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WO2007144897A1 - Composition sorbante, procédé pour sa fabrication et utilisation - Google Patents

Composition sorbante, procédé pour sa fabrication et utilisation Download PDF

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Publication number
WO2007144897A1
WO2007144897A1 PCT/IN2007/000044 IN2007000044W WO2007144897A1 WO 2007144897 A1 WO2007144897 A1 WO 2007144897A1 IN 2007000044 W IN2007000044 W IN 2007000044W WO 2007144897 A1 WO2007144897 A1 WO 2007144897A1
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Prior art keywords
adsorbent
range
nickel
sulfur
hydrogen
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Inventor
Karthik Rajendran
Bharat Lakshman Newalkar
Krupesh Sheth
Nettem Venkateswarlu Choudary
Mohammad Amir Siddiqui
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Bharat Petroleum Corp Ltd
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Bharat Petroleum Corp Ltd
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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
    • B01J20/28—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
    • B01J20/02—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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • 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
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • 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
    • B01J20/3071—Washing or leaching
    • 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
    • B01J20/3231—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
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3285—Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
    • 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
    • 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
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/58—Use in a single column

Definitions

  • the present invention relates to a novel adsorbent for use in the removal of sulfur compounds from hydrocarbon fuels.
  • the present invention relates to a novel adsorbent for use in the removal of sulfur compounds such as organic sulfides, disulfides, mercaptans, thiophenes, benzothiophenes, dibenzothiophenes, and their derivatives from hydrocarbon fuels especially; transportation fuel namely gasoline, kerosene/jet fuel, and diesel and for fuel cell applications.
  • the present invention also relates to a process for the preparation of such novel adsorbents.
  • the present invention also relates to a method for removal of sulfur compounds from hydrocarbon fuels using the adsorbents of the present invention.
  • Ultra low sulfur fuel is also essential for its use in fuel cells. This is because sulfur is a strong poison to reforming as well as fuel cell catalysts. Therefore, the sulfur content in liquid hydrocarbon fuels needs to be reduced to an ultra low level, preferably to less than about 10 ppmw for solid oxide fuel cells and to less than about 1 ppmw for polymer electrolyte membrane fuel cells.
  • Liquid transportation fuels are usually blends of suitable streams from various processing unit in petroleum refining and they contain paraffins, napthenes, aromatics and olefinic compounds and impurities such as compounds of sulfur and nitrogen. It is well known that naphtha from Fluidized Catalytic Cracking (FCC) accounts for majority of the sulfur level and olefins in gasoline pool. Sulfur can be removed from FCC naphtha by the catalytic hydrodesulphurization (HDS) process. This process, however, requires high consumption of hydrogen and significantly reduces fuel octane number due to olefin and aromatics saturation. Because gasoline contains olefins and aromatics, which have high-octane value, selective removal of sulfur without loss of octane is highly desirable.
  • FCC Fluidized Catalytic Cracking
  • HDS catalytic hydrodesulphurization
  • HDS process is not suitable for reducing sulfur content in diesel fuel to below 15 ppmw because the remaining sulfur compounds such as 4,6 dimethyl- dibenzothiophene (4,6-DMDBT) and trimethyl-dibenzothiophene (TMDBT) are refractory and very difficult to remove.
  • 4,6 dimethyl- dibenzothiophene (4,6-DMDBT) and trimethyl-dibenzothiophene (TMDBT) are refractory and very difficult to remove.
  • Newly proposed technologies identified in the EPA report include a catalytic distillation technology, called CDTech, which relies upon an HDS catalyst supported in a distillation column to provide reaction of organic sulfur compounds with diene compounds present in FCC naphtha.
  • the resultant thioether reaction product has a higher boiling point and can be removed from the bottom of the distillation column. Similar to conventional hydro treating processes, this process also uses an HDS catalyst.
  • hydrogen consumption and olefin saturation are claimed to be lower as compared to conventional hydro treating processes.
  • the operating cost for sulfur removal using the CDTech process is reported to be 25% lower than conventional hydro treating processes for the same degree of sulfur removal.
  • IRVAD adsorbs heteroatom-containing hydrocarbon compounds, including sulfur, nitrogen, and oxygen compounds, present in FCC naphtha onto an alumina-based sorbent in liquid phase (see U.S. Pat. No. 5,730,860, issued Mar 24, 1998 to Irvine).
  • the sorbent is fluidized in a tall column and continuously removed and regenerated using hydrogen in a second column.
