GB2262942A - Method of desulfurizing fuel oil - Google Patents
Method of desulfurizing fuel oil Download PDFInfo
- Publication number
- GB2262942A GB2262942A GB9127542A GB9127542A GB2262942A GB 2262942 A GB2262942 A GB 2262942A GB 9127542 A GB9127542 A GB 9127542A GB 9127542 A GB9127542 A GB 9127542A GB 2262942 A GB2262942 A GB 2262942A
- Authority
- GB
- United Kingdom
- Prior art keywords
- fuel oil
- oil
- chemically
- oxidizing agent
- desulfurizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 33
- 239000007800 oxidant agent Substances 0.000 claims abstract description 33
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 24
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract 5
- 229930192474 thiophene Natural products 0.000 claims abstract 4
- 239000003921 oil Substances 0.000 claims description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 50
- 229910052717 sulfur Inorganic materials 0.000 claims description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 35
- 239000011593 sulfur Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- -1 thiophene compound Chemical class 0.000 claims description 4
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000010779 crude oil Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000010763 heavy fuel oil Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 235000010265 sodium sulphite Nutrition 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 6
- 238000004508 fractional distillation Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229960005215 dichloroacetic acid Drugs 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method of chemically desulfurizing fuel oil comprises the steps of: treating fuel oil with an oxidizing agent to oxidize an organic sulfur compound, eg a thiophene contained in the fuel oil into a sulfur oxide having heightened boiling and melting points and a different solubility based on the molecular polarity; and separating and removing the oxidised organic sulfur compound from the fuel oil through the utilization of the change in the boiling point, melting point and/or solubility of the organic sulfur compound. The separation/removal step may involve distillation and/or adsorption and/or precipitation and/or solvent extraction.
Description
2262942 METHOD OF DESULFURIZING FUEL OIL The present invention relates to
a method of chemically desulfurizing fuel oil by which a sulfur component contained in the fuel oil can be removed in I an effective; economical and simple manner.
1 In gener'al, fuel oil, that is, an oil derived from petroleum and coal, contains organic sulfur compounds. Since these organic sulfur compounds have chemical and physical properties similar to those of the fuel oil per se, it is very difficult to remove these sulfur compounds by separating means such as distillation. In order to solve this problem, development has hitherto been made on a method wherein fuel oil is reduced in the presence of a catalyst at high temperature under high pressure through the use of hydrogen to remove organic sulfur compounds contained in the fuel oil through the conversion of the organic sulfur compounds into hydrogen sulfide, i - etc.
Further, there is a technique for removing sulfur through the oxidative decomposition of sulfurcontaining hydrocarbon oil with an oxidizing agent. Specifically, Japanese Patent Laid-Open No. 45103/1974 disclosed a method wherein heavy oil is oxidatively decomposed in liquid phase to give a product having a low metal content. Japanese Patent Laid-Open No. 112609/1977 disclosed a desulfurization method which comprises treating sulfur-containing hydrocarbon oil with an oxidizing agent, adding an alkaline substance to the treated oil and heat-treating the mixture. Japanese Patent Laid-Open No. 290793/1987 disclosed a method wherein hydrocarbon oil is brought into contact with ozone to remove sulfur as sulfur dioxide.
Further, Japanese Patent Laid-Open No. 52803/1974 disclosed a technique wherein hydrocarbon oil is oxidized in the presence of a catalyst. Specifically, in this method, a sulfur-containing hydrocarbon substance is treated with an oxidizing agent and a molybdenum metal catalyst in the presence of an alcohol to reduce the.sulfur content.
Japanese Patent Laid-Open No. 250092/1987 disclosed a technique for improving the quality of diesel oil which comprises reacting diesel oil with an i oxidizing agent L-.d separating the treated oil by extraction.
In hydrodesulfurization widely used in the art on a commercial scale, use is made of a hydrogen gas at high temperature under high pressure in the presence of a metal catalyst such as cobalt, nickel, molybdenum or tungsten. Since, however, the reaction is conducted under vigorous conditions, this method has various technical and economic problems from the viewpoint of practical use, such as necessity for using a compiicate and expensive apparatus and periodically regenerating a catalyst damaged by the action of a sulfur compound as a catalyst poison.
In the technique disclosed in the Japanese Patent Laid-Open No. 45103/1974, heavy oil is oxidatively decomposed in liquid phase and evaporated gas is cooled to separate it into a liquid product and gaseous hydrogen sulfide and sulfur dioxide. Since the liquid product is once gasified and then cooled, the yield of the 'liquid product based on the heavy oil is low disadvantageously.
