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
  • 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
  • C10G67/12—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 oxidation 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/393—Metal or metal oxide crystallite size
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
  • B01J35/45—Nanoparticles
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • 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
  • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
  • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/005—Spinels
• • 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
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/19—Catalysts containing parts with different compositions

Definitions

• the present invention relates to integrated gas phase catalytic oxidative desulfurization processes to efficiently reduce the sulfur content of hydrocarbons.
• the European Union has enacted even more stringent standards, requiring diesel and gasoline fuels sold in 2009 to contain less than 10 ppmw of sulfur.
• Other countries are following in the footsteps of the United States and the European Union and are moving forward with regulations that will require refineries to produce transportation fuels with an ultra-low sulfur level.
• Retrofitting can include one or more of integration of new reactors, incorporation of gas purification systems to increase the hydrogen partial pressure, reengineering the internal configuration and components of reactors, utilization of more active catalyst compositions, installation of improved reactor components to enhance liquid-solid contact, the increase of reactor volume, and the increase of the feedstock quality.
• Sulfur-containing compounds that are typically present in hydrocarbon fuels include aliphatic molecules such as sulfides, disulfides and mercaptans as well as aromatic molecules such as thiophene, benzothiophene and its long chain alkylated derivatives, and dibenzothiophene and its alkyl derivatives such as 4,6-dimethyl- dibenzothiophene.
• Aromatic sulfur-containing molecules have a higher boiling point than aliphatic sulfur-containing molecules, and are consequently more abundant in higher boiling fractions.
• the light gas oil fraction contains less sulfur and nitrogen than the heavy gas oil fraction (0.95 W% sulfur as compared to 1.65 W% sulfur and 42 ppmw nitrogen as compared to 225 ppmw nitrogen).
• middle distillate cut boiling in the range of 170°C - 400°C contains sulfur species including thiols, sulfides, disulfides, thiophenes, benzothiophenes, dibenzothiophenes, and benzonaphthothiophenes, with and without alkyl substituents.
• sulfur species including thiols, sulfides, disulfides, thiophenes, benzothiophenes, dibenzothiophenes, and benzonaphthothiophenes, with and without alkyl substituents.
• sulfur species are categorized based on structural groups.
• the structural groups include one group having sulfur-containing compounds boiling at less than 310°C, including dibenzothiophenes and its alkylated isomers, and another group including 1, 2 and 3 methyl- substituted dibenzothiophenes, denoted as Ci, C 2 and C 3 , respectively.
• Ci 1, 2 and 3 methyl- substituted dibenzothiophenes
• the heavy gas oil fraction contains a higher content of light sulfur-containing compounds compared to heavy gas oil.
• Light sulfur-containing compounds are structurally less bulky than dibenzothiophenes and boil at less than 310°C. Also, twice as much Ci and C 2 alky 1- substituted dibenzothiophenes exist in the heavy gas oil fraction as compared to the light gas oil fraction.
• Aliphatic sulfur-containing compounds are more easily desulfurized (labile) using conventional hydrodesulfurization methods.
• certain highly branched aliphatic molecules can hinder the sulfur atom removal and are moderately more difficult to desulfurize (refractory)using conventional hydrodesulfurization methods.
• thiophenes and benzothiophenes are relatively easy to hydrodesulfurize.
• the addition of alkyl groups to the ring compounds increases the difficulty of hydrodesulfurization.
• Dibenzothiophenes resulting from addition of another ring to the benzothiophene family are even more difficult to desulfurize, and the difficulty varies greatly according to their alkyl substitution, with di-beta substitution being the most difficult to desulfurize, thus justifying their "refractory" interpretation.
• These beta substituents hinder exposure of the heteroatom to the active site on the catalyst.
• dibenzothiophene is 57 times more reactive than the refractory 4, 6-dimethyldibenzothiphene at 250°C.
• the relative reactivity decreases with increasing operating severity. With a 50°C temperature increase, the relative reactivity of di-benzothiophene compared to 4, 6-dibenzothiophene decreases to 7.3 from 57.7.
• Oxidative desulfurization (ODS) as applied to middle distillates is attractive for several reasons.
