Indian Patents. 262582:"PROCESS FOR REDUCING THE SULFUR CONTENT OF DIESEL FUEL"

Title of Invention	"PROCESS FOR REDUCING THE SULFUR CONTENT OF DIESEL FUEL"
Abstract	The reduction in the sulfur-containing content of diesel fuel is achieved by oxidation in the presence of a catalyst followed by a liquid-liquid countercurrent extraction.

Full Text	BACKGROUND OF THE INVENTION This invention is directed to the removal of sulfur-containing compounds from diesel fuel and, more particularly, their removal by a combination of oxidation and extraction steps. PRIOR ART The removal of sulfur compounds from petroleum streams has been of considerable importance in the past and is even more so today due to environmental considerations. Gas effluent from the combustion of organic materials, such as coal, almost always contain sulfur compounds and sulfur removal processes have concentrated on removing hydrogen sulfide since it has been considered a significant health hazard and also because it is corrosive, particularly when water is present. With increasing emphasis on eliminating or minimizing sulfur discharge to the atmosphere, attention is turning to the removal of other sulfur compounds from gas streams. The removal of sulfur compounds and particularly chemically-combined sulfur, such as organosulfur compounds, from feedstreams is highly desirable to meet environmental concerns and to prevent potential catalyst deactivation as well as equipment corrosion. Typically, hydrocarbon products contain various amounts of sulfur compounds in the form of, for example, chemically-combined sulfur, such as inorganically combined sulfur and organically combined sulfur, i.e., organosulfur compounds. The presence of organosulfur compounds in hydrocarbon streams results naturally, as well as from the introduction of organosulfur compounds, into the hydrogen streams during conventional processes for producing and treating hydrocarbon products. As previously indicated, if chemically-combined sulfur, such as organosulfur compounds, are not removed from the hydrocarbon streams, the presence of organosulfur compounds in the resultant hydrocarbon products, including natural gas, paraffins, olefins and aromatics, particularly gasoline, diesel or other fuels, can cause corrosion of processing equipment and engine parts, as well as other deleterious effects, particularly when water is present. Oxidative desulfurization research for diesel and other oil streams has been ongoing for over 100 years. The following table summarizes patents granted from 1941 to 1976 addressed to oxidative desulfurization. (Table Removed) Paris-Marcano received two patents for oxidative desulfurization of petroleum using nitric acid with hydrogen peroxide, U.S.P. 5,017,280 and 5,087,350. Gore of Petrostar received two patents for oxidative desulfurization U.S. 6,274,785 and 6,160,193. Cabrerra received a patent for a complex oxidative desulfurization patent assigned to UOP 6,171,478. Kappas from Unipure received two patents for oxidative desulfurization using performic acid: U.S.P. 6,402,940 and 6,406,616. Ohsohl of Unipure has received two patents, 5,985,137 and 5,948,242, for desulfurization of crude oil. Jeanblanc received a patent, WO/001 5734, for radiative assisted oxidative desulfurization. Sulfur-containing carbonaceous materials are desulfurized by reaction with a mixture of an oxidizing agent and an oxygenated solvent such as diethyl ether under alkaline conditions at a temperature preferably ranging from ambient temperature to about 121°C and pressure of about 1 to 2 atmospheres. The use of radiation - such as X-ray, infrared, visible microwave, or ultraviolet radiation, alpha, beta or gamma radiation, other atomic radiation emanating from a radioactive material, or ultrasound - facilitates desulfurization. The products of the reaction are a desulfurized carbonaceous material in which the sulfur content is, for example, less than about 1% and separated sulfur compounds. Yen, U.S.P. 6,402,939, at Cal Tech received a patent for ultrasonic assisted oxidative desulfurization. Gunnerman has obtained several patents using ultrasonic assistance: U.S.P. 6,500,219 and 6,652,592. Stowe disclosed a process to oxidatively desulfurize hydrocarbon oil with ultrasonic assistance in U.S.P. 5,547,563.Cullen disclosed in four recent U.S. patent applications assigned to Petrosonics oxidative, reactive, ultrasonic desulfurization technology: Serial Number 10/411,796 filed April 11, 2003, Sulfone Removal Process; Serial Number 10/429,369 filed May 5, 2003, Process For Generating and Removing Sulfbxides from Fossil Fuel; Serial No. 10/431,666 filed May 8, 2003, Treatment of Crude Oil Fractions, Fossil Fuels & Products Thereof with Sonic Energy; and Serial Number 10/644,255 filed August 20, 2003, entitled Treatment of Crude Oil Fractions, Fossil Fuels & Products Thereof. Collins, in U.S. Patent 5,847,120 and 6,054,580 disclosed long-lived tetra-amidomacriocyclic ligand complexes of iron as homogeneous oxidation catalysts to promote peroxide oxidations. The complex provides a stable, long-lived oxidation catalyst or catalyst activator. Kocal in U.S. Patent 6,277,271 August 21, 2001 assigned to UOP discloses a process for the desulfurization of a hydrocarbonaceous oil This is a process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil and a recycle stream containing sulfur-oxidated compounds is contacted with a hydro desulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The residual oxidizing agent is decomposed and the resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated to produce a stream containing the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds. At least a portion of the sulfur-oxidated compounds is recycled to the hydrodesulfurization reaction zone. In another UOP assigned patent, Kocal in U.S. Patent No. 6,368,495 granted April 9, 2002 discloses the removal of sulfur-containing compounds from liquid hydrocarbon streams using hydrogen peroxide on air, with heterogeneous transition metal catalysts. The process more specifically addresses the removal of thiophenes and thlophene derivatives from a number of petroleum fractions, including gasoline, diesel fuel, and kerosene. In the first step of the process, the liquid hydrocarbon is subjected to oxidation conditions hi order to oxidize at least some of the thiophene compounds to sulfones. Then, these sulfones can be catalytically decomposed to hydrocarbons (e.g. hydroxybiphenyl) and volatile sulfur compounds (e.g., sulfur dioxide). The hydrocarbon decomposition products remain in the treated liquid as valuable blending components, while the volatile sulfur compounds are easily separable from the treated liquid using well-known techniques such as flash vaporization or distillation. Cabrera discloses in U.S. Patent 6,174,178 granted January 9, 2001, a process for the desulfurization of a hydrocarbonaceous oil. A process for the desulfurization in which the hydrocarbonaceous oil is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the desulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated after decomposing any residual oxidizing agent to produce a stream containing the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds. Shum teaches in U.S. Patent No. 4,772,731 granted September 20, 1988, the epoxidatkm of olefins with molybdenum dioxo dialkyleneglycolate compositions. Production of novel molybdenum dioxo dialkyleneglycolate compositions, especially adapted for use as catalysts in the epoxidation of olefmic compounds with an organic hydroperoxide, by reaction of molybdenum trioxide with particular dialkylene glycol compounds at specified elevated temperatures while removing water, Shum discloses in U.S. Pat. No. 5,780,655 granted July 14, 1998, an epoxidation process using an alkylammonium phosphate-stabilized peroxotungstate compound as catalyst. Olefins are selectively converted to epoxides using hydrogen peroxide as oxidant in a single liquid phase reaction, system characterized by a liquid phase comprised predominantly of an organic solvent. The reaction is catalyzed by a compound comprised of a phosphate-stabilized peroxotungstate species having a W:P atomic ratio of 2:1. This invention pertains to methods of converting olefins to epoxides in a single liquid phase using hydrogen peroxide and a catalyst in salt or acid form comprising a species corresponding to (RiNfePWjO^OH). Venturelto in U.S. Patent No. 5,274,140 discloses a process for olefin epoxidation by reaction with hydrogen peroxide according to a double phase technique (i.e., a biphasic reaction system containing both an aqueous phase and an oganic phase). The catalyst system consists of a first component which is at least one element selected from W, Mo, V or a derivative thereof and a second component which is at least one derivative selected from the derivatives of P and As. The mutual atomic ratio of the catalyst components is between 12 and 0.1, but preferably is between 1.5 and 0.25. Venturello in U.S. Patent No. 4,562,276 and 4,595,671 describes epoxidation catalysts for olefmic compounds, both in a homogeneous aqueous phase as well as in a heterogeneous phase. The catalysts correspond to the formula QaXW^O^-iu wherein Q represents a cation of an anionic salt, X is either P or As, while nK), 1, or 2. The atomic ratio of W:P, where X=P, thus must be 4. The use of such compositions in an epoxidation wherein the reactants are maintained in a single substantially organic phase is not disclosed. Bonsignore in U.S. Pat. No. 5,324,849 teaches a class of compounds based on tungsten and diphosphonic acids which contain active oxygen atoms and cationic groups derived from onium salts. Such compounds are said to catalyze olefm oxidation reactions in double phase reaction systems containing both an organic phase and an aqueous phase. The compounds contain two phosphorus atoms and five tungsten atoms and thus have a W:P atomic ratio of 5:2. However, the biphasic reaction systems of the type described in the aforementioned patents have a number of disadvantages which limit their usefulness in large scale commercial practice. The need to use a phase transfer agent contributes significantly to the cost of operation. Mass transfer problems are frequently encountered, particularly for relatively volatile olefins such as propylene. Additionally, there are considerable engineering difficulties associated with operating two phase reactors and phase separators. Thus, there is a need to develop active catalysts capable of providing high selectivity to epoxide during operation of a single phase epoxidation process. SUMMARY OF THE INVENTION The process of the present invention is directed to the desulfurization of a full-range, hydro treated diesel oil with an aqueous oxidizing agent in the presence of a catalyst and a co-catalyst, and thereafter selectively removing the oxidized compounds by solvent extraction. Optionally, the foregoing steps are followed by solvent stripping and recovery, and finally by a polishing step. BRIEF DESCRIPTION OF THE DRAWING The attached figure is a schematic drawing of the process of the present invention. Detailed Description of the Invention 9 As can be seen by reference to the attached drawing sheet, hydrotreated diesel in a storage tank 10 is fed into reactor column 12 where it is subjected to continuous oxidation by reaction with an aqueous oxidant and a complex catalyst which is fed into the top of column 12 from a storage tank 14. The aqueous oxidant can be, for example, hydrogen peroxide, sodium hypochlorite or sodium peroxysulfate which is catalyzed by a complex catalyst, followed by a continuous liquid-liquid extraction of the diesel oil by a mixture of water and a polar solvent. The process serves to desulfurize full range hydrotreated diesel oil with a boiling range of about 240°C to about 360°C. The process consists of treating the diesel oil in a countercurrent or a stirred tank reactor with an aqueous solution of hydrogen peroxide hi the presence of a catalyst and a co-catalyst which is also known as a phase transfer agent. This action results hi effecting the oxidation of the sulfur species present hi the hydrotreated (HT) diesel at a nominal level of 1000 ppm w/w of total sulfur. The sulfur species present are oxidized to their corresponding sulfoxides, sulfones, sultines, sultones, sulfonates, sulfinates, or even to sulfur dioxide and sulfur trioxide and sulfite and sulfate. The catalyst employed may be selected from a number of homogeneous or heterogeneous oxidation catalysts including tetraamidomacrocylic iron complexes, tetraalkylammonim polyoxometallates, dioxomolybdenum diglycolate, transition metal tetraphenylporphyrin, transition metal acetylacetonate, bismuthomolybdates, dioxomolybdenum aminodiglycolate, tetraalkylammonim metal sulfbtetraphenylporphyrin, molybdotungstic acid phosphonates, as well as many others. These may include quaternary ammonium salts of polyoxometallates, simple metal