In the technique disclosed in the Japanese Patent Laid-Open No. 112609/1977,.sulfur-containing hydrocarbon oil is treated with an oxidizing agent and heat treated after an alkaline substance is added thereto, and the resultant alkali sulfide and alkali salt of a sulfur oxide are removed. This method is disadvantageous in that it is necessary to provide the step of adding an alkaline substance and that the alkaline substance should be added in a sufficient amount.
In the technique disclosed in the Japanese Patent Laid-open No. 290793/1977, hydrocarbon oil is brought into contact with ozone to remove sulfur as sulfur dioxide. This method is disadvantageous in that it is necessary to use an apparatus for recovering harmful fur is sulfur dioxide and the percentage removal of sul. not very high.
In the technique disclosed in the Japanese Patent Laid-Open No. 52803/1974, a sulfur-containing hydrocarbon substance is treated with an oxidizing agent and a molybdenum metal catalyst -in the presence of an alcohol. This method is disadvantageous in that the production cos-L is high because it is necessary to use a molybdenum metal catalystin addition to an oxidizing agent.
Further, in the technique disclosed in the Japanese Patent Laid-Open No. 250092/1987, diesel oil is reacted with an oxidizing agent and the treated oil is separated by extraction. This method is 4 - disadvantageous in tha the step of extractive separation is complicate.
p In order to solve the above-described problems, the present invention provides a method of chemically desulfurizing fuel oil, comprising the steps of: treating fuel oil with an oxidizing agent; oxidizing an organic sulfur compound contained in the fuel oil into a sulfur oxide having heightened boiling point and melting point and a different solubility based on the moleculr polarity; and separating 'and removing the organic sulfur compound from the fuel oil through the utilization of the change in the boiling point, melting point and solubility of the organic sulfur compound.
Further, the present invention is characterized in that the fuel oil is selected from among naphtha (b.p.: 301C or below), gasoline (b.p.: 30 to 2201C), kerosine (b.p.: 220 to 3000C), gas oil (b.p.: 300 to 3601C), heavy fuel oil, and crude oil.
Further, the present inventi6n is characterized in that the oxidizing agent is selected from among -oxygen gas, air, ozone gas, chlorine gas, hydrogen peroxide, peracetic acid, a mixture of aqueous hydrogen peroxide with an acid, performic ac--d, a 1 mixture of aqueous hydrogen peroxide with formic acid, perbenzoic acid, a mixture of aqueous hydrogen peroxide with benzoic acid, peroxychloroacetic acid, a mixture of aqueous hydrogen peroxide with chloroacetic acid, peroxydichloroacetic acid, a mixture of aqueous hydrogen peroxide with dichloroacetic acid, peroxytrichloroacetic acid, a mixture of aqueous hydrogen peroxide with trichloroacetic acid, peroxytrifluoroacetic acid, a mixture of aqueous hydrogen peroxide with trifluoroacetic acid, peroxymethanesulfonic acid, a mixture of aqueous hydrogen peroxide with methanesulfonic acid, hypochlorous acid and an aqueous hypochlorite solution.
Further, the present invention is characterized by reacting fuel oil with a peracid oxidizing agent or a hypochlorous acid oxidizing agent at a temperature in the range of from 0 to 1400C while agitating, separating an oil phase from the reaction mixture after the reaction, adding an aqueous alkaline solution to the oil to wash the oil, washing the oil further with water, drying the washed oil, and separating the resultant sulfur oxide from the oil.
Further, the present invention is characterized by reacting fuel oil with a gaseous oxidizing age a temperature i.-- the rahge of -20 to 500C in such a manner that the gaseous oxidizing agent is bubbled through the reaction system, adding a reducing agent to the reaction mixture for washing, washing the oil further with water, drying the washed oil, and separating the resultant sulfur oxide from the oil.
Further, the present invention is characterized by reacting fuel oil with a gaseous oxidizing agent at a temperature in the range of -20 to 501C in the presence of a.,photosensitizer in such a manner that the gaseous bxidizing agent is bubbled through the reaction system while irradiating the reaction system with light, adding a reducing agent to the reaction mixture for washing, washing the oil further with water, drying the washed oil, and separating the resultant sulfur oxide from the oil.
Further, the present invention is characterized by treating fuel oil with an oxidizing agent and distilling the treated fuel oil in the boiling point range of the fuel oil before the treatment through the use of a rectifier to separate an organic sulfur compound as a distillation residue.