• mild reaction conditions e.g., temperature from room temperature up to 200°C and pressure from 1 up to 15 atmospheres, are normally used, thereby resulting a priori in reasonable investment and operational costs, especially for hydrogen consumption which is usually expensive.
• Another attractive aspect is related to the reactivity of high aromatic sulfur-containing species.
• US Patent 5,969, 191 describes a catalytic thermochemical process.
• a key catalytic reaction step in the thermochemical process scheme is the selective catalytic oxidation of organosulfur compounds (e.g., mercaptan) to a valuable chemical intermediate (e.g., CH 3 SH+20 2 - H 2 CO+S0 2 +H 2 0) over certain supported (mono- layered) metal oxide catalysts.
• the preferred catalyst employed in this process consists of a specially engineered V 2 0s/Ti0 2 catalyst that minimizes the adverse effects of heat and mass transfer limitations that can result in the over oxidation of the desired H 2 CO to CO x and H 2 0.
• the process described later by the inventors in PCT Application No. WO 2003/051798 involves contacting of heterocyclic sulfur compounds in a hydrocarbon stream, e.g., in a petroleum feedstock or petroleum product, in the gas phase in the presence of oxygen with a supported metal oxide catalyst, or with a bulk metal oxide catalyst to convert at least a portion of the heterocyclic sulfur compounds to sulfur dioxide and to useful oxygenated products as well as sulfur-deficient hydrocarbons and separately recovering the oxygenated products separately from a hydrocarbon stream with substantially reduced sulfur.
• the catalytic metal oxide layer supported by the metal oxide support is based on a metal selected from the group consisting of Ti, Zr, Mo, Re, V, Cr, W, Mn, Nb, Ta, and mixtures thereof.
• a support of titania, zirconia, ceria, niobia, tin oxide or a mixture of two or more of these is preferred.
• Bulk metal oxide catalysts based on molybdenum, chromium and vanadium can be also used.
• Sulfur content in fuel could be less than about 30-100 ppmw.
• the optimum space velocity likely will be maintained below 4800 V/V/hr and temperature will be 50°C - 200°C.
• the feed gas contained 1000 ppmw of COS, or CS 2 , CH 3 SH, CH 3 SCH 3 , CH 3 SSCH 3 , thiophene and 2,5-dimethylthiophene, 18% 0 2 in He balance.
• the formed products (formalin, CO, H 2 , maleic anhydride and S0 2 ) were monitored by temperature programmed surface reaction mass spectrometry. It was shown that the turnover frequency for COS and CS 2 oxidation varied by about one order of magnitude depending on the support, in the order Ce0 2 > Zr0 2 > Ti0 2 > Nb 2 0 5 > A1 2 0 3 - Si0 2 .
• a common catalyst for oxidative desulfurization is activated carbon (Yu, et al, "Oxidative Desulfurization of Diesel Fuels with Hydrogen Peroxide in the Presence of Activated Carbon and Formic Acid," Energy & Fuels, 19(2) pp. 447-452 (2005);Wu, et al, "Desulfurization of gaseous fuels using activated carbons as catalysts for the selective oxidation of hydrogen sulfide," Energy and Fuels, 19(5) pp. 1774-1782 (2005)).
• new grassroots integrated systems or retrofitted systems capable of desulfurizing hydrocarbon fuel streams containing different classes of sulfur-containing compounds having different reactivities to produce hydrocarbon fuels with an ultra-low sulfur level.
• the goal is achieved by integrating mild hydrodesulfurization and gas phase oxidative desulfurization of refractory organosulfur compounds, and utilizing reactions separately directed to labile and refractory classes of sulfur-containing compounds.
• These systems provide this capability by utilizing reactions separately directed to labile and refractory classes of sulfur- containing compounds.
• These new or retrofitted systems integrate mild hydrodesulfurization and gas phase oxidative desulfurization of refractory organosulfur compounds.
• labile organosulfur compounds means organosulfur compounds that can be easily desulfurized under relatively mild hydrodesulfurization pressure and temperature conditions
• refractory organosulfur compounds means organosulfur compounds that are relatively more difficult to desulfurize under mild hydrodesulfurization conditions.
