Classifications

• • 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
  • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
  • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
• • 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
  • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
  • B01J20/041—Oxides or hydroxides
• • 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
• • 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
  • B01J20/02—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
  • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
• • 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
  • B01J20/02—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
  • B01J20/16—Alumino-silicates
• • 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
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
  • F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
  • F02M27/02—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like by catalysts
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
  • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
  • F02M37/22—Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines, e.g. arrangements in the feeding system
  • F02M37/30—Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines, e.g. arrangements in the feeding system characterised by heating means
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
  • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
  • F02M37/22—Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines, e.g. arrangements in the feeding system
  • F02M37/32—Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines, e.g. arrangements in the feeding system characterised by filters or filter arrangements
  • F02M37/38—Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines, e.g. arrangements in the feeding system characterised by filters or filter arrangements with regeneration means

Definitions

• Embodiments of this invention may have been made with governmental support under Contract No. DE-FC26-02NT41219. Therefore, the U.S. Government may have a paid-up license to portions or embodiments of this invention and the right in limited circumstances to require the patent owner to license to others on reasonable terms as provided for by the terms of, Contract No. DE-FC26-02NT41219.
• the present invention relates to a fuel filter and method for the removal of sulfur containing compounds from a post-refinery fuel stream. More particularly, the disclosed inventions provide for the production of fuel streams having concentrations of sulfur containing compounds of no more than 3 ppm.
• TheTe continues to be environmental concern relating to air pollution stemming from use of internal combustion engines, especially those used in transportation applications such as cars, trucks, boats and the like, and stationary power sources such as diesel generators and the like.
• sulfur also poisons the catalytic surface of exhaust after treatment devices. By reducing sulfur in the fuel and therefore the exhaust, the useful life of exhaust after treatment devices is extended.
• New power sources such as fuel cells will also require fuel streams to have similar or lower levels of sulfur.
• Fuel cells burn hydrogen that has been reformed from various hydrocarbon fuels, such as gasoline. Sulfur will poison the active surfaces of the fuel cell, thus shortening its life.
• the U.S. EPA has enacted regulations requiring diesel fuel producers to phase in the production of low sulfur diesel fuel (equal to or less than 15 ppm sulfur) beginning in 2006 and ending in 2010. Similarly, from 2004 to 2006, gasoline sulfur levels were reduced from 50ppm to 30ppm.
• the refining industry has used several different approaches for removing sulfur from commercially available fuel feedstocks such as gasoline and diesel.
• the most common methods employed by the refinery industry for the removal of sulfur from fuels are hydrodesulfurization (HDS), Merox thiol extraction processing, and adsorption.
• sulfur polishing technology must be capable of producing fuels having particularly low concentrations of sulfur containing fuels, i.e., less than 50 ppm and more particularly less than 15 ppm.
• sulfur-polishing technology must be applicable for use in a wide variety of environments without the use of heavy, large, complex and/or expensive equipment, components, pretreatment processes, chemicals, high temperatures and pressures and the like. Ideally, pressures and temperatures would not exceed those normally experienced in an internal combustion engine (ICE) fuel system.
• ICE internal combustion engine
• sulfur-polishing technology were suitable for use in the normal fuel distribution systems employed by refineries to distribute their manufactured product.
• the components of such fuel distribution systems may be generally referred to as interim storage devices, i.e., above and below ground storage tanks, tanker trucks, filter trucks, connecting piping, metering and dispensing equipment, and the like.
• interim storage devices i.e., above and below ground storage tanks, tanker trucks, filter trucks, connecting piping, metering and dispensing equipment, and the like.
• sulfur-polishing technology that could be easily and economically utilized by any entity at any point in a fuel distribution system, i.e., refineries, blenders, distributors, processors, direct sellers of fuel and the like.
• hydrodesulfurization refers to processes that comprise adding hydrogen to a fuel gas, decomposing and converting a sulfur compound into hydrogen sulfide in the presence of a catalyst such as a Co-Mo catalyst, and desulfurizing by adsorption of hydrogen sulfide, which is a decomposition product, by means of a desulfurizing agent such as zinc oxide, iron oxide or the like.
• a catalyst such as a Co-Mo catalyst
• a desulfurizing agent such as zinc oxide, iron oxide or the like.
