked-gasoline and from about 100 parts per million sulfur by weight of the diesel fuel to about 50,000 parts per million sulfur by weight of the diesel fuel prior to the treatment of such hydrocarbon-containing fluid with a process of the present invention.
  • the amount of sulfur in the desulfurized hydrocarbon-containing fluid, such as desulfurized cracked-gasoline or desulfurized diesel fuel, following treatment in accordance with a process of the present invention is less than about 100 parts per million (ppm) sulfur by weight of hydrocarbon-containing fluid, preferably less than about 90 ppm sulfur by weight of hydrocarbon-containing fluid, and more preferably less than about 80 ppm sulfur by weight of hydrocarbon-containing fluid.
  • a stripper zone can be inserted before and/or after the regenerating of the sulfurized sorbent composition.
  • Such stripper zone preferably utilizing a stripping agent, will serve to remove a portion, preferably all, of any hydrocarbon(s) from the sulfurized sorbent composition.
  • Such stripper zone can also serve to remove oxygen and sulfur dioxide from the system prior to introduction of the regenerated sorbent composition into the activation zone.
  • Such stripping employs a set of conditions that includes total pressure, temperature, and stripping agent partial pressure.
  • the stripping when employed, is carried out at a total pressure in the range of from about 25 pounds per square inch absolute (psia) to about 500 psia.
  • the temperature for such stripping can be in the range of from about 100°F to about 1000°F.
  • Such stripping is carried out for a time sufficient to achieve the desired level of stripping.
  • Such stripping can generally be achieved in a time period in the range of from about 0.1 hour to about 4 hours, preferably in the range of from about 0.3 hour to about 1 hour.
  • the stripping agent is a composition(s) that helps to remove a hydrocarbon(s) from the sulfurized sorbent composition.
  • the stripping agent is nitrogen.
  • the regenerating is carried out under a set of conditions that includes total pressure and sulfur removing agent partial pressure. Total pressure is generally in the range of from about 25 pounds per square inch absolute (psia) to about 500 psia.
  • the sulfur removing agent partial pressure is generally in the range of from about 1 percent to about 100 percent of the total pressure.
  • the sulfur removing agent i.e., regenerating agent
  • the sulfur removing agent is a composition(s) that helps to generate gaseous sulfur-containing compounds and oxygen-containing compounds such as sulfur dioxide, as well as to burn off any remaining hydrocarbon deposits that might be present.
  • the preferred sulfur removing agent, i.e., regenerating agent, suitable for use in the regeneration zone is oxygen or an oxygen-containing gas(es) such as air.
  • Such regeneration is carried out for a time sufficient to achieve the desired level of regeneration. Such regeneration can generally be achieved in a time period in the range of from about 0.1 hour to about 24 hours, preferably in the range of from about 0.5 hour to about 3 hours.
  • the regenerating is carried out at a temperature generally in the range of from about 100°F to about 1500°F, preferably in the range of from about 800°F to about 1200°F.
  • the desulfurized sorbent composition is then subjected to activating, i.e., reducing, in an activation zone with a reducing agent, preferably hydrogen, so that at least a portion of the promoter component, preferably comprising nickel, incorporated on, in, or with the sorbent composition is reduced to thereby provide a sorbent composition comprising a reduced-valence promoter component, preferably reduced nickel.
  • a reducing agent preferably hydrogen
  • Such sorbent composition comprises a reduced- valence promoter component, preferably reduced nickel, incorporated on, in, or with such sorbent composition in an amount that provides for the removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel according to a process of the present invention.
  • the activating, i.e., reducing, of the regenerated, desulfurized sorbent composition is carried out at a temperature in the range of from about 100°F to about 1500°F and at a pressure in the range of from about 15 pounds per square inch absolute (psia) to about 1500 psia.
  • psia pounds per square inch absolute
  • Such reduction is carried out for a time sufficient to achieve the desired level of promoter component reduction.
  • Such reduction can generally be achieved in a time period in the range of from about 0.01 hour to about 20 hours.