  • the regenerated catalyst is then recycled back into the reactor.
  • the regeneration of spent sorbent produces a hydrocarbon stream containing about 1 wt % sulfur, which can be treated using conventional processes.
  • SZorb process has been developed by the Phillips Petroleum Company. It is understood that this process uses a sorbent comprising one or more metallic promoters, such as a combination of nickel and cobalt, in a zero valence state to selectively remove sulfur compounds from FCC naphtha in the presence of hydrogen. As the sorbent/catalyst becomes saturated with sulfur compounds, it is sent to a regeneration unit where it is treated with an oxygen-containing gas for removal of the sulfur as sulfur dioxide. The oxidized sorbent is further treated with hydrogen in a downstream reducing unit to reduce some of the metal oxide/s present in the sorbent composition to their reduced forms. The reduced sorbent is then fed to the sulfur removal unit, along with hydrogen, for further desulfurization of FCC naphtha.
  • metallic promoters such as a combination of nickel and cobalt
  • This process is carried out at a temperature between about 250 to about 350 0 C and a pressure of 100 to 300 psig.
  • the S-Zorb process uses conventional bubbling-bed fluidized-beds for adsorption and regeneration reactors, which have inherent limitation on throughput of the FCC naphtha feed that can be processed in this system. Phillips claims that this process can remove about 97% of the sulfur from FCC naphtha with a 1 to 1.5 point loss in octane number and with an operating cost of 1.5 to 2 cents per gallon of gasoline.
  • the need for a two-step regeneration process, consumption of hydrogen and associated octane number loss, and the use of low throughput bubbling-bed systems are some of the major drawbacks of this technology.
  • US Patent Application No. 20050098478 discloses a process for reducing refractory sulfur level using titanate based sorbents.
  • Pearce et al proposed to increase sulfur removal by treating the straight run naphtha feeds in a three-stage process in which the hydrocarbon oil is treated with sulfuric acid in the first step, a hydrotreating process employing an alumina-supported cobalt molybdate catalyst is used in the second step, and an adsorption process, preferably using zinc oxide is used for removal of hydrogen sulfide formed in the hydro treating step as the third step.
  • the process is said to be suitable only for treating feedstock that are substantially free from ethylenically or acetylenically unsaturated compounds.
  • Pearce et al disclose that the process is not suitable for treating feedstock, such as hydrocarbons obtained as a result of thermal cracking processes that contain substantial amounts of ethylenically or acetylenically unsaturated compounds such as full-range FCC naphtha, which contains about 30% olefins.
  • U.S. Patent No. 5,157,201 discloses that organic sulfur species, primarily comprising organic sulfides, disulfides, and mercaptans, can be adsorbed from olefin streams, without saturating the olefins, by contacting the feed with a metal oxide sorbent at relatively low temperatures (50 to 75 0 C), in the absence of hydrogen.
  • the metal oxide sorbent includes metal oxides selected from a group consisting of a mixture of cobalt and molybdenum oxides, a mixture of nickel and molybdenum oxides and nickel oxide supported on an inert support.
  • the adsorbed organic sulfur compounds are removed from the sorbent by purging with an inert gas while heating at a temperature of about 200 0 C.
  • Nickel based sorbent material for effectively removing lighter sulfur compounds such as mercaptans and organic sulfides and disulfides from fuel for fuel cell application.
  • performance of the sorbent compositions has not been reported for desulfurization of gasoline and diesel fuel.
  • US Patent Application No. 20030113258 illustrates a method for preparing Ni-Cu based sorbent for desulfurization of kerosene having total sulfur level of 150 ppmw for production of hydrogen via steam reforming route. But the performance of such material is not evaluated for desulfurization of heavier petroleum product namely diesel.
  • nickel based sorbents pyrophoric in nature from regeneration point of view. So far, such sorbents are effective for desulfurization of fuels having low total sulfur levels.
  • Published US Patent Application No. 20050121365 discloses a process for the desulfurization of a fuel cell feed stream passing the fedd stream over a catalyst adsorbent containing from about 30 percent to about 80 percent nickel or a nickel compound, from about 5 percent to about 45 percent silica as a carrier, from 1 percent to about 10 percent alumina as a propmoter and from about 0.1 to 15 percent magnesia as a promoter.
  • This patent application discloses a very specific embodiment of a sorbent, which it claims to be superior to the generic nickel and alumina based sorbents known but does not disclose any regenerative property of the catalyst.