• Deep desulfurization of hydrocarbon feed streams is achieved by first contacting the entire fuel stream with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone operating at mild conditions to remove labile organosulfur compounds.
• a flashing column downstream of the hydrodesulfurization reaction zone fractionates the hydrotreated effluent at a target cut point temperature to obtain two hydrocarbon fuel fractions.
• the organosulfur compounds in the first fraction, boiling at or above the target cut point temperature contains the remaining refractory organosulfur compounds, including 4,6-dimethyldibenzothiophene and its derivatives.
• a second fraction boiling below the target cut point temperature is substantially free of organosulfur compounds, since the organosulfur compounds boiling in the range of this fraction were the labile organosulfur compoundswhichwere removed in themild hydrodesulfurization step.
• the first fraction is contacted with a gaseous oxidizing agent over oxidation catalyst in a gas phase catalytic oxidation reaction zone to convert the refractory organosulfur compounds into hydrocarbons and SO x .
• the by-product SO x is removed from the liquid by a separation system including gas liquid separators and/or strippers and/or distillation columns and/or membranes. The process produces a hydrocarbon product stream that contains an ultra-low level of organosulfur compounds.
• FIG. 1 is a graph showing cumulative sulfur concentrations plotted against boiling points of three thiophenic compounds
• FIG. 2 is a schematic diagram of an integrated desulfurization system and process
• FIGs. 3 A and 3B are postulated gas phase catalytic oxidative desulfurization reaction mechanisms.
• An integrated desulfurization process is provided to produce hydrocarbon fuels with ultra-low levels of organosulfur compounds.
• the process includes the following steps:
• the fraction boiling below the target cut point temperature is substantially free of organosulfur compounds since the labile organosulfur compounds were converted during the hydrodesulfurization step.
• the organosulfur compounds in the fraction boiling at or above the target cut point temperature are primarily refractory organosulfur compounds, including aromatic molecules such as certain benzothiophenes e.g., long chain alkylated benzothiophenes), dibenzothiophene and alkyl derivatives, e.g., 4,6-dimethyldibenzothiophene.
• This fraction is contacted with a gaseous oxidant over oxidation catalyst in a gas phase catalytic oxidation reaction zone to convert the organosulfur compounds into sulfur-free hydrocarbons and SO x .
• the by-product SO x is subsequently removed in a separation zone from the liquid products by apparatus that include gas-liquid separators and/or strippers and/or distillation columns and/or membranes.
• the flashing column effluent fraction boiling below the target cut point temperature and the stream from the separation zone can be recombined to produce an ultra-low sulfur level hydrocarbon product, e.g., a full-range diesel fuel product.
• System 26 includes a hydrodesulfurization reaction zone 31, a flashing column 33, a gas phase catalytic oxidative desulfurization reaction zone 36 and a separation zone 38.
• a hydrocarbon stream 30 is introduced to the hydrodesulfurization reaction zone 31 and into contact with a hydrodesulfurization catalyst and a hydrogen feed stream 28 at mild operating conditions.
• the resulting hydrodesulfurized hydrocarbon stream 32 is substantially free of labile organosulfur compounds including aliphatic sulfur-containing compounds and thiophenes, benzothiophenes and their derivatives.
• Stream 32 is then passed to a flashing column 33 to be fractionated at a target cut point temperature range of about 300°C to about 360°C, and in certain embodiments about 340°C, into two streams 34 and 35.
• Stream 34 boiling below the target cut point temperature has an ultra-low level of organosulfur compounds.
• Stream 34 can be recovered separately or in combination with the portion boiling at or above the target cut point temperature that has been subjected to gas phase catalytic oxidative desulfurization reaction in zone 36.
• Stream 35 which boils above the target cut point temperature, is passed to the gas phase catalytic oxidative desulfurization reaction zone 36 to be contacted with a gaseous oxidizing agent and one or more catalytically active metals.
• the gaseous oxidizing agent can be an oxidant such as oxides of nitrogen, oxygen, or air, or combinations comprising any of these oxidants.
• the higher boiling point fraction, thegaseous oxidizing agent and the oxidation catalyst are maintained in contact for a period of time that is sufficient to complete the C-S bonds breaking reactions.