oxides, Venturello, Campos-Martin, Bressan, Shum, Collins-Horwitz, Beardon, Folin-Denis Reagent, Benedict, Bonsignore, Changwen Hu, Mere Te, Keggin, Dawson, Bearden, and Merox type catalysts. These may include tetraoctyl-ammonium phosphotungstate, peroxo molybdotungstic phosphonate, phosphomolybdic acid, dioxomolybdenum amino-diisopropanolate, triphosphono-polyperoxotungstate, bismuthomolybdic acid, sodium sulfophthalocyanine cobalt peroxide. The co-catalysts are employed to enhance and accelerate reactions which though favored thermodynamically, are very slow due to mass transfer issues. They may be anionic cationic and nonionic, with cationic phase transfer agents being preferred. In the present invention, the co-catalyst in each case is the quaternary amine salt used in the synthesis. These salts do not always have to be pre-formed prior to the reaction, but may be formed in-sttu, by adding the transition metal salt or acid and then adding to the same solvent sytem, for example, aqueous peroxide, the phase transfer agent, such as a quaternary ammonium halide. Representative phase transfer agents are methyltrioctyl-ammonium bromide, ceryltrimethylammonium bromide, tetrabutyl ammonium chloride, tetradecyl pyridhim chloride, and tetradecyl pyridinium bromide. The oxidation reaction takes place in a countercurrent reactor 12, which may be static, stirred, agitated, with oscillating or rotating discs, at a temperature between 50 to 1501°C preferably between about 70 and about 110°. Raffinate from the oxidation which contains residual catalyst, spent or residual oxidant, is recycled to the oxidant-catalyst storage tank 14, where make-up catalyst and oxidant are added. The concentration of the catalysts may be between about 0.001 and about 1.00, by weight % on oxidant, and preferably between about 0.01 and about 0.10 weight %. Oxidant concentrations may vary between about 1% and about 100%, by weight, but are typically between about 10% and about 50%, and in the case of hydrogen peroxide are preferably between about 15% and about 30%, by weight, in the aqueous phase. Oxidants vary by chemical type, oxidation potential, efficacy, stability, solubility and persons of ordinary skill in the art can establish readily the useful and effective concentrations of oxidant. Oxidants which can be used in the present process include hydrogen peroxide, sodium hypchlorite, sodium or potassium peroxydisulfate or peroxymonosulfate, t-butyl hydroperoxide, perchloric acid, nitric acid, sulfuric acid, performic acid, and mixtures thereof. The second step of the process involves the removal of the oxidized compounds by contacting the distillate with a selective extraction solvent in column 16. As reported in the literature concerning the ODS process, the liquid-liquid extraction technique using water-soluble polar solvents, such as DMSO, DMF, methanol, and acetonitrile, is usually employed. DMSO and DMF have a high extractability for sUlfones but have a high boiling point, which is close to the boiling point of the sulfones, and thus they may not be reused for further extraction based on recovery by distillation. Methanol and acetonitrile are preferred for use as the extraction solvent, since they have relatively low boiling points and are separated easily from the sulfones and other oxidized sulfur species by distillation. When methanol and acetonitrile are contacted with light oil, a large quantity of aromatics is extracted simultaneously with the sulfones. The addition of water, however, suppresses the extractability of the aromatics. Examples of polar solvents include those with high values of the Hildebrand solubility parameter .delta.; liquids with a .delta, higher than about 22 have been successfully used to extract these compounds. Examples of polar liquids, with their Hildebrand values, are shown in the following: Table IT. Hildebrand Values of Various Useful Polar Solvents (Table Removed) However, as will be obvious to those of ordinary skill in the art, mere polarity considerations are insufficient to define successful extraction solvents. Methanol, for instance, has sufficient polarity, but its density, 0.79 g/cc, is about the same as that of a typical light oil, making separations very difficult. Other properties to consider include boiling point, freezing point, viscosity, and surface tension. Surprisingly, the combination of the properties exhibited by DMSO make it an excellent solvent for extracting oxidized sulfur and nitrogen compounds from liquid light oil, but unfortunately it contains a large proportion of sulfur. Heteroatom solvents containing nitrogen, phosphorous, and sulfur must be very volatile to ensure stripping of the solvent out of the diesel oil. The preferred solvents in this process are acetonitrile and methanol, due to their polarity, volatility, and low cost. In the second stage or step, the oxidized sulfur compounds are extracted in countercurrent extractor 16 of the Karr, Scheibel, or other configuration of countercurrent or stirred tank extractor to remove tne oxidized sulfur compounds from the diesei oil. The extraction phase is composed of an aqueous solution containing from about 10 to about 30% water in a polar organic solvent, including acetonitrile, methanol, or other solvent. Therefore, the solvents should be sufficiently polar to be selective for polar compounds in the process of extraction. In a third stage of the process a stripper column is employed to remove traces of the solvent from the diesel oil. The solvent is recovered and sent to the solvent recovery fractionator 20. In a fourth stage of the process, the extraction-rich solvent is recovered in a stripper recovery flash evaporator (not shown). Bottoms from the evaporator are purged to a sulfone storage tank to be sold as petrochemical intermediates, or added to fuel oil or crude oil. In a fifth stage of this process, the diesel oil is passed through an adsorbent polishing column which removes the last traces of sulfur to below 10 ppm w/w from the diesel oil. Many adsorbents can be used for this purpose, including activated carbon, silica gel, alumina and other inorganic adsorbents. In a preferred embodiment of this invention, a new adsorbent comprised of polar polymers coated onto inert, but high surface area supports, such as silica gel, alumina, and activated carbon are utilized. These polymers include, among other candidates, polysulfones, polyacrylonitrile, polystyrene, polyester terepthalate, polyurethane, and other polymers which demonstrate affinity for oxidized sulfur species. The advantage of using the polymer coated onto the support is that the adsorption and desorbtion processes are rapid and reversible, and the adsorbates are easily recovered, and the column is easily regenerated by extraction with a suitable solvent and dried. EXAMPLES 1-7 Insofar as the catalyst preparations and oxidations disclosed in the following examples are concerned, guidance was provided by the following references for their respective examples. 1. Venturello , Carlo, et al ,US Patent 4,562,276, Peroxide Composition Based on Tungsten and Phosphorus or Arsenic and Processes and Uses Relative Thereto, December 31, 1985. 2. Bonsignore, Stefanio, et al, US Patent 5,324,849 Class of Peroxy Compounds Based on Tungsten and Diphoshonic Acids and Process for Obtaining Them, June 28, 1994. 3. Te, Mure, et al, Oxidation Reactivities of Dibenzothiophenes in Polyoxymetalate/HaOj and Formic Acid/H2O2 Systems, Applied Catalysis A: General 219 (2001) 267-280. 4. Shum, Wilfred, et al, Production of Molybdenum Dioxo Dialkyleneglycolate Compositions for Epoxidation of Olefms, US Patent 4,607,113, August 19, 1986. 5. Campos-Martin, I. M., et al, Highly Efficient Deep Desulfurization of Fuels by Chemical Oxidation, Green Chemistry, 2004, 6, 556-562. 6. Hu, Changwen, Catalysis by Heteropoly Compounds XXII. Reactions of Esters and Esterifications Catalyzed by Heteropolyacids in a Homogeneous Liquid Phase, Journal of Catalysisl43, 437-448 (1993). 7. Bressan, Mario, et al, Oxidation of Dibenzothiophene by Hydrogen Peroxide or Monopersulfate and Metal-Sulfophthalocyanine Catalysts, New Journal of Chemistry, 2003, 27, 989-993. EXAMPLE 1. TETRAOCTYL-AMMONIUMPHOSPHOTUNGSTATE Carlo Venturello Catalyst {(C8H17)4N}3PW4O2-4 FW 2550.99) A. Preparation of Venturello Catalyst: Sodium tungstate, Na2WO4.2H2O (3.30 g, 10 mmol) was weigned to a 250 ml beaker and 7 ml of 30% aqueous hydrogen peroxide, H2O2 was added and stirred at 25 °C until a colorless solution was obtained. To this solution, was added 1.0 ml 85 % phosphoric acid H3PO4 and the whole was diluted to 50 ml with water. To the resultant solution, 2.5 g of tetraoctylammonium chloride (Aldrich) in methylene chloride was added dropwise with stirring over about 2 min. Stirring was continued for an additional 15 mm. The organic phase was then separated, filtered, and evaporated at room temperature overnite to give 3.5 g of a colorless syrup. B. Oxidation of Arabian Light Gas Oil: A 100-ml sample of full range (FR) hydrotreated (HT) Arabian Light Gas Oil (ALGO) containing 910 ppm w/v of total sulfur was heated to 85 °C with stirring on a stirring hot plate. A 50-ml portion of 15 % w/w hydrogen peroxide in water was added then 50 mg of catalyst described above in A. Preparation of Venturello Catalyst, tris(cetyltrimethylammonium) phophotungstate (Venturello Catalyst) was added. The reaction was continued for 15 minutes then the reactants were cooled and poured into a 250-ml separatory funnel. The aqueous peroxide lower phase was withdrawn and discarded. A sample of the oil phase was analyzed by gas chromatography with a Sievers Sulfur Chemiluminescence Detector (GC-SCD), and compared with a sample of the original FR HT ALGO. The chromatogram showed the presence of apparently the same amount of sulfur, but the sulfur peaks were displaced until later in the chromatogram, indicating the formation of sulfones. Sulfur analysis showed the oxidized sample to contain 880 ppm w/v sulfur, allowing for analytical error, indicating no removal of the sulfur. C. Batch Extraction Of Oxidized Oil: The 100 ml sample of oil phase prepared in B above, Oxidation of Arabian Light Gas Oil, was extracted twice with 50 ml portions of acetonitrile containing 10 % v/v distilled water. After the second extraction, 98 ml of oil was recovered, and analyzed for total sulfur and was found to contain 60 ppm sulfur w/v. The oil sample was analyzed by GC-SCD and the original and oxidized sulfur peaks were practically all removed. The two extracts were combined and were evaporated overnight to a dry oil, and was then analyzed by GCMS and GC-SCD. The GC-SCD indicated the presence of the alkyibenzothiophene-dioxides and alkyldibenzothiophene-dioxides that were present originally in the oxidate oil. GCMS results indicated the presence of methyl, dimethyl, trimethyl, and tetramethyl benzothiophene sulfones and dibenzothiophene sulfones. D. Countercurrent Extraction Of Oxidized Oil: A 100-ml sample of full range (FR) Hydrotreated (HI) Arabian Light Gas Oil (ALGO) containing 910 ppm w/v of total sulfur was oxidized as in B above, Oxidation of Arabian Light Gas Oil, but was not extracted. The 100 ml sample of oxidized oil containing approximately 900 ppm w/v sulfur as sulfones, was transferred to a 2.5 cm by 75 cm fritted countercurrent extraction apparatus containing 50 cm of glass beads of 3 mm diameter. A Hitachi L2000 laboratory pump was used to pump 150 ml of acetonitrile:water 90:10 v/v at 10 ml/min upward through the fritt and through the oxidized oil After countercurrent extraction with the mixed polar solvent, the oil was withdrawn from the extraction apparatus and analyzed by GC-SCD and for total sulfur. No sulfur peaks were detected in the extracted oil, and total sulfur analysis gave a value of 25 ppm w/v. E. Polishing Of Extracted Oxidized Oil "With Solid Phase Adsorbant Media: A 100-ml sample of full range (FR) Hydrotreated (HT) Arabian Light Gas Oil (ALGO) containing 910 ppm w/w of total sulfur was oxidized and extracted exactly as in Examples B and C, above. The sample of oxidized and extracted oil was passed through a 2.5 cm diameter by 50 cm high fritted chromatography column containing 10 grams of Millipore Cyano Bonded solid phase extraction media. The effluent from the column was analyzed by GC-SCD and found to contain no detectable sulfur peaks. Sulfur analysis by Antek total sulfur gave a result of 8 ppm w/v. F. Polishing Oxidized Extracted Oil by Alumina: The 100-ml sample of oxidized and extracted oil prepared instep D above, Countercurrent Extraction Of Oxidized Oil, was passed through a 23 cnf diameter by50 6m height fritted chromatography column containing 10 grams of Davidson alumina. The effluent from the column was analyzed by GC-SCD and found to contain no detectable sulfur peaks. Sulfur analysis by Antek total sulfur gave a result of 5 ppm w/v. EXAMPLE 2, MOLYBDOTUNGSTIC PHOSPHONATE Stefanio Bonsignore Catalyst Mo2W7O30 2N(CH2PO)3 (FW 2217.75) A. Preparation of Bonsignore Catalyst: Weighed 3.54 grams (NH4)«Mo7O24*4H2O (FW 1235.86) 23.10 grams Na2WO4'2H2O (FW 329.86) into 250 ml beaker and added 100 ml distilled water. The solution contains 20 meq of molybdenum and 70 meq of tungsten. Stirred vigorously for 15 minmutes until the solution became clear and colorless. Transferred 3 ml of the solution to a 20 ml vial. Added 1.0 ml of 30 % hydrogen peroxide and mixed until a wine- red color developed. Added 2.00 ml of a 30 % (1.0 M) solution (2.0 millimole) of amino-tris- methylenephosphonic acid (ATMP) N(CH2PO3H2)3 (MW 299.05). The solution quickly turned greenish-yellow. B. Oxidation and Analysis of Oil: Prepared 100 ml of full range hydrotreated straight run diesel in a 400 ml beaker. Added 50 ml of 15 % hydrogen peroxide and began heating and stirring. Added 25 mg of tetradecyl ammonium bromide (TDAB) phase transfer catalyst. Added the 5.0 ml of prepared peroxo-molybdotungstate trisphosphonate catalyst into the oil-water- peroxide mixture. Continued heating to 80 °C, then held between 80-100 °C for 40 minutes. Oxidate mixture was cooled and transferred to a 250 ml separator/ funnel. The lower aqueous layer was separated and discarded, and the oil layer was transferred to a 200 ml polyethylene bottle. A: sample orthe oil was analyzed by, Sievers GC-SCD. All of the sulfur peaks were shifted to the sulfone region of the chromatogram. Apparent conversion is 100 %. EXAMPLE 3. DODECAMOLYBDOPHOSPHORIC ACID Mere Te Catalyst Phosphomolybdic Acid H3PO4Mo12O36XH2O (FW1825.25) A Preparation of Catalyst: Two grams of molybdic acid (Fisher MoO3 89.1 %) was weighed into a 400 ml beaker. 