  • Published US Patent Application No. 20050258077 discloses an adsorbent for removing sulfur compounds from the hydrocarbon streams.
  • the adsorbent composition comprises particles of nickel distributed in a phase including alumina grafted onto a mesoporous silica. This document shows that increased sorption surface area, distributing nickel in a phased a manner on a alumina grafted mesoporous silica suppoprt is rather cumbersome. Furthermore, the regeneration of the used sorbent without the consumption of hydrogen is claimed in the patent application.
  • the present invention now seeks to meet such demands by providing novel sorbent compositions having high sorption area and methods exhibiting high sorption capacity and reversibility for sulfur compounds from hydrocarbon fuels.
  • an important object of the present invention to provide an adsorbent composition exhibiting high sorption capacity for sulfur compounds from hydrocarbon fuels. It is yet another object of the present invention to provide a method for the production of a sorbent possessing high sorption capacity for sulfur compounds from hydrocarbon fuels.
  • the adsorbent composition of the present invention which comprises from about 20 percent to about 80 percent of metallic nickel or a nickel compound, from about 1 percent to about 20 percent of an aluminum compound, preferably alumina, as a binder, and from about 1 percent to about 10 percent of group IB metallic element as a promoter, wherein all percentages are by weight.
  • the present invention also relates process for reducing the sulfur content in hydrocarbon fuels and liquid hydrocarbon feedstock such as gasoline, kerosene/ aviation fuel and diesel fuel using the sorbent of the present invention BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
  • Figure 1 shows the sulfur concentration of the hydrocarbon product from adsorption column of the present invention as a function of volume processed using a preferred adsorbent of the present invention.
  • Figure 2 shows the sulfur concentration of the hydrocarbon product from adsorption column of the present invention as a function of volume processed using another preferred adsorbent of the present invention
  • the composite material useful in the ultra-deep desulfurization process of the present invention, is preferably prepared by a method comprising (a) co-precipitation of NiO precursor, Ag 2 O / Li 2 O / AuO/ SrO/ BaO promoter precursors and alumina binder using sodium carbonate as a precipitating agent at 25 0 C (b) aging of the precipitate overnight either in mother liquor providing a material having the surface area 50-200 m 2 /g or under hydrothermal /microwave-hydrothermal conditions at a temperature in the range of 1 10-150 0 C providing a material having the surface area 100-300 m 2 /g.
  • the microwave hydrothermal aging is carried out using MARS-5 unit (CEM Corporation) and hydrothermal aging is performed using high pressure reactor c) washing, drying and finally calcining the material obtained in step-b in air at 400 0 C.
  • MARS-5 unit CEM Corporation
  • hydrothermal aging is performed using high pressure reactor c) washing, drying and finally calcining the material obtained in step-b in air at 400 0 C.
  • sorbent composition is palletized to form sorbent body in various shapes such as extrudates, granules, and beads etc. using clay, preferably bentonite, and/ or alumina binder.
  • the BET surface area for the prepared compositions was estimated by measuring nitrogen uptake at -196 0 C using Autosorb-lC unit (Quantachrome, USA).
  • the feed having desired sulphur level is passed through the reactor from bottom to top flow at a predetermined processing rate.
  • the samples were collected at different time interval and analyzed for the total and individual sulfur concentration.
  • the total sulfur content is measured using Thermo Euroglass Total Sulfur analyzer (Model: TS 3000) as per ASTM D5453 method.
  • the individual sulfur concentration is measured using GCSCD (Model: GC Clarus 500/Sievers 350) technique.
  • the sulfur concentration as a function of volume processed is monitored.
  • the fuel which may be treated include LPG, gasoline, kerosene, aviation fuel and diesel fuel having sulfur not more than 2000 ppmw.
  • the invention provides materials and a method for producing ultra low sulfur content transportation fuels for motor vehicles as well as for applications such as fuel cells.
  • the materials and method of the invention may be used at near ambient or elevated temperatures and pressure without directly contacting the hydrogen gas with fuels.
  • Organo-sulfur species such as sulfides, disulfides, mercaptins, thiopenes, benzothiopenes, dibenzothiopenes, substituted thiopenes/ benzothioenes are removed by selective sorption onto a sorbent material, when the procedures and materials of the invention are employed to desulfurize hydrocarbon fuel.
  • sulfur compounds When applied to gasoline, sulfur compounds are removed from the gasoline with little or no loss of aromatics, olefinic hydrocarbons or open chain and cyclic paraffinic hydrocarbons.