• the gas phase catalytic oxidative desulfurization zone 36 at least a substantial portion of the aromatic sulfur-containing compounds and their derivatives boiling at or above the target cut point are converted to SO x .
• Stream 37 from the gas phase catalytic oxidative desulfurization zone 36 is passed to the separation zone 38 to remove the SO x as discharge gas stream 39 and obtain a hydrocarbon stream 40 that contains an ultra-low level of sulfur, i.e., less than 15 ppmw.
• Streams 34 and 40 can be combined to provide a hydrocarbon product 41 that contains an ultra-low level of sulfur. In alternative embodiments, the products can be separately recovered.
• the oxidation catalyst can be selected from one or more homogeneous or heterogeneous catalysts having metals from Group IB, IIB, IIIB and IIIA of the Periodic Table, including those selected from the group consisting of Cu, Ce, Zn and Al.
• the gas phase catalytic compositions described herein are made by preparing an aqueous solution of the nitrates of Cu, Zn, and Al, and optionally Ce, and then combining this solution with an aqueous alkaline solution which contains NaOH, and/or one or more of (NH 4 ) 2 C0 3 , Na 2 C0 3 and NH 4 C0 3 .
• These solutions are combined at a temperature which may range from about 50°C to about 65°C, and at a pH in the range of from about 6.5 to about 14.
• the resulting hydroxides, carbonates, and/or hydroxycarbonates precipitate are filtered, washed, and dried for at least ten hours at a temperature of at least 100°C.
• the resulting dried material is then calcined for about 2-4 hours at a temperature of at least 450°C to form compositions described in Examples 2-12.
• the precipitate may be aged prior to the filtering and washing, as elaborated in the examples.
• the catalytic compositions comprise oxides of Cu, Zn, and Al in defined weight percent ranges, and optionally Ce.
• the weight percentages are in the range of from 5 to 20 weight percent ZnO, from 10 to 50 weight percent CuO, and from 20 to 70 weight percent of A1 2 0 3 .
• Ce 2 0 3 When Ce 2 0 3 is present, its amount is in the range of from 0.1 to 10 weight percent of the composition.
• the compositions exhibit X-ray amorphous phase with highly dispersed oxides of Zn, Cu, and optionally Ce.
• the aforementioned structure has the chemical formula Cu x Zni -x Al 2 0 4 , which is in accordance with the standard formula for spinels, i.e., "MA1 2 0 4 ,” where "M” signifies a metal or combination of metals.
• the ZnO and CuO are present as highly dispersed crystals. If Ce 2 0 3 is present, it is in particle form, with particles ranging in diameter from 5 nm to 10 nm.
• x is in the range of from 0.1 to 0.6, and in further embodiments from 0.2 to 0.5.
• compositions described herein preferably are granular in nature, and may be formed into various shapes such as cylinder, sphere, trilobe, or quatrolobe.
• the granules of the compositions preferably have diameters ranging from 1 mm to 4 mm.
• the compositions have specific surface areas in the range of from 10 m 2 /g to 100 m 2 /g, in certain embodiments from 50 m 2 /g to 100 m 2 /g, with pores ranging from 8 nm to 12 nm, in certain embodiments from 8 nm to 10 nm.
• the weight percentages are in the range of from 20-45 for CuO, from 10-20 for ZnO, and from 20-70 for A1 2 0 3 , in certain embodiments from 30-45 for CuO, from 12-20 for ZnO, and from 20-40 for A1 2 0 3 .
• the catalytic compositions are used in reactors such as fixed beds, ebullated beds, moving beds or fluidized beds.
• the binder may be, e.g., polyethylene oxide, polyvinyl alcohol, aluminum pseudoboehmite, silica gel, or mixtures thereof.
• the binder may be added in amounts ranging from about 1 wt% to about 20 wt% of the precipitate.
• the resulting mixture may be extruded through, e.g., a forming dye, and then dried, preferably at room temperature for 24 hours, followed by drying at about 100°C for 2-4 hours.
• the extrusion product is then heated slowly, e.g., by increasing temperatures by 2-5°C every minute until a temperature of 500°C is reached, followed by calcinations at 500°C for 2-4 hours.