• this process has been employed in a large- scale plant, but is difficult to apply to a small-sized apparatus, especially to onboard vehicle desulfurization fuel filters.
• a process of removing a sulfur compound at normal temperatures by use of an adsorbent needs neither heat or hydrogen as in a hydrodesulfurization process or a thermal adsorption process, and thus, is a simple desulfurization process.
• hydrodesulfurization processes are unsuitable for use as sulfur polishing processes, especially with respect to on board sulfur polishing processes.
• U.S. Patent 5,454,933 discloses the treatment of a hydrodesulfurized fuel with a solid adsorbent material.
• solid adsorbents include silica gel, activated alumina, zeolites, supported CoMo sorbents, activated coke, and activated carbon.
• U.S. Patent 6,533,924 discloses a fuel processing method for the removal of sulfur present in an undiluted oxygenated hydrocarbon fuel which contains an oxygenate and is used to power an internal combustion engine in a mobile environment, such as an automobile or the like, or in a stationary environment.
• U.S. Patent Application Publication No. U.S. 2001/0035006 Al discloses an exhaust gas catalyst comprising: a sulfur trap warm-up catalyst, housed within the exhaust stream and comprising a sulfur scavenger component; and a NOx adsorber catalyst housed within the exhaust stream downstream from said sulfur trap in an underfloor position.
• the sulfur scavenging component comprises metallic trapping elements including silver, aluminum, barium, cerium, cobalt, copper, zinc, and the like that may be applied to supporting materials such as high surface area materials such as alumina, (including gamma alumina, alpha alumina, theta alumina, and the like) zeolite, zirconia, silica, and the like.
• U.S. Patent Application Publication No. U.S. 2002/0028505 Al discloses a desulphurization apparatus to be mounted in automobiles, which is arranged between a fuel tank and an injector of an engine, the apparatus comprising a combination of a sulfur-containing compound adsorbent for adsorbing and concentrating the sulfur-containing compound and a sulfur-containing compound oxidizing agent or oxidation catalyst for oxidizing the adsorbed sulfur-containing compound, the apparatus further comprising a means for recovering and removing the resulting sulfur-containing oxide.
• the disclosed process requires passing the post refinery fuel stream through a fuel filter to provide a clean fuel stream having a reduced concentration of sulfur-containing compounds relative to the post- refinery fuel stream, wherein the fuel filter comprises an adsorbent comprising an inorganic oxide having a surface acidity characterized by a pKa of least -3.
• Figure 1 provides a schematic illustration of one embodiment of the disclosed fuel filter comprising a single column.
• Figure 2 illustrates another embodiment of the disclosed fuel filter comprising a single column with a guard bed.
• Figure 3 illustrates an alternative embodiment of the disclosed fuel filter of Figure 2 comprising a single column with a guard bed.
• Figure 4 provides a schematic illustration of another embodiment of the disclosed fuel filter comprising a single column with dual guard beds.
• Figure 5 provides a schematic illustration of yet another embodiment of the disclosed fuel filter comprising dual columns with a single guard bed.
• Figure 6 provides a schematic illustration of another embodiment of the disclosed fuel filter comprising dual columns with dual guard beds.
• Figure 7 illustrates an alternative embodiment of the disclosed fuel filter of Figure 6 comprising dual columns with dual guard beds.
• Figure 8 illustrates the correlation between surface acidity as measured by the visual color change method and sulfur removal capacity.
• Figure 9 illustrates the effect of varying surface acidity upon the sulfur removal capacity of a single refractory inorganic oxide.
• Figure 10 is a schematic illustration of an internal combustion engine and NOx adsorber with a disclosed fuel filter.
• post refinery fuel stream or “post refinery fuel” as used herein broadly refers to a fuel or fuel stream (used interchangeably herein) that is manufactured by a petroleum refinery.
• post refinery fuel refers to a fuel manufactured by a petroleum refinery employing at least one sulfur removing technology.
• a post refinery fuel stream will comprise sulfur containing compound(s) in a concentration of no more than 2000 ppm.
• a post refinery fuel stream will comprise sulfur-containing compound(s) in a concentration of no more than 100 ppm.
• a post refinery fuel stream will comprise sulfur-containing compound in a concentration of no more than 15 ppm.
• a post refinery fuel stream contains a population of sulfur species present as various substituted alkyl, benzo, and dibenzothiophenes.