Further, the present invention is characterized by treating fuel oil with an oxidizing agent, distilling the treated fuel oil in the boiling point 1 - - t range of the fuel oil before thi- reatment through the use of a rectifier, and passing the resultant distillate through a column packed with an adsorbant selected from among activated carbon, silica gel and alumina or a combination of two or more of them to adsorb a sulfur component.
Further, the present invention is characterized by treating fuel oil with. an oxidizing agent, cooling the treated fuel oil to such a temperature that insoluble components precipitate, allowing the cooled fuel oil to stand, separating an oil component by means of a filter or a separator, and distilling the oil component in the boiling point range of the fuel oil before the treatment through the use of a rectifier to separate an organic sulfur compound as a low-temperature insoluble and a distillation residue.
Further, the present invention is characterized by treating fuel oil with an oxidizing agent, cooling the treated fuel oil to such a temperature that insoluble components prec ipitate, allowing the cooled fuel oil to stand, separating an oil component by means of a filter or a separator, distilling the o'Ll component in the boiling point range of the fuel oil before the treatment through the use oil a rectifier, and passing the resultant distillate through a cc-lumn packed with an adsorban selected from among activated barbon, silica gel and alumina or a combination of two or more of them to adsorb a sulfur component remaining in the distillate, thereby refining the fuel oil.
Although organic sulfur compounds contained in fuel oil are classified into many types and complicate, it is known that they are mainly chemically stable thiophene compounds having a divalent sulfur atom.
1 The present invention is based on the fact that physical and chemical properties inherent in an organic sulfur compound, that is, the boiling point, melting point, solubility in an organic solvent and other properties, undergo a remarkable change depending upon its-state of oxidation, that is, when a divalent sulfur atom is bonded to an oxygen atom by oxidation to yield a sulfoxide, a sulfone and a sulfonic acid containing a sulfur atom having a higher valency.
Accordingly, the present invention is characterized by oxidizing an organic sulfur compound contained in fuel oil into a corresponding compound, such as a sulfoxide, a sulfone or a sulfonic acid through the use of an oxidizing agent commercially available at a low cost, such as oxygen gas or air, ozone, hydrogen peroxide, peracid or hypochlorous acid, and simply and effectively removing the sulfur component by the conventional refining method, such as distillation, extraction with a solvent, lowtemperature separation or column chromatography through the utilization of a remarkable rise in the boiling point and melting point and a difference in the solubility based on the molecular polarity caused by the above-described conversion.
The fuel oil to be used in the present invention may be any of petroleum and liquefied coal oil, that is, crude oil, natural asphalt or bitumen and their distillation fraction, topped crude, vacuum residue, pitchy material obtained from the residue, gasoline, kerosine, gas oil, heavy oil, shale oil, liquefied coal, etc. They may be used in the oxidation as such or in the form of a mixture with other organic solvent.
The oxidizing agent to be used in the present invention may be a reagent commonly used in the oxidation of an organic sulfur compound, and examples thereof include oxygen gas/ air, ozone, chlorine gas, hydrogen peroxide, peracetic acid, a mixture of aqueous hydrogen peroxide with an acid, pe_rformlc 1 acid, a mixture of aqueous hydrogen peroxide with formic acid, perbenzoic acid, a mixture of aqueous hydrogen peroxide with benzoic acid, peroxychloroacetic acid, a mixture of aqueous hydrogen peroxide with chloroacetic acid, peroxydichloroacetic acid, a mixture of aqueous hydrogen peroxide with dichloroacetic acid, peroxytrichloroacetic acid, a mixture of aqueous hydrogen peroxide with trichloroacetic acid, peroxytrifluorQacetic acid, a mixture of aqueous hydrogen peroxide with trifluoroacetic acid, peroxymethanesulfonic acid, a mixture of aqueous hydrogen peroxide with methanesulfonic acid, hypochlorous acid and an aqueous hypochlorite solution.
The oxidation,method may be any of a method wherein the fuel oil is used as a reaction solvent as such and a method wherein a mixed solvent comprising the fuel oil and various organic solvents is used for the purpose of increasing the solubility of the oxidizing agent in the fuel oil. For example, in an oxidization reaction wherein oxygen is used as an oxidizing agent, use is made of singlet oxygen formed by irradiation with a tungsten lamp in the presence of a photosensitizer. A direct oxidation reaction wherein use is made of ozone may also be used according to the conventional method. In the reaction with an organic peracid or a mixture of hydrogen peroxide with various acids, the system often becomes heterogeneous since the organic peracid and the mixtures are hardly soluble in the fuel oil, so that the conversion generally lowers. In this case, it is possible to remarkably improve the conversion by a method wherein a solvent capable of remarkably improving the mutual solubility, such as ac&tone, is added, or a method wherein the reaction is conducted while forcibly dispersing and agitating the reaction solution by mechanical means or by means of an ultrasonic homogenizer.