40 ml distilled water was added. NaOH pellets 0.25 g were added and the mixture was stirred until all dissolved. Two grams of ammonium para-molybdate (NH4)6Mo7O244H2O)was added and swirled with NaOH pellets 0.5 g added. This mixture was stirred for 10 minutes until all dissolved. 5.0 ml of 85 % phosphoric acid was added and stirring continued. Then 3.0 ml of concentrated nitric acid was added, with continuous stirring. The solution gave a very faint yellow tinge. B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 400 ml beaker. 50 ml of 15 % hydrogen peroxide was added. Two ml of the catalyst solution above was added with stirring as the sample was heated. 50 mg of hexadecylpyridinium chloride (Aldrich) was added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous layer was removed and discarded. The oil was transferred to a 200 ml polyethylene bottle, and was analyzed by Sievers GC-SCD. Approximately 20 % of the sulfur peaks shifted to later retention times, indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones. EXAMPLE 4. DIOXOMOLYBDENUM AMINO-DHSOPROPANOLATE Wilfred Shum Catalyst MoOzNBKCHCH3CH2O)2 (FW 763.03) A, Catalyst Preparation: Ammonium paramolybdate 17.7 grams (FW 1235.86) was weighed into a 400 ml beaker and 125 ml distilled water was added. 40 ml of aqueous 40 % diisopropanol amine (technical grade) was added with stirring. The solution was heated to 135 °C with stirring. A slow stream of air was bubbled through the solution as it was heated for eight hours. B. Oxidation and Analysis of Oil: 100 ml of Hydrotreated Diesel was added to a 400 ml beaker. 50 ml of 15 % hydrogen peroxide was added. Two ml of the catalyst solution above was added with stirring as the sample was heated. 50 mg of tetra-octyl ammonium bromide was added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous layer was removed and discarded. The oil was transferred to a 200 ml polyethylene bottle, and was analyzed by Sievers GC-SCD. Approximately 10 % of the sulfur peaks shifted to later retention tunes, indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones. EXAMPLE 5. TRIPHOSPHONO-POLYPEROXOTUNGSTATE J. M. Campos-Martin Catalyst N(CH2PO)3 (WO5)9 (FW 2571.54) A. Preparation of Catalyst: Sodium tungstate Na2W(V2H:zO (3.0 grams) was dissolved hi 10 ml of 30 % hydrogen peroxide, to form a bright yellow solution. Three ml of a 30 % solution of amino (tris) methylenephosphonic (N(CH2PO3H2)3acid were added. The solution turned colorless immediately. This solution was diluted to 30 ml with distilled water. B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 400 ml beaker and 50 ml of 15 % hydrogen peroxide was added. Two ml of the catalyst solution above was added with stirring as the sample was heated; 50 mg of hexadecyltrimethyl ammonium bromide was added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous layer was removed and discarded. The oil was transferred to a 200 ml polyethylene bottle and was analyzed by Sievers GC-SCD. Approximately 90 % of the sulfur peaks shifted to later retention times indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones. EXAMPLE 6. BISMUTHOMOLYBDIC ACID Changwen Hu H5BiMo12O404H2O (FW 2077.34) A. Preparation of Catalyst: Bismuth nitrate 2.0 grams Bi(NO3)2'2H2O was dissolved in 50 ml of distilled water in a 250 ml beaker concentrated nitric acid was added dropwise until the solution was complete. Ammonium paramolybdate (NH4)6Mo7O24H2O 25.0 grams was weighed into a 400 ml beaker and was dissolved in 150 ml distilled water with vigorous stirring. A white precipitate formed immediately and was aged at 50 °C for 6 hours. The product was filtered, washed with distilled water, then dried overnite. The sample was broken up to powder and mixed, then calcined for 12 hours at 450 °C. B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 400 ml beaker. 50 ml of 15 % hydrogen peroxide was added. 100 mg of the catalyst was added with stirring as the sample was heated. 50 mg of tetraoctyl ammonium bromide was added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous layer was removed and discarded. The oil was transferred to a 200 ml polyethylene bottle, and was analysed by Stem GC-SCD. At least 95 % of the sulfur peaks shifted to later retention times, indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones. EXAMPLE 7. SODIUM SULFOPHTHALOCYANINE COBALT PEROXIDE Mario Bressan Catalyst Na4C32H12N8S4O12Co[II])O2 (FW 1011.64) A. Preparation of Catalyst: Commercial UOP cobalt sulfophthalocyanine (Merox catalyst) 0.50 g was dissolved in 100 ml 10 % NaOH to prepare a 5000 ppm stock catalyst solution. 4.0 ml of the catalyst solution was added to 36 ml of an aqueous solution 3.8625% KHSO5 potassium monopersuifate (0.25 Molar) from Mallinkrodt. The catalyst solution was placed in a vial until used for oxidation. Final concentrations of the catalyst solution are 500 ppm of cobalt sulfophthalocyanine and 0.225M in potassium monopersuifate. B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 500-ml Erlenmeyer flask, and a condensor was fitted to the flask; 40 ml of the catalyst- monopersuifate solution was added and 60ml of acetonitrile was added with stirring as the sample was heated. The mixture was heated to 83 °C and held between 80MOO°C with total reflux and vigorous stirring for 3 hours. The sample was cooled at 5°C for two hours, and the two phases were separated. The contents of the Erlenmeyer flask were transferred to a 250-ml separatory funnel, and the lower aqueous-acetonitrile layer was removed and discarded. The oil was transferred to a 200-ml polyethylene bottle, and was analyzed by Sievers GC-SCD. Approximately 50% of the sulfur peaks were removed from the oil and some were shifted to later retention times, indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones. Approximately half of the sulfur was removed from the oil and transferred to the acetonitrile-water phase. WE CLAIM:- 1. A process for reducing the sulfur content of diesel fuel, comprising the steps of: a) contacting a diesel fuel containing sulfur compounds in a reactor with an oxidant selected from the group consisting of sulfuric acid, peracetic acid, hydrogen peroxide, sodium hypochlorite, perchloric acid, nitric acid, sodium or potassium peroxidisulfate or peroxymonosuifate, and mixtures thereof, in the presence of a homogeneous or heterogeneous oxidation catalyst selected from the group of peroxo molybdotungstic phosphonate, phosphomolybdic acid, dioxomolybdenum amino-diisopropanolate, triphosphono-polyperoxotungstate, bismuthomolybdic acid, sodium sulfophthalocyanine cobalt peroxide, tetraamidomacrocyclic iron complexes, dioxomolybdenum diglycolate, transition metal tetraphenylporphyrin, transition metal acetylacetonate, bismuthomolybdates, dioxomolybdenum aminodiglycoiate, tetraalkylammonium metal sulftetraphenylporphyrin, molybdotungstic acid phosphonates, quaternary ammonium salts of polyoxometallates and simple metal oxides, and at a temperature of about 50°C to about 1 S0°C for a period of time sufficient to oxidize die sulfur compounds; and b) removing the oxidized sulfur compounds from the diesel fuel by a liquid-liquid countercurrent extraction with a water-soluble polar solvent 2. The process according to claim 1, including the steps of: a) stripping the solvent from the diesel fuel; and b) polishing the diesel fuel by passing it through an adsorbent to remove the remaining sulfur compounds. 3. The process according to claim 1, wherein the reactor is a countercuirent reactor. 4. The process according to claim 1, wherein the reactor is stirred, agitated, oscillated, or static. 5. The process according to claim 1, wherein the solvent is selected from the group consisting of aqueous solutions of acetonitrile and methanol. 6. The process according to claim 2, wherein the polishing is effected by an adsorbent bed consisting of polar organic groups coated or bound to a support selected from silica, alumina, or carbon. 7. The process according to claim 1, wherein the catalyst is tetraoctyl-ammonium phosphotungstate. 8. The process according to claim I, wherein the catalyst is a tetraalkylammonium polyoxometallate. 9. The process according to claim 1, wherein the catalyst is selected from the group consisting of Venturello, Campos-Martin, Bressan, Shum, Gollins-Horwitz, Beardon, Merox, Benedict, Bonsignore, Changwen Hu, and Mere Te types of catalysts. 10. The process of claim 5, wherein the solvent contains from about 10% to 30% water by volume. 11. The process of claim 11, wherein the solvent contains 10% water by volume. 12. The process of claim 1, wherein the concentration of sulfur in the treated diesel fuel is reduced to less than 10ppm. 13. A process for reducing the sulfur content of diesel fuel comprising: a) introducing an aqueous oxidant and a heterogeneous or homogenous catalyst selected from the group consisting of peroxo molybdotungstic phosphonate, phosphomolybdic acid, dioxomolybdenum amino-diisopropanolate, triphosphono-polyperoxotungstate, bismuthomolybdic acid, sodium sulfophthalocyanirie cobalt peroxide, tetraamidomacrocyclic iron complexes, dioxomolybdenum diglycoiate, transition metal tetraphenylporphyrin, transition metal acetylacetonate, bismuthomolybdates, dioxomolybdenum aminodiglycolate, tetraalkylammonium metal sulfotetraphenylpotphyrin, molybdotungstic acid phosphonates, quaternary ammonium salts of polyoxometallates and simple metal oxides into the top of a reactor column; b) contacting the oxidant and catalyst in countercurrent flow in the reactor with a diesel fuel boiling in the range of about 240°C to about 360°C; c) continuously oxidizing the sulfur compounds in the diesel oil; d) continuously extracting oxidized compounds from the diesel oil produced in the reactor by contact with an aqueous solution of a polar solvent in a column; e) removing traces of solvent from the hydrotreated diesel oil in a stripper column; f) recovering the aqueous solvent; and g) adsorbing any remaining traces of sulfur from the hydrotreated diesel oil with adsorbates selected from the group consisting of activated carbon, silica gel and alumina. 14. The process according to claim 13, wherein the catalyst is tetraoctyl-arnmonium phosphotungstate. 15. The process according to claim 13, wherein the catalyst is a tetraalkylammonium polyoxometallate. 16. The process of claim 13, wherein the solvent is selected from aqueous solutions of methanol and acetonitrile. 17. The process according to claim 13, wherein the concentration of sulfur in the hydrotreated diesel fuel is reduced to less than 10ppm. 18. The process of claim 6 in which the solid support is coated with polar polymers selected from the group consisting of polysulfone, polyacrylonitrite, polystyrene, polyester terephthlate and polyurethane. 19. The process of claim 1, wherein the catalyst is peroxo molybdotungstic phosphonate. 20. The process of claim 13, wherein (he catalyst is peroxo molybdotutigstic phosphonate. 21. The process of claim 1 in which the diesel fuel to be treated is a low sulfur hydrotreated diesel containing about 1000ppm by weight of sulfur. 22. The process of claim 1 in which the solvent is composed of approximately 10 to 30% water. 23. The process of claim 13 in which the solvent is composed of approximately 10 to 30% water. 24. A process for reducing the sulfur content of diesel fuel, substantially as hereinbefore described with reference to the foregoing description and drawing.