• fuel filter' is intended to describe a fuel filter designed to remove sulfur-containing compounds found in fuels. It is understood than in accordance with exemplary embodiments a separate fuel filter may be provided to remove additional contaminants from the fuel (e.g., a typical non-sulfur removing fuel filter). Alternatively, a single fuel filter configured for both removal and release of sulfur-containing compounds and filtering of other contaminants is contemplated to be within the scope of alternative embodiments of the disclosed fuel filters and methods of using the same. The disclosed fuel filters and methods can be used with power sources such as internal combustion engines and fuel cells employed in both stationary systems and motor vehicles.
• the disclosed fuel filters and methods can be used at any point or location in traditional fuel distribution systems that distribute post refinery fuel streams to remove sulfur containing compounds that may be undesirably present in a post refinery fuel.
• Illustrative examples of internal combustion engines include gasoline powered engines and diesel engines.
• the disclosed fuel filters and methods are also generally suitable for use with fuel cells having an anode, a cathode, and an electrolyte in between the two electrodes wherein typically an oxidation reaction (e.g., H 2 ⁇ 2H + + 2e) takes place at the anode and a reduction reaction (e.g., O 2 + 2H 2 O + 4e ⁇ 4OH " ) takes place at the cathode.
• an oxidation reaction e.g., H 2 ⁇ 2H + + 2e
• a reduction reaction e.g., O 2 + 2H 2 O + 4e ⁇ 4OH "
• fuel cells include Proton Exchange Membrane or Polymer Electrolyte Membrane (PEM) fuel cells, phosphoric acid (PA) fuel cells, molten carbonate (MC) fuel cells, solid oxide (SO) fuel cells, and alkaline fuel cells.
• PEM Proton Exchange Membrane or Polymer Electrolyte Membrane
• PA phosphoric acid
• MC molten carbonate
• SO solid oxide
• alkaline fuel cells alkaline fuel cells.
• Illustrative examples of stationary systems include generators and power plants.
• motor vehicles include cars, trucks, boats, personal water craft, semi-trucks, construction devices such as bulldozers and cranes, small engine devices such as lawn mowers and tractors, and the like.
• the fuel filter for removing or reducing the concentration of sulfur containing compounds will be installed on such motor vehicles such that any fuels introduced into the vehicle must pass through the fuel filter before entering the internal combustion engine.
• the fuel filter for removing sulfur-containing compounds i.e., a sulfur reducing or removing fuel filter may be referred to as an on-board vehicle sulfur polishing or desulfurization component or process.
• the sulfur removing filter will be used as an on-board vehicle dsulfurization component that is part of an emission control system wherein the filter releases captured sulfur containing compounds into the fuel stream during a regeneration process of a NOx adsorber, wherein the regeneration of the NOx adsorber is conducted in accordance with technologies known to those skilled in the related arts.
• the disclosed fuel filters and methods can be used at any point or location in traditional fuel distribution systems that distribute post refinery fuel streams to remove sulfur containing compounds that may be undesirably present in a post refinery fuel. Such fuel distribution systems may be characterized by (i) a refinery that manufactures the post refinery fuel stream and (ii) one or more interim storage devices.
• a fuel distribution system may also include (iii) one or more fuel consuming articles or vehicles having a power source for which consumers introduce fuel.
• Illustrative examples of interim storage devices include underground and above ground storage tanks, tanker trucks, fuel discharge or dispensing devices, connecting piping, and the like.
• Fuel consuming articles or vehicles having a power source that consumes fuel include the descriptions above for motor vehicles and stationary systems.
• Illustrative post-refinery fuel streams include gasoline, kerosene, heating oil, jet fuel, cracked-gasoline, blends containing 'gas to liquid fuels' derived from natural gas, blends containing 'coal to liquid fuels * derived from coal, biofuels such as ethanol, blends contains biofuels, or diesel fuel.
• the fuel will be diesel fuel.
• gasoline denotes a mixture of hydrocarbons boiling in the range of from about 1 OO.degree. F. to about 400.degree. 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, naphtha, alkylate, isomerate, reformate, and the like and combinations thereof.
• cracked-gasoline denotes a mixture of hydrocarbons boiling in the range of from about lOO.degree. F. to about 400.degree. F., or any fraction thereof, that are products from either thermal or catalytic processes that crack larger hydrocarbon molecules into smaller molecules.