The reaction in the present invention is conducted under atmospheric pressure at a temperature in the range of from 0 to 2000C. When the reaction is conducted in an aqueous caustic alkali solution in the Ct4 presence of oxygen gas, the pressure and the rea &.On temperature are 1 to 30 atm, preferably 15 atm, and 250 to 4000C, respectively. On the other hand, when the reaction is conducted in an aqueous caustic alkali solution in the presence of oxygen gas, the pressure and the reaction temperature are 1 to 30 atm, preferably 15 atm, and 250 to 4000C, preferably 3700C, respectively.
In general, the removal of a sulfur component from the fuel oil according to the present invention can be simply conducted by a distillation procedure through the utilization of the rise of the boiling point of an organic sulfur compound formed by the oxidation. Further, techniques wherein use is made of a change in the solubility and melting point, such as extraction with a solvent, low-temperature separation and column chr9matography, may be used alone or in a combination of two or more of them.
FUNCTION In the above-described method of chemically desulfurizing fuel oil to remove a sulfur component contained therein, the sulfur content of gasoline, kerosine, gas oil and heavy oil can be reduced to 0.03% or less. Themechanism of function of the present invention is based on the fact that physical and chemical properties inherent in an organic sulfur compound, that is, the boiling point, melting point, solubility in an organic solvent and other properties, undergo a remarkable change depending upon its state of oxidation. For example, the boiling point of dimethyl sulfide is 380C under atmospheric pressure, while the boiling point of dimethyl sulfoxide formed by the oxidation of dimethyl sulfide is 1890C.
- 13 Further, dimethyl sulfone formed by the oxidation of dimethyl sulfide is in a state of crystal having a melting point of 1101C under atmospheric pressure which is difficult to distill. It is known that all - of these oxidation products have a larger polarity than those of the corresponding dimethyl sulfide, which causes the solubility in an organic solvent to be remarkably changed.
[Examples]
The present invention will now be described with reference to the following Examples.
Example 1 ml of a fuel oil (combustible sulfur content: 0.063% by weight) obtained by frictional distillation in a boiling temperature range of from 220 to 3001C was cooled to OOC in a'200-ml round-bottomed hard glass flask equipped with a homogenizer agitator, a reflux condenser and a gas introduction tube, and agitation was conducted for 2 hr while blowing air containing ozone (about 1.0%) into the fuel oil. After the supply of ozone was stopped, the temperature of the whole flask was lowered to - 201C and agitation was continued for additional one hr. Then the precipitated solid matter was quickly separated by filtration. The filtrate was washed with a 2 N - 14 aqueous sodium sulfite 'solution and further with distilled water, and the resultant organic phase was distilled by means of a rectifier to collect fractions having boiling points in the range of from 220 to 300C. The total sulfur content in the resultant refined oil was 0.022%.
Example 2
A 200-ml round-bottomed hard glass flask equipped with a homogenizer agitator, a reflux condenser and a gas introduction tube was charged with added 50 ml of a fuel oil (combustible sulfur content: 0.023% by weight) obtained by fractional distillation in a boiling temp6rature range of from 70 to 2200C, 20 ml of methanol and 0.15 g of a photosensitizer (Rose Bengal), and the mixture was irradiated with a 300-W halogen lamp at roO'M temperature for 6 hr while blowing oxygen gas into the mixture After the reaction, the reaction mixture was washed with a 2 N aqueous sodium sulfite solution and further with distilled water, and distilled by means of a rectifier. The total sulfur content in the resultant fractions having boiling points in the range of from 70 to 2200C was 0. 012%.
Example 3 ml of a fuel oil (combustible sulfur content:
0.527% by weight) obtained by fractional distillation in a boiling temperature range of from 300 to 3601C was put in a 200-ml round-bottomed hard glass flask equipped with a homogenizer agitator and a reflux condenser, and 5 ml of aqueous hydrogen peroxide (30%) and 10 ml of formic acid were added thereto. After, a reaction was allowed to proceed while agitating the mixture at 40C for I hr and then at 800C for 2 hr, an upper layer of the reaction mixture separated into two layers was separated by means of a separatory funnel, washed with a 2 N aqueous sodium sulfite solution and further with distilled water, and the resultant organic phase was distilled by means of a rectifier to collect fractions having boiling points in the range of from 220 to 3500C. The total sulfur content in the refined oil was 0.043-%. This oil was passed through a glass column packed with 20 g of alumina to give a refined oil having a total sulfur content of 0.011%.