Full Text

BACKGROUND OF THE INVENTION
This invention is directed to the removal of sulfur-containing compounds from diesel fuel and, more particularly, their removal by a combination of oxidation and extraction steps.
PRIOR ART
The removal of sulfur compounds from petroleum streams has been of considerable importance in the past and is even more so today due to environmental considerations. Gas effluent from the combustion of organic materials, such as coal, almost always contain sulfur compounds and sulfur removal processes have concentrated on removing hydrogen sulfide since it has been considered a significant health hazard and also because it is corrosive, particularly when water is present. With increasing emphasis on eliminating or minimizing sulfur discharge to the atmosphere, attention is turning to the removal of other sulfur compounds from gas streams.
The removal of sulfur compounds and particularly chemically-combined sulfur, such as organosulfur compounds, from feedstreams is highly desirable to meet environmental concerns and to prevent potential catalyst deactivation as well as equipment corrosion.
Typically, hydrocarbon products contain various amounts of sulfur compounds in the form of, for example, chemically-combined sulfur, such as inorganically combined sulfur and organically combined sulfur, i.e., organosulfur compounds.
The presence of organosulfur compounds in hydrocarbon streams results naturally, as well as from the introduction of organosulfur compounds, into the hydrogen streams during conventional processes for producing and treating hydrocarbon products.
As previously indicated, if chemically-combined sulfur, such as organosulfur compounds, are not removed from the hydrocarbon streams, the presence of organosulfur compounds in the resultant hydrocarbon products, including natural gas, paraffins, olefins and aromatics, particularly gasoline, diesel or other fuels, can cause corrosion of processing equipment and engine parts, as well as other deleterious effects, particularly when water is present.
Oxidative desulfurization research for diesel and other oil streams has been ongoing for over 100 years. The following table summarizes patents granted from 1941 to 1976 addressed to oxidative desulfurization.