• 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, fluid catalytically cracked gasoline, heavy oil cracked gasoline, and the like and combinations thereof.
• diesel fuel denotes a mixture of hydrocarbons boiling in the range of from about 300.degree. F. to about 750.degree. 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.
• the sulfur containing compounds removed by the disclosed fuel filter may in general be any sulfur containing compound normally found in fuels intended for use in internal combustion engines.
• the disclosed fuel filters may remove one or more of such compounds from a fuel stream.
• sulfur or "sulfur containing compound” 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 disclosed process, 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 trisulf ⁇ des, organic tetrasulf ⁇ des, benzothiophene, alkyl thiophenes, alkylated benzothiophenes, dibenzothiophenes, alkylated 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 present invention, wherein each R can be an alkyl or cycloalkyl or aryl group containing one carbon atom to ten carbon atoms.
• the sulfur-containing compounds removed by the disclosed filter or process will be sulfur containing aromatic compounds.
• the sulfur containing compounds removed by the disclosed fuel filter include benzothiophene, dibenzothiophene, and derivatives thereof.
• the disclosed fuel filters and methods are suitable for use with the interim storage devices of a traditional fuel distribution system. It will be appreciated that such methods and fuel filters may be employed at numerous locations within such interim storage devices.
• a fuel desulfurization filter could be incorporated into the dispensing device at the point of use or at the entrance or exit of an interim storage device.
• a fuel desulfurization filter could be incorporated at one or more central distribution points.
• the disclosed fuel filters and methods may be used to bring post refinery fuels back into compliance. That is, post refinery fuels can become contaminated at any point along the post refinery fuel distribution chain and a once compliant post refinery fuel may thereafter possess levels of sulfur containing compounds outside legally allowed limits.
• the disclosed fuel filters and methods could be employed in mobile filter trucks that could be used where needed to ensure that a post refinery fuel possesses acceptable levels of sulfur containing compounds.
• the disclosed fuel filters are also suitable for use with commercially available post refinery fuels directly inserted into motor vehicles by a vehicle operator through a fuel intake opening in the vehicle.
• the post refinery fuels will be unadulterated, that is, they will not be subject to any pretreatment steps prior to passing through the disclosed fuel filters except for those employed by the original manufacturing refinery. Such fuels may be referred to as unadulterated post refinery fuels.
• Fuels or fuel streams that pass through the disclosed fuel filters and methods in any of the foregoing embodiments may be referred to as 'clean fuels' or 'polished fuels'.
• an unfiltered or 'contaminated' post refinery fuel streams may comprise sulfur concentrations of from about 6 ppm to 500 ppm.
• the disclosed filters and method may be used with post refinery fuel streams having sulfur concentrations of from about 15 ppm or less.
• the disclosed filters and method may be used with post refinery fuel streams having sulfur concentrations of from about 9 ppm or less.
• the disclosed filters and method may be used with refinery fuel streams having sulfur concentrations of from about 6 ppm to about 15 ppm.
• the disclosed method will result in filtered or clean fuel streams having a reduced concentration of sulfur or sulfur containing compounds as compared to the unfiltered or contaminated post refinery fuel. In another embodiment, the disclosed method will result in filtered or clean fuel streams having a reduced concentrations of sulfur or sulfur containing compounds of 15 ppm or less. In another embodiment, the disclosed method will result in filtered or clean fuel streams having a reduced concentrations of sulfur or sulfur containing compounds of 3 ppm or less
• the disclosed fuel filters comprise an adsorbent comprising an inorganic oxide having a surface acidity characterized by a pKa of at least —3.
• the disclosed fuel filters will comprise an adsorbent consisting essentially of an inorganic oxide having a surface acidity characterized by a pK a of at least -3.
• inorganic oxide refers to porous materials having pores large enough to adsorb sulfur-containing aromatic compounds.
• the inorganic oxides may be characterized by a surface area of at least 50 m 2 /g, while in another embodiment, the inorganic oxides may be characterized by a surface area of from about 150 m 2 /g to about 500 m 2 /g.
• suitable inorganic oxides will have pores in excess of 50 angstroms.