  • PNA polynuclear aromatics
  • the spent sorbent can be regenerated either by hydrogen in the single step or in two steps via oxidation and reduction step using air and hydrogen, respectively.
  • the present invention provides several advantages. These advantages include but are not limited to the following:
  • Sulfur removal may be performed at near ambient temperature and pressure, and does not require direct contact of hydrogen, like catalytic hydrodesulfurization (HDS) process
  • Spent sorbent may be easily regenerated.
  • the selective sorption of sulfur compounds may be either used as an independent process at non-refinery locations or with the hydrodesulfurization of the concentrated sulfur fraction as an integrated process.
  • An adsorbent is prepared by mixing 2 M aqueous nickel nitrate solution and 0.6 M aqueous aluminum nitrate solution to form mixture-1.
  • 2.4 M aqueous sodium carbonate solution is added to mixture- 1 to co-precipitate the carbonate of aluminum, nickel to form the mixture-2.
  • obtained mixture-2 is aged under hydrothermal conditions at 15O 0 C overnight and subsequently filtered, washed and dried at 110 0 C for over night to form the mixture-3. Then the mixture-3 is heated in the presence of air, to 500 0 C at the heating rate of 2 0 C per minute, with intermediate holding for 2 hours at
  • Another sorbent is prepared by mixing 1.8 M aqueous nickel nitrate solution, 0.025 M aqueous copper nitrate solution and 0.6 M aqueous aluminum nitrate solution and by co-precipitating the precursors using 2.5 M aqueous sodium carbonate solution to form mixture-1.
  • mixture-1 is filtered, washed and dried at 110 0 C for over night to form the mixture-2.
  • the mixture-2 is heated in the presence of air, to 500 0 C at the heating rate of 2 0 C per minute with intermediate holding for 2 hours at 200 0 C, and held for 10 hours at 500 0 C, to form the mixture-3.
  • the obtained mixture is labeled as sorbent B.
  • Example 3 Example 3:
  • Another sorbent composition is prepared by mixing 2 M aqueous nickel nitrate solution 0.08 M aqueous lithium nitrate solution and 0.6 M aqueous aluminum nitrate solution to form mixture-1.
  • 2.4 M aqueous sodium carbonate solution is added to mixture- 1 to co-precipitate the carbonate of aluminum, lithium and nickel to form the mixture-2.
  • obtained mixture-2 is aged under microwave-hydrothermal conditions at 15O 0 C for 2-4 hr. and subsequently filtered, washed and dried at 110 0 C for over night to form the mixture-3.
  • mixture-2 is aged under microwave- hydrothermal conditions at 15O 0 C for 2-4 hr. and subsequently filtered, washed and dried at 1 10 0 C for over night to form the mixture-3. Then the mixture-3 is heated in the presence of air, to 500 0 C at the heating rate of 2 0 C, with intermediate holding for 2 hours at 200 0 C, and held for 10 hours at 500 0 C, to form the mixture-4.
  • obtained product is labeled as sorbent D.
  • sorbent E and F are prepared using 0.015 M and 0.033 M aqueous silver nitrate solution, respectively and adopting the similar procedure as described above.
  • sorbent G is prepared by mixing 0.013 M aqueous gold chloride solution , 2 M aqueous nickel nitrate solution and 0.6 M aqueous aluminum nitrate solution as per the procedure described in example 1.
  • sorbent H is prepared, as mentioned in patent application no 20040063576 using Nickel nitrate, magnesium nitrate and aluminum nitrate.
  • Sorbents employed in example 5 were regenerated in a single step under the flow of 120 cc/min of hydrogen at 430 0 C for 4 hours, and sulfur-uptake capacity measured as per the procedure described in example 5.
  • the uptake capacities for regenerated sorbent are listed in Table- 1.
  • Example 7
  • Sorbents employed in example 5 were regenerated in two steps, first by heating at 43O 0 C under the flow of air followed by heating at 43O 0 C under the flow of hydrogen (120ml/min). Sulfur-uptake capacity of thus regenerated sorbents was measured as per the procedure described in example 5 and listed in Table- 1.
  • the total sulfur content is measured using Thermo Euroglass Total Sulfur analyzer (Model: TS 3000) as per ASTM D5453 method.
  • the desulfurization treatment for the feed having total sulphur of 540 ppmw is carried out as per the procedure described above.
  • the feed is passed through the reactor at 170 0 C with a processing rate, WHSV, of 1 Hr " '.