(Table Removed)
Paris-Marcano received two patents for oxidative desulfurization of petroleum using
nitric acid with hydrogen peroxide, U.S.P. 5,017,280 and 5,087,350. Gore of Petrostar received two patents for oxidative desulfurization U.S. 6,274,785 and 6,160,193. Cabrerra received a patent for a complex oxidative desulfurization patent assigned to UOP 6,171,478. Kappas from Unipure received two patents for oxidative desulfurization using performic acid: U.S.P. 6,402,940 and 6,406,616. Ohsohl of Unipure has received two patents, 5,985,137 and 5,948,242, for desulfurization of crude oil.
Jeanblanc received a patent, WO/001 5734, for radiative assisted oxidative desulfurization. Sulfur-containing carbonaceous materials are desulfurized by reaction with a mixture of an oxidizing agent and an oxygenated solvent such as diethyl ether under alkaline conditions at a temperature preferably ranging from ambient temperature to about 121°C and pressure of about 1 to 2 atmospheres. The use of radiation - such as X-ray, infrared, visible microwave, or ultraviolet radiation, alpha, beta or gamma radiation, other atomic radiation emanating from a radioactive material, or ultrasound - facilitates desulfurization. The products of the reaction are a desulfurized carbonaceous material in which the sulfur content is, for example, less than about 1% and separated sulfur compounds.
Yen, U.S.P. 6,402,939, at Cal Tech received a patent for ultrasonic assisted oxidative desulfurization. Gunnerman has obtained several patents using ultrasonic assistance: U.S.P. 6,500,219 and 6,652,592. Stowe disclosed a process to oxidatively desulfurize hydrocarbon oil with ultrasonic assistance in U.S.P. 5,547,563.Cullen disclosed in four recent U.S. patent applications assigned to Petrosonics oxidative, reactive, ultrasonic desulfurization technology: Serial Number 10/411,796 filed April 11, 2003, Sulfone Removal Process; Serial Number 10/429,369 filed May 5, 2003, Process For Generating
and Removing Sulfbxides from Fossil Fuel; Serial No. 10/431,666 filed May 8, 2003, Treatment of Crude Oil Fractions, Fossil Fuels & Products Thereof with Sonic Energy; and Serial Number 10/644,255 filed August 20, 2003, entitled Treatment of Crude Oil Fractions, Fossil Fuels & Products Thereof.
Collins, in U.S. Patent 5,847,120 and 6,054,580 disclosed long-lived tetra-amidomacriocyclic ligand complexes of iron as homogeneous oxidation catalysts to promote peroxide oxidations. The complex provides a stable, long-lived oxidation catalyst or catalyst activator.
Kocal in U.S. Patent 6,277,271 August 21, 2001 assigned to UOP discloses a process for the desulfurization of a hydrocarbonaceous oil This is a process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil and a recycle stream containing sulfur-oxidated compounds is contacted with a hydro desulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The residual oxidizing agent is decomposed and the resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated to produce a stream containing the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds. At least a portion of the sulfur-oxidated compounds is recycled to the hydrodesulfurization reaction zone.
In another UOP assigned patent, Kocal in U.S. Patent No. 6,368,495 granted April 9, 2002 discloses the removal of sulfur-containing compounds from liquid hydrocarbon streams using hydrogen peroxide on air, with heterogeneous transition metal catalysts. The

process more specifically addresses the removal of thiophenes and thlophene derivatives from a number of petroleum fractions, including gasoline, diesel fuel, and kerosene. In the first step of the process, the liquid hydrocarbon is subjected to oxidation conditions hi order to oxidize at least some of the thiophene compounds to sulfones. Then, these sulfones can be catalytically decomposed to hydrocarbons (e.g. hydroxybiphenyl) and volatile sulfur compounds (e.g., sulfur dioxide). The hydrocarbon decomposition products remain in the treated liquid as valuable blending components, while the volatile sulfur compounds are easily separable from the treated liquid using well-known techniques such as flash vaporization or distillation.
Cabrera discloses in U.S. Patent 6,174,178 granted January 9, 2001, a process for the desulfurization of a hydrocarbonaceous oil. A process for the desulfurization in which the hydrocarbonaceous oil is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level and then contacting the resulting hydrocarbonaceous stream from the desulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated after decomposing any residual oxidizing agent to produce a stream containing the sulfur-oxidated compounds and a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds.
Shum teaches in U.S. Patent No. 4,772,731 granted September 20, 1988, the epoxidatkm of olefins with molybdenum dioxo dialkyleneglycolate compositions. Production of novel molybdenum dioxo dialkyleneglycolate compositions, especially adapted for use as catalysts in the epoxidation of olefmic compounds with an organic hydroperoxide, by reaction of
molybdenum trioxide with particular dialkylene glycol compounds at specified elevated temperatures while removing water,
Shum discloses in U.S. Pat. No. 5,780,655 granted July 14, 1998, an epoxidation process using an alkylammonium phosphate-stabilized peroxotungstate compound as catalyst. Olefins are selectively converted to epoxides using hydrogen peroxide as oxidant in a single liquid phase reaction, system characterized by a liquid phase comprised predominantly of an organic solvent. The reaction is catalyzed by a compound comprised of a phosphate-stabilized peroxotungstate species having a W:P atomic ratio of 2:1. This invention pertains to methods of converting olefins to epoxides in a single liquid phase using hydrogen peroxide and a catalyst in salt or acid form comprising a species corresponding to (RiNfePWjO^OH).
Venturelto in U.S. Patent No. 5,274,140 discloses a process for olefin epoxidation by reaction with hydrogen peroxide according to a double phase technique (i.e., a biphasic reaction system containing both an aqueous phase and an oganic phase). The catalyst system consists of a first component which is at least one element selected from W, Mo, V or a derivative thereof and a second component which is at least one derivative selected from the derivatives of P and As. The mutual atomic ratio of the catalyst components is between 12 and 0.1, but preferably is between 1.5 and 0.25.
Venturello in U.S. Patent No. 4,562,276 and 4,595,671 describes epoxidation catalysts for olefmic compounds, both in a homogeneous aqueous phase as well as in a heterogeneous phase. The catalysts correspond to the formula QaXW^O^-iu wherein Q represents a cation of an anionic salt, X is either P or As, while nK), 1, or 2. The atomic ratio of W:P, where X=P, thus must be 4. The use of such compositions in an epoxidation wherein the reactants are maintained in a single substantially organic phase is not disclosed.
Bonsignore in U.S. Pat. No. 5,324,849 teaches a class of compounds based on tungsten and diphosphonic acids which contain active oxygen atoms and cationic groups derived from onium salts. Such compounds are said to catalyze olefm oxidation reactions in double phase reaction systems containing both an organic phase and an aqueous phase. The compounds contain two phosphorus atoms and five tungsten atoms and thus have a W:P atomic ratio of 5:2.
However, the biphasic reaction systems of the type described in the aforementioned patents have a number of disadvantages which limit their usefulness in large scale commercial practice. The need to use a phase transfer agent contributes significantly to the cost of operation. Mass transfer problems are frequently encountered, particularly for relatively volatile olefins such as propylene. Additionally, there are considerable engineering difficulties associated with operating two phase reactors and phase separators. Thus, there is a need to develop active catalysts capable of providing high selectivity to epoxide during operation of a single phase epoxidation process.
SUMMARY OF THE INVENTION
The process of the present invention is directed to the desulfurization of a full-range, hydro treated diesel oil with an aqueous oxidizing agent in the presence of a catalyst and a co-catalyst, and thereafter selectively removing the oxidized compounds by solvent extraction. Optionally, the foregoing steps are followed by solvent stripping and recovery, and finally by a polishing step.
BRIEF DESCRIPTION OF THE DRAWING
The attached figure is a schematic drawing of the process of the present invention.
Detailed Description of the Invention
9
As can be seen by reference to the attached drawing sheet, hydrotreated diesel in a storage tank 10 is fed into reactor column 12 where it is subjected to continuous oxidation by reaction with an aqueous oxidant and a complex catalyst which is fed into the top of column 12 from a storage tank 14. The aqueous oxidant can be, for example, hydrogen peroxide, sodium hypochlorite or sodium peroxysulfate which is catalyzed by a complex catalyst, followed by a continuous liquid-liquid extraction of the diesel oil by a mixture of water and a polar solvent.
The process serves to desulfurize full range hydrotreated diesel oil with a boiling range of about 240°C to about 360°C. The process consists of treating the diesel oil in a countercurrent or a stirred tank reactor with an aqueous solution of hydrogen peroxide hi the presence of a catalyst and a co-catalyst which is also known as a phase transfer agent. This action results hi effecting the oxidation of the sulfur species present hi the hydrotreated (HT) diesel at a nominal level of 1000 ppm w/w of total sulfur. The sulfur species present are oxidized to their corresponding sulfoxides, sulfones, sultines, sultones, sulfonates, sulfinates, or even to sulfur dioxide and sulfur trioxide and sulfite and sulfate.
The catalyst employed may be selected from a number of homogeneous or heterogeneous oxidation catalysts including tetraamidomacrocylic iron complexes, tetraalkylammonim polyoxometallates, dioxomolybdenum diglycolate, transition metal tetraphenylporphyrin, transition metal acetylacetonate, bismuthomolybdates, dioxomolybdenum aminodiglycolate, tetraalkylammonim metal sulfbtetraphenylporphyrin, molybdotungstic acid phosphonates, as well as many others. These may include quaternary ammonium salts of polyoxometallates, simple metal oxides, Venturello, Campos-Martin, Bressan, Shum, Collins-Horwitz, Beardon, Folin-Denis Reagent, Benedict, Bonsignore, Changwen Hu, Mere Te, Keggin, Dawson, Bearden,
and Merox type catalysts. These may include tetraoctyl-ammonium phosphotungstate, peroxo molybdotungstic phosphonate, phosphomolybdic acid, dioxomolybdenum amino-diisopropanolate, triphosphono-polyperoxotungstate, bismuthomolybdic acid, sodium sulfophthalocyanine cobalt peroxide.
The co-catalysts are employed to enhance and accelerate reactions which though favored thermodynamically, are very slow due to mass transfer issues. They may be anionic cationic and nonionic, with cationic phase transfer agents being preferred. In the present invention, the co-catalyst in each case is the quaternary amine salt used in the synthesis.
These salts do not always have to be pre-formed prior to the reaction, but may be formed in-sttu, by adding the transition metal salt or acid and then adding to the same solvent sytem, for example, aqueous peroxide, the phase transfer agent, such as a quaternary ammonium halide. Representative phase transfer agents are methyltrioctyl-ammonium bromide, ceryltrimethylammonium bromide, tetrabutyl ammonium chloride, tetradecyl pyridhim chloride, and tetradecyl pyridinium bromide.
The oxidation reaction takes place in a countercurrent reactor 12, which may be static, stirred, agitated, with oscillating or rotating discs, at a temperature between 50 to 1501°C preferably between about 70 and about 110°. Raffinate from the oxidation which contains residual catalyst, spent or residual oxidant, is recycled to the oxidant-catalyst storage tank 14, where make-up catalyst and oxidant are added.
The concentration of the catalysts may be between about 0.001 and about 1.00, by weight % on oxidant, and preferably between about 0.01 and about 0.10 weight %. Oxidant concentrations may vary between about 1% and about 100%, by weight, but are typically between about 10% and about 50%, and in the case of hydrogen peroxide are preferably between
about 15% and about 30%, by weight, in the aqueous phase. Oxidants vary by chemical type, oxidation potential, efficacy, stability, solubility and persons of ordinary skill in the art can establish readily the useful and effective concentrations of oxidant. Oxidants which can be used in the present process include hydrogen peroxide, sodium hypchlorite, sodium or potassium peroxydisulfate or peroxymonosulfate, t-butyl hydroperoxide, perchloric acid, nitric acid, sulfuric acid, performic acid, and mixtures thereof.
The second step of the process involves the removal of the oxidized compounds by contacting the distillate with a selective extraction solvent in column 16. As reported in the literature concerning the ODS process, the liquid-liquid extraction technique using water-soluble polar solvents, such as DMSO, DMF, methanol, and acetonitrile, is usually employed. DMSO and DMF have a high extractability for sUlfones but have a high boiling point, which is close to the boiling point of the sulfones, and thus they may not be reused for further extraction based on recovery by distillation. Methanol and acetonitrile are preferred for use as the extraction solvent, since they have relatively low boiling points and are separated easily from the sulfones and other oxidized sulfur species by distillation. When methanol and acetonitrile are contacted with light oil, a large quantity of aromatics is extracted simultaneously with the sulfones. The addition of water, however, suppresses the extractability of the aromatics. Examples of polar solvents include those with high values of the Hildebrand solubility parameter .delta.; liquids with a .delta, higher than about 22 have been successfully used to extract these compounds. Examples of polar liquids, with their Hildebrand values, are shown in the following:
Table IT. Hildebrand Values of Various Useful Polar Solvents