• Illustrative examples of suitable inorganic oxides include alumina, kaolinite (either sodium, ammonium or hydrogen forms), montmorillonite (either sodium, ammonium or hydrogen forms), silca magnesia, alumina-boria, activated alumina, zeolites, aluminosilicates, silica gels, clay, active clay, silicon dioxide, mesoporous silica porous material (FSM), silica alumina compounds, silica, alumina phosphate compounds, super acids, super acids- sulfated, titania , sulfated zironia, titanium dioxide, hafnium oxide, and mixtures thereof and the like.
• FSM mesoporous silica porous material
• suitable inorganic oxides will be at least one of alumina, zeolite, silica alumina compounds, silica, alumina phosphate compounds, super acids, silica gels, titanates, zironia, titanium dioxide, hafnium oxide, and mixtures thereof.
• the inorganic oxide will be alumina.
• alumina as used herein refers to AI 2 O3.
• the inorganic oxide will be at least one of gamma alumina, eta alumina, and mixtures thereof. However, not withstanding the foregoing, only those inorganic oxides having a surface acidity characterized by a pKg of at least —3 are suitable for use in the disclosed fuel filters and methods.
• surface acidity refers to a surface that has an acidity measurable by visual color change via an acid base indicator such as dicinnamalacetone.
• the disclosed fuel filters will comprise an adsorbent comprising, consisting essentially of, or consisting of, an inorganic oxide having a surface acidity characterized by a pK a of least -3. In one embodiment, the disclosed fuel filters will comprise an adsorbent comprising, consisting essentially of, or consisting of, an inorganic oxide having a surface acidity characterized by a pK a of least -6. In another embodiment, the disclosed fuel filters will comprise an adsorbent comprising, consisting essentially of, or consisting of, an inorganic oxide having a surface acidity characterized by a pK a of least -8.
• the disclosed fuel filters will comprise an adsorbent comprising, consisting essentially of, or consisting of an inorganic oxide having a surface acidity characterized by a pK a of from about -3 to about —8. It will be appreciated the function of the adsorbent is the adsorption and removal of sulfur-containing compounds from a fuel stream.
• Suitable inorganic oxides may be obtained by the calcination of an otherwise suitable inorganic oxide.
• otherwise suitable inorganic oxides will those be inorganic oxides which lack the requisite surface acidity but which are otherwise as described above.
• suitable inorganic oxides will be obtained by the calcination of inorganic oxides which lack the requisite surface acidity but which are otherwise as described above and which are commercially available.
• suitable inorganic oxides will be obtained by heating a commercially available and otherwise suitable inorganic oxide to a temperature of at least 4000 0 C. In another embodiment, suitable inorganic oxides will be obtained by heating an otherwise suitable and commercially available inorganic oxide to a temperature of from 400 to 800 0 C. In one exemplary embodiment, suitable inorganic oxides will be obtained by heating an otherwise suitable and commercially available inorganic oxide to a temperature of from 400 to 450 0 C under a flow of nitrogen. After preparation, the sorbent may be stored under dry nitrogen until use. It will be appreciated that the disclosed absorbents may in one embodiment comprise metals and metal oxides such as Group VIIIA metals, Group IVA, Group IVB and the like.
• the disclosed adsorbents may optionally be untreated with any metals or metal oxides other than those discussed above in the context of inorganic oxides. That is, in one embodiment, the disclosed adsorbents will consist essentially of the inorganic oxide having a surface acidity characterized by a pK a of at least -3. In another exemplary embodiment, the disclosed adsorbents will consist essentially of an inorganic oxide having a surface acidity characterized by a pK a of at least -3 and that is substantially free of the metals and metal oxides traditionally employed as desulfiirization catalysts or absorbents.
• the disclosed adsorbents will consist essentially of an inorganic oxide having a surface acidity characterized by a pK a of at least -3 and that is substantially free of the metals and metal oxides such as Group VIIIA metals, Group IVA, Group IVB and the like.
• the fuel filter will comprise at least one column comprising the disclosed adsorbents. As illustrated in Figure 1 , at least one column 10 will have a first opening 10 through which unfiltered fuel will enter the column 10 and a second opening 14 through which filtered fuel will exit the column 10. During the normal operation of the fuel filter, the concentration of a sulfur-containing compound in the 'clean' fuel exiting the opening 14 will be less than the concentration of the sulfur-containing compound in the 'contaminated' fuel entering the opening 12.