  • the samples were collected at different time interval and analyzed for the total sulfur concentration.
  • the total sulfur content is measured as per the ASTM method D5453.
  • the sulfur concentration as a function of volume processed is depicted in Fig. 1 which demonstrates the elution of the sulfur concentration in the product as a function of volume of feed processed.
  • the eluted cumulative sulfur concentration is found to be less than 10 ppmw for the processed feed of 12 cc/g of sorbent C.
  • Example 9 Example 9:
  • the desulfurization treatment using sorbent D as per the procedure described in example 8 for feed containing total sulfur level of about 500 ppmw, in terms of heavy refractory sulfur species, is performed.
  • the feed is passed thro' the reactor with a processing rate, WHSV, of 2 Hr '1 .
  • the samples were collected at different time interval and analyzed for the total and individual sulfur concentration as mentioned above.
  • the profile for sulfur concentration as a function of feed processed volume is shown in Figure 2.
  • the eluted cumulative sulfur concentration is found to be less than 20 ppmw for the processed feed of 6 cc/g under the experimental conditions

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  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne une composition adsorbante pour utilisation dans l'élimination de composés soufrés de combustibles hydrocarbures. L'adsorbant comprend un ou plusieurs éléments choisis dans le groupe 3d et le groupe VIII de la table périodique, et un promoteur choisi parmi un ou plusieurs éléments des groupes 3d, IB, IIA et IA, imprégnés ou co-précipités sur un support constitué d'un élément choisi dans le groupe IIIA ou IVA.
PCT/IN2007/000044 2006-06-12 2007-02-02 Composition sorbante, procédé pour sa fabrication et utilisation Ceased WO2007144897A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN912/MUM/2006 2006-06-12
IN912MU2006 2006-06-12

Publications (1)

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WO2007144897A1 true WO2007144897A1 (fr) 2007-12-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8939014B2 (en) 2011-04-06 2015-01-27 Exxonmobil Research And Engineering Company Identification and use of an isomorphously substituted molecular sieve material for gas separation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060498A (en) * 1972-06-02 1977-11-29 Hitachi, Ltd. Process for steam reforming of hydrocarbons
WO2001044407A1 (fr) * 1999-12-14 2001-06-21 Philips Petroleum Company Processus de desulfuration et nouveau systemes sorbants bimetalliques associes
EP1270069A1 (fr) * 2000-03-31 2003-01-02 Idemitsu Kosan Co., Ltd. Agent desulfurant pour hydrocarbures derives de petrole, procede de fabrication d'hydrogene pour pile a combustible et procede de fabrication d'agent desulfurant a base de nickel
US20030183802A1 (en) * 2002-03-28 2003-10-02 Price Ashley G. Desulfurization and novel compositions for same
EP1378290A1 (fr) * 2002-07-02 2004-01-07 ConocoPhilips Company Catalyseurs contenants du nickel stabilisé par de l'argent ou de l'or et procédé pour la fabrication de gaz de synthèse
WO2005016503A2 (fr) * 2003-08-13 2005-02-24 Haldor Topsøe A/S Procedes catalytiques de reduction et d'oxydation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060498A (en) * 1972-06-02 1977-11-29 Hitachi, Ltd. Process for steam reforming of hydrocarbons
WO2001044407A1 (fr) * 1999-12-14 2001-06-21 Philips Petroleum Company Processus de desulfuration et nouveau systemes sorbants bimetalliques associes
EP1270069A1 (fr) * 2000-03-31 2003-01-02 Idemitsu Kosan Co., Ltd. Agent desulfurant pour hydrocarbures derives de petrole, procede de fabrication d'hydrogene pour pile a combustible et procede de fabrication d'agent desulfurant a base de nickel
US20030183802A1 (en) * 2002-03-28 2003-10-02 Price Ashley G. Desulfurization and novel compositions for same
EP1378290A1 (fr) * 2002-07-02 2004-01-07 ConocoPhilips Company Catalyseurs contenants du nickel stabilisé par de l'argent ou de l'or et procédé pour la fabrication de gaz de synthèse
WO2005016503A2 (fr) * 2003-08-13 2005-02-24 Haldor Topsøe A/S Procedes catalytiques de reduction et d'oxydation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8939014B2 (en) 2011-04-06 2015-01-27 Exxonmobil Research And Engineering Company Identification and use of an isomorphously substituted molecular sieve material for gas separation

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