(Table Removed)
However, as will be obvious to those of ordinary skill in the art, mere polarity considerations are insufficient to define successful extraction solvents. Methanol, for instance, has sufficient polarity, but its density, 0.79 g/cc, is about the same as that of a typical light oil, making separations very difficult. Other properties to consider include boiling point, freezing point, viscosity, and surface tension. Surprisingly, the combination of the properties exhibited by DMSO make it an excellent solvent for extracting oxidized sulfur and nitrogen compounds from liquid light oil, but unfortunately it contains a large proportion of sulfur. Heteroatom solvents containing nitrogen, phosphorous, and sulfur must be very volatile to ensure stripping of the solvent out of the diesel oil. The preferred solvents in this process are acetonitrile and methanol, due to their polarity, volatility, and low cost.
In the second stage or step, the oxidized sulfur compounds are extracted in countercurrent extractor 16 of the Karr, Scheibel, or other configuration of countercurrent or stirred tank
extractor to remove tne oxidized sulfur compounds from the diesei oil. The extraction phase is composed of an aqueous solution containing from about 10 to about 30% water in a polar organic solvent, including acetonitrile, methanol, or other solvent. Therefore, the solvents should be sufficiently polar to be selective for polar compounds in the process of extraction.
In a third stage of the process a stripper column is employed to remove traces of the solvent from the diesel oil. The solvent is recovered and sent to the solvent recovery fractionator 20.
In a fourth stage of the process, the extraction-rich solvent is recovered in a stripper recovery flash evaporator (not shown). Bottoms from the evaporator are purged to a sulfone storage tank to be sold as petrochemical intermediates, or added to fuel oil or crude oil.
In a fifth stage of this process, the diesel oil is passed through an adsorbent polishing column which removes the last traces of sulfur to below 10 ppm w/w from the diesel oil. Many adsorbents can be used for this purpose, including activated carbon, silica gel, alumina and other inorganic adsorbents. In a preferred embodiment of this invention, a new adsorbent comprised of polar polymers coated onto inert, but high surface area supports, such as silica gel, alumina, and activated carbon are utilized. These polymers include, among other candidates, polysulfones, polyacrylonitrile, polystyrene, polyester terepthalate, polyurethane, and other polymers which demonstrate affinity for oxidized sulfur species. The advantage of using the polymer coated onto the support is that the adsorption and desorbtion processes are rapid and reversible, and the adsorbates are easily recovered, and the column is easily regenerated by extraction with a suitable solvent and dried.
EXAMPLES 1-7
Insofar as the catalyst preparations and oxidations disclosed in the following examples are concerned, guidance was provided by the following references for their respective examples.
1. Venturello , Carlo, et al ,US Patent 4,562,276, Peroxide Composition Based on Tungsten
and Phosphorus or Arsenic and Processes and Uses Relative Thereto, December 31, 1985.
2. Bonsignore, Stefanio, et al, US Patent 5,324,849 Class of Peroxy Compounds Based on
Tungsten and Diphoshonic Acids and Process for Obtaining Them, June 28, 1994.
3. Te, Mure, et al, Oxidation Reactivities of Dibenzothiophenes in Polyoxymetalate/HaOj
and Formic Acid/H2O2 Systems, Applied Catalysis A: General 219 (2001) 267-280.
4. Shum, Wilfred, et al, Production of Molybdenum Dioxo Dialkyleneglycolate
Compositions for Epoxidation of Olefms, US Patent 4,607,113, August 19, 1986.
5. Campos-Martin, I. M., et al, Highly Efficient Deep Desulfurization of Fuels by Chemical
Oxidation, Green Chemistry, 2004, 6, 556-562.
6. Hu, Changwen, Catalysis by Heteropoly Compounds XXII. Reactions of Esters and
Esterifications Catalyzed by Heteropolyacids in a Homogeneous Liquid Phase, Journal of
Catalysisl43, 437-448 (1993).
7. Bressan, Mario, et al, Oxidation of Dibenzothiophene by Hydrogen Peroxide or
Monopersulfate and Metal-Sulfophthalocyanine Catalysts, New Journal of Chemistry, 2003, 27,
989-993.
EXAMPLE 1. TETRAOCTYL-AMMONIUMPHOSPHOTUNGSTATE Carlo Venturello Catalyst {(C8H17)4N}3PW4O2-4 FW 2550.99)
A. Preparation of Venturello Catalyst: Sodium tungstate, Na2WO4.2H2O (3.30 g, 10 mmol) was weigned to a 250 ml beaker and 7 ml of 30% aqueous hydrogen peroxide, H2O2 was added and stirred at 25 °C until a colorless solution was obtained. To this solution, was added 1.0 ml 85 % phosphoric acid H3PO4 and the whole was diluted to 50 ml with water. To the resultant solution, 2.5 g of tetraoctylammonium chloride (Aldrich) in methylene chloride was added dropwise with stirring over about 2 min. Stirring was continued for an additional 15 mm. The
organic phase was then separated, filtered, and evaporated at room temperature overnite to give 3.5 g of a colorless syrup.
B. Oxidation of Arabian Light Gas Oil: A 100-ml sample of full range (FR) hydrotreated
(HT) Arabian Light Gas Oil (ALGO) containing 910 ppm w/v of total sulfur was heated to 85 °C
with stirring on a stirring hot plate. A 50-ml portion of 15 % w/w hydrogen peroxide in water
was added then 50 mg of catalyst described above in A. Preparation of Venturello Catalyst,
tris(cetyltrimethylammonium) phophotungstate (Venturello Catalyst) was added. The reaction
was continued for 15 minutes then the reactants were cooled and poured into a 250-ml separatory
funnel. The aqueous peroxide lower phase was withdrawn and discarded. A sample of the oil
phase was analyzed by gas chromatography with a Sievers Sulfur Chemiluminescence Detector
(GC-SCD), and compared with a sample of the original FR HT ALGO. The chromatogram
showed the presence of apparently the same amount of sulfur, but the sulfur peaks were
displaced until later in the chromatogram, indicating the formation of sulfones. Sulfur analysis
showed the oxidized sample to contain 880 ppm w/v sulfur, allowing for analytical error,
indicating no removal of the sulfur.
C. Batch Extraction Of Oxidized Oil: The 100 ml sample of oil phase prepared in B above,
Oxidation of Arabian Light Gas Oil, was extracted twice with 50 ml portions of acetonitrile
containing 10 % v/v distilled water. After the second extraction, 98 ml of oil was recovered, and
analyzed for total sulfur and was found to contain 60 ppm sulfur w/v. The oil sample was
analyzed by GC-SCD and the original and oxidized sulfur peaks were practically all removed.
The two extracts were combined and were evaporated overnight to a dry oil, and was then
analyzed by GCMS and GC-SCD. The GC-SCD indicated the presence of the
alkyibenzothiophene-dioxides and alkyldibenzothiophene-dioxides that were present originally in the oxidate oil. GCMS results indicated the presence of methyl, dimethyl, trimethyl, and tetramethyl benzothiophene sulfones and dibenzothiophene sulfones.
D. Countercurrent Extraction Of Oxidized Oil: A 100-ml sample of full range (FR)
Hydrotreated (HI) Arabian Light Gas Oil (ALGO) containing 910 ppm w/v of total sulfur was
oxidized as in B above, Oxidation of Arabian Light Gas Oil, but was not extracted. The 100 ml
sample of oxidized oil containing approximately 900 ppm w/v sulfur as sulfones, was transferred
to a 2.5 cm by 75 cm fritted countercurrent extraction apparatus containing 50 cm of glass beads
of 3 mm diameter. A Hitachi L2000 laboratory pump was used to pump 150 ml of
acetonitrile:water 90:10 v/v at 10 ml/min upward through the fritt and through the oxidized oil
After countercurrent extraction with the mixed polar solvent, the oil was withdrawn from the
extraction apparatus and analyzed by GC-SCD and for total sulfur. No sulfur peaks were
detected in the extracted oil, and total sulfur analysis gave a value of 25 ppm w/v.
E. Polishing Of Extracted Oxidized Oil "With Solid Phase Adsorbant Media: A 100-ml
sample of full range (FR) Hydrotreated (HT) Arabian Light Gas Oil (ALGO) containing 910
ppm w/w of total sulfur was oxidized and extracted exactly as in Examples B and C, above. The
sample of oxidized and extracted oil was passed through a 2.5 cm diameter by 50 cm high fritted
chromatography column containing 10 grams of Millipore Cyano Bonded solid phase extraction
media. The effluent from the column was analyzed by GC-SCD and found to contain no
detectable sulfur peaks. Sulfur analysis by Antek total sulfur gave a result of 8 ppm w/v.
F. Polishing Oxidized Extracted Oil by Alumina: The 100-ml sample of oxidized and
extracted oil prepared instep D above, Countercurrent Extraction Of Oxidized Oil, was passed
through a 23 cnf diameter by50 6m height fritted chromatography column containing 10 grams of Davidson alumina. The effluent from the column was analyzed by GC-SCD and found to contain no detectable sulfur peaks. Sulfur analysis by Antek total sulfur gave a result of 5 ppm w/v.
EXAMPLE 2, MOLYBDOTUNGSTIC PHOSPHONATE Stefanio Bonsignore Catalyst Mo2W7O30 2N(CH2PO)3 (FW 2217.75)
A. Preparation of Bonsignore Catalyst: Weighed 3.54 grams (NH4)«Mo7O24*4H2O (FW
1235.86) 23.10 grams Na2WO4'2H2O (FW 329.86) into 250 ml beaker and added 100 ml
distilled water. The solution contains 20 meq of molybdenum and 70 meq of tungsten. Stirred
vigorously for 15 minmutes until the solution became clear and colorless. Transferred 3 ml of
the solution to a 20 ml vial. Added 1.0 ml of 30 % hydrogen peroxide and mixed until a wine-
red color developed. Added 2.00 ml of a 30 % (1.0 M) solution (2.0 millimole) of amino-tris-
methylenephosphonic acid (ATMP) N(CH2PO3H2)3 (MW 299.05). The solution quickly turned
greenish-yellow.
B. Oxidation and Analysis of Oil: Prepared 100 ml of full range hydrotreated straight run
diesel in a 400 ml beaker. Added 50 ml of 15 % hydrogen peroxide and began heating and
stirring. Added 25 mg of tetradecyl ammonium bromide (TDAB) phase transfer catalyst. Added
the 5.0 ml of prepared peroxo-molybdotungstate trisphosphonate catalyst into the oil-water-
peroxide mixture. Continued heating to 80 °C, then held between 80-100 °C for 40 minutes.
Oxidate mixture was cooled and transferred to a 250 ml separator/ funnel. The lower aqueous layer was separated and discarded, and the oil layer was transferred to a 200 ml
polyethylene bottle. A: sample orthe oil was analyzed by, Sievers GC-SCD. All of the sulfur peaks were shifted to the sulfone region of the chromatogram. Apparent conversion is 100 %.
EXAMPLE 3. DODECAMOLYBDOPHOSPHORIC ACID
Mere Te Catalyst Phosphomolybdic Acid H3PO4Mo12O36XH2O (FW1825.25)
A Preparation of Catalyst: Two grams of molybdic acid (Fisher MoO3 89.1 %) was weighed into a 400 ml beaker. 40 ml distilled water was added. NaOH pellets 0.25 g were added and the mixture was stirred until all dissolved. Two grams of ammonium para-molybdate (NH4)6Mo7O244H2O)was added and swirled with NaOH pellets 0.5 g added. This mixture was stirred for 10 minutes until all dissolved. 5.0 ml of 85 % phosphoric acid was added and stirring continued. Then 3.0 ml of concentrated nitric acid was added, with continuous stirring. The solution gave a very faint yellow tinge.
B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 400 ml beaker. 50 ml of 15 % hydrogen peroxide was added. Two ml of the catalyst solution above was added with stirring as the sample was heated. 50 mg of hexadecylpyridinium chloride (Aldrich) was added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous layer was removed and discarded. The oil was transferred to a 200 ml polyethylene bottle, and was analyzed by Sievers GC-SCD. Approximately 20 % of the sulfur peaks shifted to later retention times, indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones.
EXAMPLE 4. DIOXOMOLYBDENUM AMINO-DHSOPROPANOLATE Wilfred Shum Catalyst MoOzNBKCHCH3CH2O)2 (FW 763.03)
A, Catalyst Preparation: Ammonium paramolybdate 17.7 grams
(FW 1235.86) was weighed into a 400 ml beaker and 125 ml distilled water was added. 40 ml of aqueous 40 % diisopropanol amine (technical grade) was added with stirring. The solution was heated to 135 °C with stirring. A slow stream of air was bubbled through the solution as it was heated for eight hours.
B. Oxidation and Analysis of Oil: 100 ml of Hydrotreated Diesel was added to a 400 ml
beaker. 50 ml of 15 % hydrogen peroxide was added. Two ml of the catalyst solution above
was added with stirring as the sample was heated. 50 mg of tetra-octyl ammonium bromide was
added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring
for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the
lower aqueous layer was removed and discarded. The oil was transferred to a 200 ml
polyethylene bottle, and was analyzed by Sievers GC-SCD. Approximately 10 % of the sulfur
peaks shifted to later retention tunes, indicating oxidation of benzothiophenes and
dibenzothiophenes to their respective sulfones.
EXAMPLE 5. TRIPHOSPHONO-POLYPEROXOTUNGSTATE J. M. Campos-Martin Catalyst N(CH2PO)3 (WO5)9 (FW 2571.54)
A. Preparation of Catalyst: Sodium tungstate Na2W(V2H:zO (3.0 grams) was dissolved hi 10 ml of 30 % hydrogen peroxide, to form a bright yellow solution. Three ml of a 30 % solution of amino (tris) methylenephosphonic (N(CH2PO3H2)3acid were added. The solution turned colorless immediately. This solution was diluted to 30 ml with distilled water.
B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 400 ml beaker and 50 ml of 15 % hydrogen peroxide was added. Two ml of the catalyst solution above was added with stirring as the sample was heated; 50 mg of hexadecyltrimethyl ammonium bromide was added, and the solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes. The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous layer was removed and discarded.
The oil was transferred to a 200 ml polyethylene bottle and was analyzed by Sievers GC-SCD. Approximately 90 % of the sulfur peaks shifted to later retention times indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones.
EXAMPLE 6. BISMUTHOMOLYBDIC ACID Changwen Hu H5BiMo12O404H2O (FW 2077.34)
A. Preparation of Catalyst: Bismuth nitrate 2.0 grams Bi(NO3)2'2H2O was dissolved in 50
ml of distilled water in a 250 ml beaker concentrated nitric acid was added dropwise until the
solution was complete. Ammonium paramolybdate (NH4)6Mo7O24H2O 25.0 grams was
weighed into a 400 ml beaker and was dissolved in 150 ml distilled water with vigorous stirring.
A white precipitate formed immediately and was aged at 50 °C for 6 hours. The product was
filtered, washed with distilled water, then dried overnite. The sample was broken up to powder
and mixed, then calcined for 12 hours at 450 °C.
B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 400 ml
beaker. 50 ml of 15 % hydrogen peroxide was added. 100 mg of the catalyst was added with
stirring as the sample was heated. 50 mg of tetraoctyl ammonium bromide was added, and the
solution was heated to 80 °C and held between 80-100 °C with vigorous stirring for 30 minutes.
The sample was cooled and transferred to a 250 ml separatory funnel, and the lower aqueous
layer was removed and discarded. The oil was transferred to a 200 ml polyethylene bottle, and
was analysed by Stem GC-SCD. At least 95 % of the sulfur peaks shifted to later retention times, indicating oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones.
EXAMPLE 7. SODIUM SULFOPHTHALOCYANINE COBALT PEROXIDE Mario Bressan Catalyst Na4C32H12N8S4O12Co[II])O2 (FW 1011.64)
A. Preparation of Catalyst: Commercial UOP cobalt sulfophthalocyanine (Merox catalyst)
0.50 g was dissolved in 100 ml 10 % NaOH to prepare a 5000 ppm stock catalyst solution. 4.0
ml of the catalyst solution was added to 36 ml of an aqueous solution 3.8625% KHSO5
potassium monopersuifate (0.25 Molar) from Mallinkrodt. The catalyst solution was placed in a
vial until used for oxidation. Final concentrations of the catalyst solution are 500 ppm of cobalt
sulfophthalocyanine and 0.225M in potassium monopersuifate.
B. Oxidation and Analysis of Oil: 100 ml of hydrotreated diesel was added to a 500-ml
Erlenmeyer flask, and a condensor was fitted to the flask; 40 ml of the catalyst- monopersuifate
solution was added and 60ml of acetonitrile was added with stirring as the sample was heated.
The mixture was heated to 83 °C and held between 80MOO°C with total reflux and vigorous
stirring for 3 hours. The sample was cooled at 5°C for two hours, and the two phases were
separated. The contents of the Erlenmeyer flask were transferred to a 250-ml separatory funnel,
and the lower aqueous-acetonitrile layer was removed and discarded. The oil was transferred to
a 200-ml polyethylene bottle, and was analyzed by Sievers GC-SCD. Approximately 50% of the
sulfur peaks were removed from the oil and some were shifted to later retention times, indicating
oxidation of benzothiophenes and dibenzothiophenes to their respective sulfones. Approximately
half of the sulfur was removed from the oil and transferred to the acetonitrile-water phase.