• the disclosed fuel filter will further comprise at least one guard bed 16 as illustrated in either Figure 2 or Figure 3.
• the at least one guard bed 16 may have a first opening 18 through which fuel enters the guard bed, and a second opening 20 though which fuel exits the guard bed.
• the guard bed 16 will connected to the at least one column 10 via a hollow conduit 22 through which fuel may pass and be transferred.
• the at least one guard bed 16 may be contiguously attached to column 10 such that fuel enters through a first opening 16, passes through both the guard bed 16 and the column 10, and subsequently exits through the second opening 14 of column 10.
• the disclosed fuel filter may comprise at least one column 10 that is linked to two guard beds 24 and 26 via conduits 28 and 30.
• the incoming fuel may enter one or both of the guard beds 24 and 26. After exiting from one or both of guard beds 24 and 26, the fuel will be transferred to column 10 via conduit 30.
• the fuel entering the column 10 will pass through first opening 12 and exit column 10 via second opening 14.
• the fuel filter may comprise multiple or dual columns 32 and 34 and a multiple or single guard bed 44.
• Dual columns 32 and 34 respectively have first openings 36 and 38 through which fuel may enter, and second openings 40 and 42 through which fuel may exit.
• Single guard bed 44 is connected to dual columns 32 and 34 via conduit 46.
• Conduit 46 in one embodiment will have conduits 48 and 50 arrayed such that fuel may enter one or both of columns 32 and 34, either sequentially or simultaneously.
• the disclosed fuel filter may comprise two guard beds 52 and 54 and two columns 56 and 58.
• the guard beds 52 and 54 may be respectively connected to columns 56 and 58 via conduits 60 and 62.
• the guard beds 52 and 54 may be directly attached to columns 56 and 58 without the use of any hollow conduits.
• the fuel may enter one or both of the guard beds 52 and 54 as well as one or both of columns 56 and 58.
• the invention also provides a method for removing a sulfur-containing compound from a post refinery fuel stream.
• the disclosed method comprises removing a sulfur-containing compound from a fuel by passing the fuel through the disclosed fuel filters capable of removing a sulfur containing compound.
• the disclosed methods and processes may further comprise storing the removed sulfur containing compound, releasing a portion of the stored sulfur-containing compound, and sending the portion to an emission control device.
• a sulfur-containing compound is removed from a fuel stream as the fuel is passed through the disclosed fuel filters.
• the sulfur-containing compound is removed as the fuel is passed through at least one column comprising the disclosed adsorbents as discussed above.
• the sulfur-containing compound removed from a fuel stream by the disclosed fuel filter will be stored by the fuel filter.
• the removed sulfur containing compound will be stored in the at least one column comprising the disclosed adsorbent.
• the removed sulfur-containing compound will be stored in the disclosed adsorbent.
• the disclosed fuel filter will remove a quantity of sulfur containing compounds.
• the adsorbent may become incapable of storing any additional sulfur-containing compound even though additional storage is desired.
• the disclosed fuel filter may be regenerated.
• Non-limiting examples of determining when the fuel filter has become saturated with sulfur-containing compounds are: measuring via sensors the sulfur content of the fuel before and after the fuel filter wherein sulfur measurement equal to or close to those of measurement entering the filter will indicate that the filter is no longer removing sulfur from the fuel; providing sensors to determine how much sulfur the engine is putting out in the exhaust stream; providing sensors in the fuel storage tank to determine the base line in parts per million of the sulfur in the fuel of the vehicle; and providing pressure sensors before and after the fuel filter, wherein any of the aforementioned methods are facilitated through the microprocessor or controller and various sensors communicating therewith as illustrated in Figure 10.
• Regeneration of the fuel filter as used herein refers to the release of at least a portion of the stored sulfur-containing compound, i.e., desulfation. Such release or regeneration may be accomplished by one or more methods.
• the regeneration of the fuel filter may be accomplished by heating the fuel filter to an elevated temperature.
• at least one column of the fuel filter will be heated by a heating element (illustrated in Figure 10) wherein either the adsorbent member of the fuel filter, the fuel or both are heated to a temperature that is greater than the highest normal operating temperature of the fuel stream, wherein the captured sulfur containing compounds will be released into the fuel stream.
• the heating element is a resistive type-heating element wherein an applied current or voltage from a power supply is used to increase the temperature of the fuel or the adsorbent material in order to release the captured sulfur containing compounds.
