CA2393398A1 - Desulfurization process and novel bimetallic sorbent systems for same - Google Patents

Desulfurization process and novel bimetallic sorbent systems for same Download PDF

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Publication number
CA2393398A1
CA2393398A1 CA002393398A CA2393398A CA2393398A1 CA 2393398 A1 CA2393398 A1 CA 2393398A1 CA 002393398 A CA002393398 A CA 002393398A CA 2393398 A CA2393398 A CA 2393398A CA 2393398 A1 CA2393398 A1 CA 2393398A1
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accordance
sorbent
particulate
range
bimetallic promotor
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CA002393398A
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French (fr)
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CA2393398C (en
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Gyanesh P. Khare
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China Petroleum and Chemical Corp
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    • 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
    • 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
    • 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
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J20/3206—Organic carriers, supports or substrates
    • 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
    • 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
    • B01J20/34—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
    • 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
    • C10G25/12—Recovery of used adsorbent
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • 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
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/515—Specific contaminant removal
    • Y10S502/517—Sulfur or sulfur compound removal

Abstract

Novel sorbent systems for the desulfurization of cracked-gasoline are provided which are comprised of a bimetallic promotor on a particulate support such as that formed of zinc oxide and an inorganic or organic carrier. Such bimetallic promotors are formed of at least two metals of the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molydenum, tungsten, silver, tin , antimony and vanadium with the valence of same being reduced, preferably to zero. Processes for the production of such sorbents are provided wherein the sorbent is prepared from impregnated particulate supports or admixed to the support composite prior to particulation, drying, and calcination. Further disclosed is the use of such novel sorbents in the desulfurization of cracked-gazoline whereby there is achieved not only removal of sulfur but also an increase in the olefin retention in the desulfurized product. Such sorbents can also be utilized for the treatment of other sulfur-containing streams such as diesel fuels.

Claims (24)