• the feedstock i.e., the sulfur containing hydrocarbon
• the hydrocarbon feedstream is a straight run gas oil boiling in the range of about 180°C to about 450°C, typically containing up to about 2 weight % sulfur, although one of ordinary skill in the art will appreciate that other hydrocarbon streams can benefit from the practice of the system and method of the present invention.
• the operating conditions for the gas phase catalytic oxidative desulfurization zone 36 include: a weight hourly space velocity (WHSV) in the range of from 1 h “1 to 20 h “1 , in certain embodiments 5 h “1 to 15 h “1 , and in further embodiments 8 h “1 to 10 h “1 ; a gas hourly space velocity (GHSV)in the range of from 1,000 h “1 to 20,000 h “1 , in certain embodiments 5,000 h “1 to 15,000 h “1 , and in further embodiments 5,000 h “1 to 10,000 h “1 ; an operating pressure in the range of from about 1 bar to about 30 bars, in certain embodiments about 1 bar to about 10 bars, and in further embodiments about 1 bar to about 5 bars; and an operating temperature in the range of from about 200°C to about 600°C, in certain embodiments about 250°C to about 550°C, and in further embodiments about 300°C to about 500°C.
• WHSV weight hourly space velocity
• the molar ratio of 0 2 : C is generally about 1 : 100 to about 1 : 10, in certain embodiments about 1 :50 to about 1 : 10, and in further embodiments about 1 :20 to about 1 : 10.
• the molar ratio of 0 2 : S is generally about 1 : 1 to about 150: 1, in certain embodiments about 10: 1 to about 100: 1, and in further embodiments about 20: 1 to about 50: 1.
• the hydrodesulfurization reaction zone is operated under mild conditions.
• mild operating conditions are relative and the range of operating conditions depends on the feedstock being processed.
• these mild operating conditions as used in conjunction with hydrotreating a mid-distillate stream include: a temperature in the range of from about 300°C to about 400°C, in certain embodiments from about 320°C to about 380°C; a reaction pressure in the range of from about 20 bars to about 100 bars, in certain embodiments from about 30 bars to about 60 bars; a hydrogen partial pressure of below about 55 bars, in certain embodiments from about 25 bars to about 40 bars; a feed rate in the range of from about 0.5 hr "1 to about 10 hr "1 , in certain embodiments from about 1.0 hr "1 to about 4 hr "1 ; and a hydrogen feed rate in the
• the hydrodesulfurization catalyst can be, for instance, an alumina base containing cobalt and molybdenum or nickel and molybdenum.
• the apparatus and process for reduction of sulfur levels of hydrocarbon streams described herein includes integration of mild hydrodesulfurization with a gas phase catalytic oxidation reaction zone, in which the refractory organosulfur compounds are desulfurized by breaking the C-S bonds as shown in FIG. 3 A and/or FIG. 3B.
• the sulfur in the hydrocarbon molecules are converted into SO x and purged from the system in the gas phase through flashing.
• the present process and system offers distinct advantages when compared to conventional processes for deep desulfurization of hydrocarbon fuel.
• the addition of a flash column into an the apparatus and process of the invention that integrates a hydrodesulfurization zone and a gas phase catalytic oxidative desulfurization zone uses low cost units in both zones as well as more favorable conditions in the hydrodesulfurization zone, i.e., milder pressure and temperature and reduced hydrogen consumption. Only the fraction boiling at or above the target cut point temperature is oxidized in gas phase to convert the refractory sulfur-containing compounds to SO x .
• Traditional methods first oxidize the organosulfur compounds to sulfoxides and sulfones and then remove them from the hydrocarbon mixture.
• the present invention selectively breaks the C-S bonds in the organosulfur compounds to produce low-sulfur hydrocarbons and SO x . This results in more cost-effective desulfurization of hydrocarbon fuels, particularly removal of the refractory sulfur-containing compounds, thereby efficiently and economically achieving ultra-low sulfur content fuel products. Furthermore, the high operating costs and undesired side reactions that can negatively impact certain desired fuel characteristics are avoided using the process and apparatus of the present invention.