  • At least a portion of the resulting activated (i.e., reduced) sorbent composition can be returned to the desulfurization zone.
  • the steps of desulfurizing, regenerating, activating (i.e., reducing), and optionally stripping before and/or after such regenerating can be accomplished in a single zone or vessel or in multiple zones or vessels.
  • the steps of desulfurizing, regenerating, activating, and optionally stripping before and/or after such regenerating are accomplished in a single zone or vessel.
  • the steps of desulfurizing, regenerating, activating, and optionally stripping before and/or after such regenerating are accomplished in multiple zones or vessels.
  • a desulfurized hydrocarbon-containing fluid resulting from the practice of a process of the present invention is a desulfurized cracked-gasoline
  • desulfurized cracked-gasoline can be used in the formulation of gasoline blends to provide gasoline products suitable for commercial consumption and can also be used where a cracked- gasoline containing low levels of sulfur is desired.
  • a desulfurized hydrocarbon-containing fluid resulting from the practice of a process of the present invention is a desulfurized diesel fuel
  • such desulfurized diesel fuel can be used in the formulation of diesel fuel blends to provide diesel fuel products suitable for commercial consumption and can also be used where a diesel fuel containing low levels of sulfur is desired.
  • Sorbent A (Control) was a spray-dried sorbent material prepared in the following manner. A 20 gram quantity of sodium pyrophosphate was dissolved in 2224 grams of distilled water to provide a solution. To the solution was added 200 grams of Vista DISPAL 180 alumina with vigorous stirring. While the alumina slurry was being mixed with a high shear mixer, a 628 gram quantity of Celite Filter Cel (Celite Corporation, Lo poc, California) and a 788 gram quantity of zinc oxide were added to the slurry and further mixed for about 15 minutes. The resulting mixed slurry was sieved through, a 25 mesh screen.
  • the resulting sieved slurry was then spray-dried using a Niro Mobile Minor spray dryer equipped with a fountain head (Niro, Inc., Columbia, Maryland).
  • the operating conditions of the spray dryer included an inlet temperature of 320°C and an outlet temperature of about 100°C to about 120°C.
  • the spray-dried material was then dried in an oven at 150°C for three hours and then calcined at 635°C for one hour to thereby obtain a dried and calcined spray-dried sorbent material.
  • a 100 gram quantity of the thus dried and calcined spray-dried sorbent material (149 micron to 74 micron fraction) was then spray impregnated with a solution of 59.4 grams of nickel nitrate hexahydrate (Ni(NO 3 ) 2 »6H 2 O) in 62.9 grams of distilled water.
  • the thus-impregnated material was then dried in an oven which was increased from an ambient temperature at 3°C per minute to 150°C and maintained at 150°C for three hours and then increased at a rate of 3°C per minute to 635°C and maintained at 635°C for one hour to thereby obtain a nickel-impregnated spray-dried sorbent material.
  • a 50 gram quantity of the thus dried and calcined nickel-impregnated spray-dried sorbent material was then spray impregnated with a solution of 37.1 grams of nickel nitrate hexahydrate (Ni(NO 3 ) 2 »6H 2 O) in 7.5 grams of distilled water.
  • the thus-impregnated material was then dried in an oven which was increased from an ambient temperature at 3°C per minute to 150°C and maintained at 150°C for three hours and then increased at a rate of 3°C per minute to 635°C and maintained at 635°C for one hour to thereby obtain a twice-nickel-impregnated spray-dried sorbent material (Control Sorbent A).
  • Control Sorbent A contained a final total of about 21 weight percent nickel based on the total weight of the material.
  • the physical and chemical characteristics of Control Sorbent A are included in Table I.
  • the Davison Index, as described herein, was determined using a 5 gram quantity of -100 to +200 mesh fraction of Control Sorbent A.
  • Sorbent B (Invention) was a spray-dried sorbent material prepared in the following manner. A 20 gram quantity of sodium pyrophosphate was dissolved in 3000 grams of distilled water to provide a solution. To the solution was added 200 grams of Vista DISPAL 180 alumina with vigorous stirring.