WE CLAIM:-
1. A process for reducing the sulfur content of diesel fuel, comprising the steps of:
a) contacting a diesel fuel containing sulfur compounds in a reactor with an oxidant selected from the group consisting of sulfuric acid, peracetic acid, hydrogen peroxide, sodium hypochlorite, perchloric acid, nitric acid, sodium or potassium peroxidisulfate or peroxymonosuifate, and mixtures thereof, in the presence of a homogeneous or heterogeneous oxidation catalyst selected from the group of peroxo molybdotungstic phosphonate, phosphomolybdic acid, dioxomolybdenum amino-diisopropanolate, triphosphono-polyperoxotungstate, bismuthomolybdic acid, sodium sulfophthalocyanine cobalt peroxide, tetraamidomacrocyclic iron complexes, dioxomolybdenum diglycolate, transition metal tetraphenylporphyrin, transition metal acetylacetonate, bismuthomolybdates, dioxomolybdenum aminodiglycoiate, tetraalkylammonium metal sulftetraphenylporphyrin, molybdotungstic acid phosphonates, quaternary ammonium salts of polyoxometallates and simple metal oxides, and at a temperature of about 50°C to about 1 S0°C for a period of time sufficient to oxidize die sulfur compounds; and
b) removing the oxidized sulfur compounds from the diesel fuel by a liquid-liquid countercurrent extraction with a water-soluble polar solvent
2. The process according to claim 1, including the steps of:
a) stripping the solvent from the diesel fuel; and
b) polishing the diesel fuel by passing it through an adsorbent to remove the remaining sulfur compounds.