• a gas oil fraction was subjected to hydrodesulfurization in a hydrotreating vessel using an alumina base containing cobalt and molybdenum as hydrotreating catalyst.
• the hydrotreating vessel was operatedat 42 Kg/cm 2 hydrogen partial pressure at the reactor outlet, weighted average bed temperature of 332°C, liquid hourly space velocity of 3.2 h "1 and hydrogen to oil ratio of 300 liters/liters.
• the sulfur content of the gas oil was reduced to 1, 100 ppmw from 11,500 ppmw.
• the hydrotreated feedstock was fractionated in an atmospheric distillation column to split the gas oil into two fractions: a Light Gas Oil fraction (LGO) that boils at 340°C and less and a Heavy Gas Oil fraction (HGO) that boils at 340°C and higher.
• LGO Light Gas Oil fraction
• HGO Heavy Gas Oil fraction
• the sulfur content of the LGO fraction was less than 10 ppmw.
• Examples 2-13 are provided which describe methods to make the gaseous oxidative desulfurization catalyst material (2-12) and tests using those catalysts (13).
• solution A [65] 37.5 g of Cu(N0 3 ) 2 (0.2 moles), 13.3 g of Zn(N0 3 ) 2 (0.07 moles) and 50.1 g of A1(N0 3 ) 3 (0.235 moles) were dissolved in 500 ml of distilled water, to form what shall be referred to as "solution A" hereafter.
• the pH of the solution was 2.3.
• Solution A was heated to 65°C and solution B was added to solution A at a rate of about 5 ml/minute with constant agitation, until all of solution B was added.
• the resulting mixture had a pH of 11.0.
• a precipitate formed which was aged for 6 hours at 65°C.
• the solution was cooled to room temperature and filtered with a Buchner funnel. Precipitate was washed with distilled water. Analysis of the precipitate showed that nearly all (about 99%) of the Cu, Zn and Al precipitated out of the solution.
• the calcined product contained 36 wt% elemental Cu, 12.1 wt% elemental Zn, 14.2 wt% elemental Al and 0.02 wt% elemental Na. (In all of the examples which follow, weight percent is given in terms of the pure element, rather than the oxide.) In order to determine the weight percent of the oxide in the composition, one divides the amount of element by its molecular weight, multiplies by the molecular weight of the oxide, and then normalizes to 100%. As an example, for the composition described herein, the wt% of Cu (36) is divided by the molecular weight of Cu, which is 63.54 to yield 0.567.
• the atomic ratio of Cu:Zn:Al was 3 : 1 :2.8.
• the product had a specific surface area of 94 m 2 /g, a pore volume of 0.24 cmVg, and an average pore diameter of 9.5 nm. It exhibited highly dispersed CuO and ZnO, with an X-ray amorphous phase.
• "X-ray amorphous oxide phase" as used herein means that, when observed via high resolution transmission electron microscopy ("HRTEM"), crystalline particles ranging from 2-10 nm, and usually 2-5 nm, were observed. Lattice parameters were very close to those of spinels and its chemical composition found from EDX corresponded to the formula Cuo. 3 Zno. 7 Al 2 0 4 .
• Solution A was heated to 65°C, and solution C was added gradually to solution A, with constant agitation.
• the combined solution had a pH of 7.6.
• the resulting compound contained 26.3 wt% elemental Cu, 15.8 wt% elemental Zn, 22.3 wt% elemental Al, and the atomic ratio of Cu:Zn:Al was 1.7: 1 :3.5.
• the compound had a specific surface area of 82 m 2 /g, a pore volume of 0.29 cmVg, and an average pore diameter of 12 nm. It exhibited an X-ray amorphous oxide phase (Cuo.45Zn 0 .55Al 2 04), and highly dispersed CuO, which contained less than 50% of the total copper.
• Solution A was heated to 50°C, and solution B was added gradually, at a rate of 4 ml/min, with constant agitation.
• the resulting solution had a pH was 10.0.
• the precipitate was filtered and washed with room temperature distilled water. Following washing, the precipitate was analyzed and found to contain about 99% of the Cu, Zn and Al of the amount initially contained in the solution, and a high amount of Na.