  • alumina slurry was being mixed using a high shear mixer, a 314 gram quantity of Celite Filter Cel (Celite Corporation, Lompoc, California) and a 788 gram quantity of zinc oxide were added to the slurry and further mixed for about 20 minutes. A 187.2 gram quantity of bentonite 325 and an additional 1000 gram quantity of distilled water were then added to the slurry. The resulting mixed slurry was sieved through a 25 mesh screen. The resulting sieved material was then spray-dried using a Niro Mobile Minor spray dryer equipped with a fountain head (Niro, Inc., Columbia, Maryland).
  • the operating conditions of the spray dryer included an inlet temperature of 320°C and an outlet temperature of about 100°C to about 120°C.
  • the spray-dried material was then dried in an oven at 150°C and then calcined at 635°C for one hour to thereby obtain a dried and calcined spray-dried sorbent material.
  • a 100 gram quantity of the thus dried and calcined spray-dried sorbent material (149 micron to 74 micron fraction) was then spray impregnated with a solution of 59.4 grams of nickel nitrate hexahydrate (Ni(NO 3 ) 2 »6H 2 O) in 20.4 grams of distilled water.
  • the thus-impregnated material was then dried in an oven which was increased from an ambient temperature at 3°C per minute to 150°C and maintained at 150°C for one hour and then increased at a rate of 3°C per minute to 635°C and maintained at 635°C for one hour to thereby obtain a nickel-impregnated spray-dried sorbent material.
  • a 50 gram quantity of the thus dried and calcined nickel-impregnated spray-dried sorbent material was then spray impregnated with a solution of 22.3 grams of nickel nitrate hexahydrate (Ni(NO 3 ) 2 «6H 2 O) in 13 grams of distilled water.
  • the resulting twice- nickel-impregnated spray-dried material was then dried in an oven which was increased from an ambient temperature at 3°C per minute to 150°C and maintained at 150°C for one hour and then increased at a rate of 3°C per minute to 635°C and maintained at 635°C for one hour to thereby obtain a twice-nickel-impregnated spray-dried sorbent material.
  • Invention Sorbent B contained a final total of about 23 weight percent nickel based on the total weight of the material and about 10 weight percent bentonite based on the total weight of the material.
  • Invention Sorbent B The physical and chemical characteristics of Invention Sorbent B are included in Table I.
  • This example illustrates the performance of Control Sorbent A and Invention Sorbent B described herein in Example I in a desulfurization process.
  • Control Sorbent A Ten grams of Control Sorbent A were placed on a frit in a 1-inch diameter quartz reactor tube having a length of about 12 inches.
  • gaseous cracked-gasoline was pumped upwardly through the reactor at a rate of 13.4 miUiliters per hour (mL/HR).
  • the gaseous cracked-gasoline had a motor octane number (MON) of 80, an olefin content of 24.9 weight percent, 340 parts per million sulfur by weight sulfur-containing compounds based on the total weight of the gaseous cracked-gasoline, and about 95 weight percent thiophenic compounds (such as, for example, alkyl benzothiophenes, alkyl thiophenes, benzothiophenes and thiophenes) based on the weight of sulfur-containing compounds in the gaseous cracked-gasoline.
  • MON motor octane number
  • olefin content 24.9 weight percent
  • sulfur-containing compounds based on the total weight of the gaseous cracked-gasoline
  • thiophenic compounds such as, for example, alkyl benzothiophenes, alky
  • the reactor was maintained at a temperature of 700°F and at a pressure of 15 pounds per square inch absolute (psia). Hydrogen flow was at 150 standard cubic centimeters per minute (seem) diluted with 150 seem of nitrogen.
  • Control Sorbent A was reduced with hydrogen flowing at a rate of 300 seem at a temperature of 700°F for a period of one hour. Each cycle consisted of four hours with the product sulfur (ppm) for each cycle being measured at one hour intervals over each four-hour cycle period. After each cycle, Control Sorbent A was regenerated at 900°F for 1.5 hours with a mixture of oxygen and nitrogen containing four volume percent oxygen, then purged with nitrogen, and then reduced in hydrogen flowing at a rate of 300 seem for one hour at 700°F. Control Sorbent A was tested over two cycles.