3. The process according to claim 1, wherein the reactor is a countercuirent reactor.
4. The process according to claim 1, wherein the reactor is stirred, agitated, oscillated, or static.
5. The process according to claim 1, wherein the solvent is selected from the group consisting of aqueous solutions of acetonitrile and methanol.

6. The process according to claim 2, wherein the polishing is effected by an adsorbent bed consisting of polar organic groups coated or bound to a support selected from silica, alumina, or carbon.
7. The process according to claim 1, wherein the catalyst is tetraoctyl-ammonium phosphotungstate.
8. The process according to claim I, wherein the catalyst is a tetraalkylammonium polyoxometallate.
9. The process according to claim 1, wherein the catalyst is selected from the group consisting of Venturello, Campos-Martin, Bressan, Shum, Gollins-Horwitz, Beardon, Merox, Benedict, Bonsignore, Changwen Hu, and Mere Te types of catalysts.
10. The process of claim 5, wherein the solvent contains from about 10% to 30% water by volume.
11. The process of claim 11, wherein the solvent contains 10% water by volume.
12. The process of claim 1, wherein the concentration of sulfur in the treated diesel fuel is reduced to less than 10ppm.
13. A process for reducing the sulfur content of diesel fuel comprising:
a) introducing an aqueous oxidant and a heterogeneous or homogenous catalyst selected from the group consisting of peroxo molybdotungstic phosphonate, phosphomolybdic acid, dioxomolybdenum amino-diisopropanolate, triphosphono-polyperoxotungstate, bismuthomolybdic acid, sodium sulfophthalocyanirie cobalt peroxide, tetraamidomacrocyclic iron complexes, dioxomolybdenum diglycoiate, transition metal tetraphenylporphyrin, transition metal acetylacetonate, bismuthomolybdates, dioxomolybdenum aminodiglycolate, tetraalkylammonium metal sulfotetraphenylpotphyrin, molybdotungstic acid phosphonates, quaternary ammonium salts of polyoxometallates and simple metal oxides into the top of a reactor column;

b) contacting the oxidant and catalyst in countercurrent flow in the reactor with a diesel fuel boiling in the range of about 240°C to about 360°C;
c) continuously oxidizing the sulfur compounds in the diesel oil;
d) continuously extracting oxidized compounds from the diesel oil produced in the reactor by contact with an aqueous solution of a polar solvent in a column;
e) removing traces of solvent from the hydrotreated diesel oil in a stripper column;
f) recovering the aqueous solvent; and
g) adsorbing any remaining traces of sulfur from the hydrotreated diesel oil with adsorbates selected from the group consisting of activated carbon, silica gel and alumina.

14. The process according to claim 13, wherein the catalyst is tetraoctyl-arnmonium phosphotungstate.
15. The process according to claim 13, wherein the catalyst is a tetraalkylammonium polyoxometallate.
16. The process of claim 13, wherein the solvent is selected from aqueous solutions of methanol and acetonitrile.
17. The process according to claim 13, wherein the concentration of sulfur in the hydrotreated diesel fuel is reduced to less than 10ppm.
18. The process of claim 6 in which the solid support is coated with polar polymers selected from the group consisting of polysulfone, polyacrylonitrite, polystyrene, polyester terephthlate and polyurethane.
19. The process of claim 1, wherein the catalyst is peroxo molybdotungstic phosphonate.
20. The process of claim 13, wherein (he catalyst is peroxo molybdotutigstic phosphonate.

21. The process of claim 1 in which the diesel fuel to be treated is a low sulfur hydrotreated diesel containing about 1000ppm by weight of sulfur.
22. The process of claim 1 in which the solvent is composed of approximately 10 to 30% water.
23. The process of claim 13 in which the solvent is composed of approximately 10 to 30% water.
24. A process for reducing the sulfur content of diesel fuel, substantially as hereinbefore described with reference to the foregoing description and drawing.

Documents:

2051-delnp-2008-abstract.pdf

2051-delnp-2008-assignment.pdf

2051-DELNP-2008-Claims-(15-10-2008).pdf

2051-DELNP-2008-Claims-(29-05-2009).pdf

2051-delnp-2008-claims.pdf

2051-delnp-2008-Correspondence Others-(16-06-2014).pdf

2051-delnp-2008-Correspondence Others-(18-06-2014).pdf

2051-delnp-2008-Correspondence Others-(19-11-2013).pdf

2051-DELNP-2008-Correspondence-Others-(15-10-2008).pdf

2051-DELNP-2008-Correspondence-Others-(29-05-2009).pdf

2051-delnp-2008-correspondence-others.pdf

2051-delnp-2008-description (complete).pdf

2051-delnp-2008-drawings.pdf

2051-delnp-2008-form-1.pdf

2051-delnp-2008-form-13-(15-10-2008).pdf

2051-delnp-2008-Form-13-(16-06-2014).pdf

2051-delnp-2008-form-13-(29-05-2009).pdf

2051-delnp-2008-form-2.pdf

2051-delnp-2008-form-26.pdf

2051-delnp-2008-form-3.pdf

2051-delnp-2008-Form-5-(16-06-2014).pdf

2051-delnp-2008-form-5.pdf

2051-delnp-2008-pct-304.pdf

2051-DELNP-2008-PCT-409-(15-10-2008).pdf

2051-DELNP-2008-PCT-416-(15-10-2008).pdf

4800_Petition for Form3-1.pdf

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Patent Number

262582

Indian Patent Application Number

2051/DELNP/2008

PG Journal Number

35/2014

Publication Date

29-Aug-2014

Grant Date

28-Aug-2014

Date of Filing

10-Mar-2008

Name of Patentee

SAUDI BASIC INDUSTRIES CORPORATION

Applicant Address

R-3296, ADMINISTRATION BUILDING, DHAHRAN 31311, SAUDI ARABIA

Inventors:

#	Inventor's Name	Inventor's Address
1	MARTINIE, GARY, D	882 NW 45TH STREET, POMPANO BEACH, FL 33064, U.S.A
2	AL-SHAHRANI, FARHAN, M	WOLFSON COLLEGE, LINTON ROAD, OXFORD OX2 6UD, U.K.
3	DABBOUSI, BASHIR, O	KING FAHAD UNIVERSITY OF PETROLEUM & MINERALS, HOUSE # 3207, DHAHRAN, 31311, SAUDI ARABIA

PCT International Classification Number

C10G 45/00

PCT International Application Number

PCT/US2006/029574

PCT International Filing date

2006-07-28

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	11/222,729	2005-09-08	U.S.A.