• the dark brown precipitate was calcined at 500°C for 2 hours.
• the resulting product contained 40.5 wt% elemental Cu, 13.3 wt% elemental Zn, 13.8 wt% elemental Al, and 0.47 wt% elemental Na.
• the atomic ratio of the components Cu:Zn:Al was 3.1 : 1 :2.5.
• the composition had a specific surface area of 62 m 2 /g, a pore volume of 0.15 cmVg, and an average pore diameter of 8.7 nm.
• the composition exhibited an X-ray amorphous oxide phase (Cuo. 2 Zn 0 .8Al 2 04), and a highly dispersed crystal phase which contained most of the Cu.
• Example 2 The steps of Example 2 were followed, but the precipitate was filtered hot, and without aging.
• the calcined composition contained 40.2 wt% elemental Cu, 9.7 wt% elemental Zn, 17.2 wt% elemental Al, and 0.22 wt% elemental Na.
• the atomic ratio of Cu:Zn: Al was 4.2: 1 :4.3.
• the specific surface area was 75 m 2 /g, and the pore volume was 0.29 cmVg. Average pore diameter was 12.5 nm.
• the phase composition was highly dispersed, crystalline phases of CuO, ZnO, and A1 2 0 3 .
• Example 3 was followed except 0.18 g of Ce(N0 3 ) 3 (5.5 x 10 "4 moles) was also added in the preparation of solution A. After the precipitate was formed, it was aged for 6 hours at 55°C. Analysis of the calcined composition showed 20.9 wt% elemental Cu, 17.1 wt% elemental Zn, 23.9 wt% elemental Al and 0.5 wt% elemental Ce. The atomic ratio of Cu:Zn:Ce:Al was 3.0: 1 :0.01 :3.8. The composition had a specificsurface area of 83 m 2 /g, a pore volume of 0.20 cmVg, and an average pore diameter of 10.0 nm.
• the resulting calcined composition contained 20.2 wt% elemental Cu, 15.1 wt% elemental Zn, 20.2 wt% elemental Al and 8.5 wt% elemental Ce.
• Atomic ratios of Cu:Zn:Ce:Al were 1 :35: 1 :0.25:3.2.
• the specific surface area was 125 m 2 /g, with a pore volume of 0.3 cmVg. Average pore diameter was 8.0 nm.
• it exhibited an X-ray amorphous oxide phase and a formula of Cuo.5Zn 0 .5Al 2 0 4 . It also exhibited a Ce phase with particles not greater than 10 nm in diameter.
• solution A contained 9.4 g of Cu(N0 3 ) 2 (0.05 moles), 13.3 g of Zn(N0 3 ) 2 (0.07 moles) and 27.7 g of A1(N0 3 ) 2 (0.13 moles) in 500 ml of distilled water.
• Solution A had a pH of 2.6.
• Solution B contained 53.0 g of Na 2 C0 3 (0.5 moles) and 18 g of NaOH (0.45 moles) in 600 ml of water.
• Solution B had a pH of 13.7.
• the solutions were mixed and the resulting precipitate was separated, as in Example 2.
• the calcined composition contained 10 wt% elemental Cu, 20.0 wt% elemental Zn, 21.3 wt% elemental Al and 0.65 wt% elemental Na.
• the atomic ratio of Cu:Zn:Al was 0.5: 1 :2.5, with a specific surface area of 112 m 2 /g, a pore volume of 0.30 cmVg, and average pore diameter of 10.8 nm.
• the composition exhibited an X-ray amorphous oxide phase formula Cuo. 33 Zn 0 .67Al 2 04, and contained a highly dispersed crystalline ZnO phase.
• solutions A and C were prepared in the same manner as the solutions in Example 3.
• the resulting calcined product contained 10.0 wt% elemental Cu, 12.1 wt% elemental Zn, 33.8 wt% elemental Al and 0.05 wt% elemental Na.
• the atomic ratio for Cu:Zn:Al was 0.84: 1 :6.7.
• the specific surface area was 100 m 2 /g, the pore volume was 0.35 cmVg, and the average pore diameter was 11.0 nm.