  • TOS denotes Time on Stream in hours
  • test data clearly demonstrate that use of a sorbent composition of the present invention to remove sulfur from cracked-gasoline containing 340 parts per million sulfur by weight sulfur-containing compounds based on the total weight of the cracked-gasoline results in a significant reduction of the sulfur content of such cracked-gasoline, generally to a level of about 5 to 45 parts per million sulfur.
  • test data further demonstrate that a sorbent composition which contained about 10 weight percent of an attrition-resistance-enhancing component (bentonite) distributed throughout a sorbent composition prepared according to a process of the present invention desulfurized the cracked-gasoline as effectively as Control Sorbent A, while Invention Sorbent B exhibited superior attrition resistance.
  • an attrition-resistance-enhancing component bentonite
  • Invention Sorbent B which contained an attrition- resistance-enhancing component (bentonite), exhibited a very high effectiveness to remove sulfur which was comparable to Control Sorbent A which did not contain an attrition-resistance-enhancing component, yet Invention Sorbent B exhibited superior attrition resistance properties.
  • Invention Sorbent B exhibited excellent sulfur removal performance and little or no loss in sulfur removal efficiency during the 8 cycles of operation conducted in Example II.
  • the improvement in sorbent attrition resistance is believed to be due to a novel process of making the inventive sorbent composition by a process of utilizing an attrition-resistance-enhancing component and a support component to provide a material which is subsequently promoted with a promoter component and then reduced to produce a sorbent composition with enhanced attrition resistance compared to a sorbent composition which does not contain such attrition-resistance- enhancing component.

Abstract

L'invention concerne une composition de sorbant pouvant être utilisée pour la désulfuration d'un fluide à teneur en hydrocarbures, tel que l'essence de craquage ou le carburant diesel. La composition de sorbant contient un composant de base, un composant améliorant la résistance à l'attrition et un composant accélérateur. L'agent accélérateur est présent à un état de valence réduite. Une telle composition de sorbant peut être généralement préparée par un procédé consistant à incorporer un composant de base et un composant améliorant la résistance à l'attrition accompagnés d'un accélérateur que l'on réduit de manière à réduire l'état de valence dudit accélérateur.
EP01964246A 2000-08-31 2001-08-21 Desulfuration et nouveaux sorbants permettant cette desulfuration Withdrawn EP1334165A4 (fr)

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JP5755999B2 (ja) * 2011-10-31 2015-07-29 大阪瓦斯株式会社 脱硫剤の製造方法、脱硫剤、および、炭化水素の脱硫方法
JP6371102B2 (ja) * 2014-04-24 2018-08-08 日揮触媒化成株式会社 金属担持成形体、その製造方法、吸着脱硫触媒、吸着脱硫方法、水素製造方法、および、燃料電池システム
JP5911551B2 (ja) * 2014-10-27 2016-04-27 大阪瓦斯株式会社 脱硫剤の製造方法および炭化水素の脱硫方法
KR102067339B1 (ko) * 2018-06-25 2020-01-16 주식회사 세일에프에이 유해가스 제거용 촉매가 함유된 고강도 펠릿 조성물 및 이의 제조방법
CN115722261A (zh) * 2021-08-31 2023-03-03 中国石油化工股份有限公司 降低汽油中苯含量和硫含量的含磷催化剂及其制备方法和应用

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CN107474870B (zh) * 2016-06-07 2019-11-15 中国石油化工股份有限公司 一种吸附剂的硫化方法

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JP2004507355A (ja) 2004-03-11
WO2002018517A1 (fr) 2002-03-07
AR031395A1 (es) 2003-09-24
CA2420338A1 (fr) 2002-03-07
AU2001285123A1 (en) 2002-03-13
KR20030029864A (ko) 2003-04-16
NO20030977D0 (no) 2003-02-28
EG22849A (en) 2003-09-30
BR0113620A (pt) 2003-07-15
NO20030977L (no) 2003-04-24

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