• other equivalent heating devices are contemplated for use in exemplary embodiments of the present invention.
• At least one column of the fuel filter will be heated to a temperature that is equal to or greater than about 100 0 C. In another embodiment, the at least one column of the fuel filter will be heated to a temperature that is equal to or below the boiling point of the fuel.
• the fuel filter may be regenerated by the use of a heated fuel stream or by displacement by a solvent other than the fuel, wherein the solvent is released from a solvent reservoir in fluid communication with the fuel stream and is capable of releasing the captured sulfur containing compounds from the adsorbent member.
• the solvent is released from the reservoir and then recaptured by a suitable filter or alternatively the solvent is a material capable of being consumed by the internal combustion engine without damaging the same or the associated emission control devices.
• the portion of the stored sulfur-containing compound released by the regeneration of the fuel filter is sent through an internal combustion engine and into an emission control device, especially a post-combustion emission control device.
• Emission control device refers to nitrogen oxide or 'NOx * adsorbers used to remove nitrogen oxides from the exhaust streams of both mobile and stationary internal combustion engines.
• the emission control device will be a Lean NOx Trap or LNT.
• 'Post- combustion' refers to a device positioned to receive the products of combustion from an internal combustion engine, i.e., located downstream from the internal combustion engine.
• the released portion will be sent through the engine and into the emission control device so that it enters the emission control device at a time or operation in the device's operational cycle when the effect of the increased concentration of sulfur is minimized.
• the portion may be sent through the engine and into a post combustion emission device such as a NOx adsorber at a time during its cycle that is less sensitive to high sulfur levels.
• a post combustion emission device such as a NOx adsorber
• the portion of sulfur containing compound released by the regeneration of the disclosed fuel filter will be sent to a NOx adsorber at a time when the NOx adsorber and/or NOx adsorber catalyst is undergoing a regenerative process either for NOx or desulfation.
• the catalysts in NOx adsorbers typically undergo regenerative processes designed to increase the efficiency of the catalyst/NOx adsorber.
• a first type of regenerative process is designed to convert the nitrogen oxides to nitrogen.
• contaminants such as sulfur containing compounds are driven off. The later process is sometimes referred to as desulfation and typically occurs at higher temperatures.
• the portion of the sulfur containing compound released by the regeneration of the disclosed fuel filter will be sent to a NOx adsorber at a time when the NOx adsorber and/or NOx adsorber catalyst is undergoing a regenerative process that results in the removal or release of nitrous oxides via reduction.
• the portion of the sulfur containing compound released by the regeneration of the disclosed fuel filter will be sent to a NOx adsorber at a time when the NOx adsorber and/or NOx adsorber catalyst is undergoing a regenerative process that results in the liberation of the sulfur containing compounds, i.e., desulfation.
• the release of the portion and its sending to an emission control device will occur over a short period of time relative to the regeneration period of the fuel filter.
• the regeneration period of the fuel filter approximates the regeneration period of the emission control device.
• the regeneration period of the emission control device will be maximized as the fuel filter will reduce the amount of sulfur being deposited on the NOx adsorber thus, regeneration periods can be less frequent and at longer intervals.
• a method and apparatus for extending the life cycle of an emission control device 70 in fluid communication with the exhaust of an internal combustion engine 72 includes the disclosed fuel filter for removing and storing sulfur-containing compounds from a post refinery fuel stream is illustrated schematically in Figure 10. As illustrated, the internal combustion engine receives fuel from a fuel storage tank 74 via the fuel filter.
• a non-limiting example of an apparatus, method or means for monitoring and controlling the release of stored sulfur containing compounds into the fuel stream is illustrated in Figure 10.
• the emission control device is a post combustion emission control device that receives the gaseous products of combustion from the combustion chamber of the internal combustion engine.
• the apparatus, method or means for monitoring and controlling the release of stored sulfur containing compounds is an on-board control apparatus comprising a plurality of sensors 78 each providing signals to a microprocessor or controller 80 comprising programmable logic that is configured to receive signals from the plurality of sensors and provide signals to the fuel filter and its associated heater element, the internal combustion engine, fuel delivery and ignition systems to vary the air to fuel flow mixture, if necessary (e.g., lean or rich operation to increase exhaust temperature) and heater elements of the emission control device wherein and upon receipt of the appropriate signals (e.g., fuel filter sulfur capacity reached and emission control device operating in or at a desulfurization or regeneration mode) the microprocessor will instruct the release of the sulfur into the fuel stream wherein the same can be received by the emission control device without adversely affecting the same.