• the composition exhibited the same X-ray amorphous oxide phase formula Cuo.4Zn 0 .6Al 2 04, and there was a ⁇ - ⁇ 1 2 0 3 phase as well.
• Solution A contained 9.4 g of Cu(N0 3 ) 2 (0.05 moles), 3.8 g of Zn(N0 3 ) 2 (0.02 moles), and 95.8 g of A1(N0 3 ) 2 (0.45 moles) dissolved in 500 ml distilled water.
• Solution A had a pH of 2.25.
• Solution C contained 53.0 g of ( H 4 ) 2 CO 3 (0.55 moles) dissolved in 600 ml of distilled water. The pH of solution C was 8.0.
• solution A contained 46.9 g of Cu(N0 3 ) 2 (0.25 moles), 13.3 g of Zn(N0 3 ) 2 (0.07 moles), and 42.6 g of A1(N0 3 ) 2 (0.20 moles) dissolved in 500 ml of distilled water.
• Solution A had a pH of 2.3.
• Solution B contained 53.0 g of Na 2 C0 3 (0.5 moles) and 12 g of NaOH (0.3 moles) in 600 ml distilled water.
• Solution B had a pH of 13.3.
• Precipitation conditions were same as those of Example 2, which did not permit total precipitation of Al. In fact, while the precipitation of Cu and Zn was 99% that of Al did not exceed 80%.
• the resulting composition contained 50 wt% elemental Cu, 25.2 wt% elemental Zn, 7.4 wt% elemental Al and 0.85 wt% elemental Na.
• the atomic ratio of Cu:Zn: Al was 2.0: 1.0:0.7.
• the specific surface area was 50 m 2 /g, the pore volume was 0.20 cmVg, and the average pore diameter was 15.2 nm.
• the formula of the composition was Cuo. 33 Zn 0 .67Al 2 0 4 , with highly dispersed crystalline CuO and ZnO phases.
• solution A did not contain A1(N0 3 ) 2 , but only 7.5 g of Cu(N0 3 ) 2 (0.04 moles), 3.8 g of Zn(N0 3 ) 2 (0.02 moles) and 45.7 g of Ce(N0 3 ) 3 (0.14 moles) dissolved in 500 ml of distilled water.
• Solution A had a pH of 4.2.
• Solution D contained 15.0 g of ( H 4 ) 2 C0 3 (0.16 moles) and 18.0 g of H 4 HCO 3 (0.23 moles) in 600 ml distilled water. Solution D has a pH of 8.0.
• the composition contained 6.5 wt% elemental Cu, 3.85 wt% elemental Zn and 78 wt% elemental Ce.
• the atomic ratio of components Cu:Zn:Ce was 1.7: 1 :9.5, and the specific surface area was 85 m 2 /g, with pore volume of 0.23 cmVg and average pore diameter of 10.9 nm.
• the observed composition by XRD was a highly dispersed crystalline Ce0 2 phase. Crystalline phases of Cu and Zn were not detected.
• GHSV gas volume rate (in liters/hour per liter of catalyst)
• WHSV weight hourly space velocity: feed rate (Kg/hours) over the weight of the catalyst.
• 0 2 /S refers to the rate at which oxygen was introduced to the material being tested.
• S and HC refer to "sulfur” and “hydrocarbon,” respectively.
• compositions contain defined amounts of the metallic oxides.
• the weight percentages permitted by the invention are 5 to less than 20 weight percent zinc oxide, from 10 to 50 weight percent copper oxide, and from 20 to 70 weight percent of aluminum oxide.
• cerium oxide When cerium oxide is present, its amount can range from 0.1 to 10 wt percent of the composition.
• the aforementioned structure has a lattice parameter corresponding to spinel according to HRTEM data and the chemical formula Cu x Zni -x Al 2 0 4 found from EDX analysis.
• the standard formula for spinels is MA1 2 0 4 , where "M” signifies a metal or combination of metals.
• the ZnO and CuO are present as highly dispersed crystals. If Ce 2 0 3 is present, it is in particle form, with particles ranging in diameter from 5 nm to 10 nm. In certain embodiments x ranges from 0.1 to 0.6, and in further embodiments from 0.2 to 0.5.

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