1. A sorbent composition suitable for removal of sulfur from cracked-gasolines which is comprised of (a) a bimetallic promotor, and (b) a particulated support wherein said bimetallic promotor is present in a substantially reduced valence state and in an amount which effects the removal of sulfur from a stream of cracked-gasoline when contacted with same under desulfurization conditions.
2. A sorbent composition in accordance with claim 1, wherein said bimetallic promotor is formed of any two or more metals which are nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony or vanadium.
3. A sorbent composition in accordance with claim 2, wherein the ratio of the metals of said bimetallic promotor is in the range of about 20:1 to about 1:20.
4. A sorbent composition in accordance with claim 3, wherein said bimetallic promotor is comprised of nickel and cobalt.
5. A sorbent composition in accordance with claim 4, wherein the ratio of nickel to cobalt is about 1:1.
6. A sorbent composition in accordance with claim 5, wherein said nickel and said cobalt are present in an amount in the range of about 5 to about 40 weight percent, based on the total weight of the sorbent composition.
7. A sorbent composition in accordance with claim 3, wherein said bimetallic promotor is comprised of nickel and copper.
8. A sorbent composition in accordance with claim 7, wherein the ratio of nickel to copper is about 3:1.
9. A sorbent composition in accordance with claim 1, wherein said particulate support is comprised of zinc oxide and an inorganic or organic carrier.
10. A sorbent composition in accordance with claim 9, wherein said particulate support is comprised of zinc oxide, silica and alumina.
11. A sorbent composition in accordance with claim 10, wherein said zinc oxide is present in an amount in the range of about 10 to about 90 weight percent, said silica is present in an amount in the range of about 5 to about weight percent, and said alumina is present in an amount in the range of about 5 to about 30 weight percent.
12. A sorbent composition in accordance with claim l, wherein said composition is a particulate in the form of one of granule, extrudate, tablet, sphere, pellet or microsphere.
13. A process for the production of a sorbent composition according to any one of the preceding claims which comprises:
(a) impregnating the particulate support with the bimetallic promotor;
(b) drying the impregnated particulate of step (a);
(c) calcining the dried particulate of step (b); and thereafter (d) reducing the resulting calcined particulate of step (c) with a suitable reducing agent under suitable conditions to produce a particulate composition.
14. A process in accordance with claim 13, wherein said particulate is dried at a temperature in the range of about 65.5°C to about 177°C (about 150°F to about 350°F).
15. A process in accordance with claim 13, wherein said particulate is calcined at a temperature in the range of about 204°C to about 815.5°C (about 400°F to about 1500°F).
16. A process for the production of a sorbent composition according to any one of claims 1-12, which comprises:
(a) incorporating the bimetallic promotor into a non-particulated support composition;
(b) particulating the resulting bimetallic promotor-support composition;
(c) drying the bimetallic promotor containing particulate;
(d) calcining the dried bimetallic promotor containing particulate of step (c); and thereafter (e) reducing the resulting calcined particulate of step (d) with a suitable reducing agent under suitable conditions to produce a particulate.
17. A process for the removal of sulfur from a stream of a cracked-gasoline or diesel fuel which comprises:
(a) contacting said stream with a sorbent composition according to any one of claims 1-12, wherein said metals of said bimetallic promotor enhance olefin retention in said stream under conditions such that there is formed a desulfurized fluid stream of cracked-gasoline and a sulfurized sorbent;
(b) separating the resulting desulfurized fluid stream from said sulfurized sorbent;
(c) regenerating at least a portion of the separated sulfurized sorbent in a regeneration zone so as to remove at least a portion of the sulfur absorbed thereon;
(d) reducing the resulting desulfurized sorbent in an activation zone so as to provide a reduced valence bimetallic promotor therein which will effect the removal of sulfur from a stream of cracked-gasoline when contacted with same;
and (e) returning at least a portion of the resulting desulfurized, reduced bimetallic promotor containing sorbent to said desulfurization zone.
18. A process in accordance with claim 17, wherein said stream is cracked gasoline.
19. A process in accordance with claim 17, wherein said desulfurization is carried out at a temperature in the range of about 37.7°C to about 538°C (about 100°F to about 1000°F) and at a pressure in the range of about 0.10 to about 10.34 MPa (about 15 to 1500 psia) for a time sufficient to affect the removal of sulfur from said stream.
20. A process in accordance with claim 17, wherein said regeneration is carried out at a temperature in the range of about 37.7°C to about 815.5°C (about 100°F to about 1500°F) and a pressure in the range of about 0.7 to about 10.34 (about 10 to about 1500 psia) for a time sufficient to effect the removal of at least a portion of sulfur from the sulfurized sorbent.
21. A process in accordance with claim 20, wherein there is employed air as a regeneration agent in said regeneration zone.
22. A process in accordance with claim 20, wherein said regenerated sorbent is subjected to reduction with hydrogen in an activation zone which is maintained at a temperature in the range of about 37.7°C to about 815.5°C (about 100°F to about 1500°F) and at a pressure in the range of about 0.10 to about 10.34 MPa (about 15 to 1500 psia) and for a period of time sufficient to effect a substantial reduction of the valence of the metal content of the bimetallic promotor of said sorbent.
23. A process in accordance with claim 22, wherein said separated sulfurized sorbent is stripped prior to introduction into said regeneration zone.
24. A process in accordance with claim 22, wherein the regenerated sorbent is stripped prior to introduction to said activation zone.
CA002393398A 1999-12-14 2000-12-11 Desulfurization process and novel bimetallic sorbent systems for same Expired - Lifetime CA2393398C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/460,067 US6274533B1 (en) 1999-12-14 1999-12-14 Desulfurization process and novel bimetallic sorbent systems for same
US09/460,067 1999-12-14
PCT/US2000/042740 WO2001044407A1 (en) 1999-12-14 2000-12-11 Desulfurization process and novel bimetallic sorbent systems for same

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CA2393398A1 true CA2393398A1 (en) 2001-06-21
CA2393398C CA2393398C (en) 2009-11-17

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US (2) US6274533B1 (en)
EP (1) EP1252256B1 (en)
JP (1) JP4532804B2 (en)
KR (1) KR100743323B1 (en)
CN (1) CN1382199B (en)
AU (1) AU767207B2 (en)
BR (1) BRPI0015509B1 (en)
CA (1) CA2393398C (en)
ES (1) ES2741926T3 (en)
MX (1) MXPA02004516A (en)
WO (1) WO2001044407A1 (en)

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