• the appropriate signals e.g., fuel filter sulfur capacity reached and emission control device operating in or at a desulfurization or regeneration mode
• a controller operating in response to a computer program may implement the processing of the above description.
• the controller may include, but not be limited to, a processor(s), computer(s), memory, storage, registers), timing, interrupt(s), communication interfaces, and input/output signal interfaces, as well as combinations comprising at least one of the foregoing.
• algorithms for implementing exemplary embodiments of the present invention can be embodied in the form of computer-implemented processes and apparatuses for practicing those processes.
• the algorithms can also be embodied in the form of computer program code containing instructions embodied in tangible media, such as floppy diskettes, CD-ROMs, hard drives, or any other computer-readable storage medium, wherein, when the computer program code is loaded into and executed by a computer and/or controller, the computer becomes an apparatus for practicing the invention.
• the algorithms can also be embodied in the form of computer program code, for example, whether stored in a storage medium, loaded into and/or executed by a computer, or transmitted over some transmission medium, such as over electrical wiring or cabling, through fiber optics, or via electromagnetic radiation, wherein, when the computer program code is loaded into and executed by a computer.
• computer program code segments configure the microprocessor to create specific logic circuits.
• These instructions may reside, for example, in RAM of the computer or controller. Alternatively, the instructions may be contained on a data storage device with a computer readable medium, such as a computer diskette.
• the instructions may be stored on a magnetic tape, conventional hard disk drive, electronic read-only memory, optical storage device, or other appropriate data storage device.
• the computer- executable instructions may be lines of compiled C++ compatible code.
• the controller includes logic for evaluating signals from the plurality of sensors to determine if the sulfur from the fuel filter is to be released into the fuel stream during a desulfurization or regeneration process of the emission control device.
• a means for controlling the release of the sulfur will comprise a circuit and sensor for identifying a predetermined temperature or pressure in either the engine or the emission control device that signals the appropriate time for release.
• the most acidic dye indicator (9,10-Anthraquinone) turns from colorless to a bright yellow if the acid strength is at least about that of sulfuric acid.
• the results and the correlation to sulfur removal capacity are set forth in Figure 8.
• the semi-quantitative surface acidity values are charted on the left Y-axis, and the bar height corresponds to surface acidity as measured using the dye indicators.
• the values plotted represent the minimum acidity, since no dye indicators were available to assess acidity more strong than a pKa of -8.2.
• the right Y-axis (blue line) indicates the relative sulfur capacity as determined using the stirred reactor sulfur uptake protocol employed in Example 2 below.
• the surface acidity of the ⁇ -alumina was determined using the procedure found in Benesi, H.A., J. Am. Chem. Soc, 1956, 78, 5490-5494.
• the indicators used in this work were methyl red, methyl yellow, crystal violet, dicinnamalacetone, and anthraquinone.
• Solutions of the colorimteric indicators were prepared by dissolving 3 mg of the indicator in 15 mL of cyclohexane. In some cases the solid indicator did not completely dissolve in the cyclohexane.
• the calcined alumina in the different humidity levels was tested for its surface acidity by adding 0.2 g of hydrated alumina to 2 mL of the indicator solution.
• the color change was noted and correlated with the pKa of the indicator.
• the extent of sulfur removal of the alumina at each hydration level was measured using a static uptake procedure.
• the alumina (0.15 g) was added to a vial containing 15 mL of ultra-low sulfur dies ⁇ l fuel (ULSD).
• ULSD ultra-low sulfur dies ⁇ l fuel
• the mixture was stirred for 19 hours while it was heated to 60 0 C. After 19 hours, the stirring was stopped and the solids settled to the bottom of the vial.
• a portion of the diesel fuel was removed and analyzed for sulfur using an Antek Model 9000VLLS analyzer.
• the surface acidity of the 77-alumina at the various hydration levels is correlated with the sulfur removal of the ⁇ -alumina in Figure 9. It can be seen that increasing the surface acidity of the inorganic oxide increases the ability of the adsorbent to remove sulfur containing compounds from a fuel.

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