- Example 4 ml of a fuel oil (combustible sulfur content: 0.527% by weight) obtained by fractional distillation in a boiling temperature range of from 300 to 3600C wag put in a 200-ml round-bottomed hard glass flask equipped with a homogenizer agitator and a reflux condenser, and 5 ml of aqueous hydrogen peroxide (30%) 16 and 10 ml of dichloroacetic acid were added thereto. After a reaction was allowed to proceed while agitating the mixture at 401C for 3 hr, an upper layer of the reaction mixture separated into two layers was separated by means of-a separatory funnel and washed with a 2 N aqueous sodium sulfite solution and further with distilled water, and the resultant organic phase was distilled by means of a rectifier to collect fractions having boiling points in the range of from 300 to 3600C, The total sulfur content in the refined oil was 0.022%. This oil was passed through a glass column packed with 20 g of silica gel to give a refined oil,having a total sulfur content of 0.008%. Example 5 50 ml of a fuel oil (combustible sulfur content: 0.023% by weight) 'obtained by fractional distillation in a boiling temperature range of from 70 to 2201C and 10 ml of distilled water were put in a 200-ml roundbottomed hard glass flask equipped with a homogenizer agitator, a reflux condenser and a gas introduction tube, and a reaction was allowed to proceed at O'C for one hr with agitation while blowing chlorine gas into the mixture. After the reaction, the resultant organic phase was separated and washed with a 2 N aqueous sodium sulfite solution, and the resultant organic phase was distilled by means of a rectifier. The total sulfur content in the fractions having boiling points in the range of from 70 to 220C was 0.007%.
Example 6 ml of a fuel oil (combustible sulfur content: 0.527% by weight) obtained by fractional distillation in a boiling temperature range of from 300 to 3600C was put in a 200-ml round-bottomed hard glass flask equipped with a homogenizer agitator and a reflux condenser, and 20 ml of an aqueous sodium hyposulfite solution (Cl: 5%) was added thereto. After a reaction was allowed to proceed at 30C for 3 hr while agitating, an upper layer of the reaction mixture separated into two layers was separated by means of a separatory funnel, washed with a 2 N aqueous sodium sulfite solution and further with distilled water, and the resultant organic phase was distilled by means of a rectifier to collect fractions having boiling points in the range of from 300 to 3600C. The total sulfur content in the refined oil was 0.108%.
Example 7 50 ml of a commercially available heavy oil A (combustible sulfur content: 0.833% by weight) was pult 'pped in a 200-ml round-bottomed hard glass flask equ t with a homogenizer agitator and a reflux condenser, and 5 ml of aqueous hydrogen peroxide (30%) and 10 ml of trifluoroacetic acid were added thereto. After a reaction was allowed to proceed at 201C for one hr while agitating, an upper layer of the resultant reaction mixture separated into two layers was separated by means of a separatory funnel and washed with a 2 N aqueous sodium sulfite solution and further with distilled 'water. 100 ml of petroleum ether (b.p.: 35 to Gb'c) was added thereto and the mixture was cooled to -400C and allowed to stand for 2 hr. An upper layer of the Mixture separated into two layers was separated, dried and passed through a glass column packed with 10 g of alumina and 10 g of silica gel in two layers. The petroleum ether was removed from the resultant oil by distillation. The total sulfur content in the residue was 0.145%. Example 8 50 ml of a fuel oil (combustible sulfur content: 0. 527% by weight) obtained by fractional distillation in a boiling temperature range of from 300 to 3601C was put in a 200-ml round-bottomed hard glass flask equipped with a homogenizer agitator and a reflux condenser, and 5 ml of aqueous hydrogen peroxide (30%) and 10 ml of trifluoroacetic acid were added therelto.
19 - 1 After a reaction was allowed to proceed at 200C for one hr while agitating, an upper layer of the resultant reaction mixture separated into two layers was separated by means of a separatory funnel and washed with a 2 N aqueous sodium sulfite solution and further with distilled water. The resultant organic phase was distilled by means of a rectifier to collect fractions haying boiling points in the range of from 300 to 360, which were passed through a glass column packed with 10 g of alumina and 10 g of silica gel in two layers. The total sulfur content in the refined oil was 0.005% 2
Claims (1)
- CLAIMS:(1) A method of chemically desulfurizing fuel oil, comprising the steps of: treating fuel oil with an oxidizing agent; oxidizing an organic sulfur compound contained in the fuel oil into a sulfur oxide having heightened boiling point and melting point and a different solubility based on the molecular polarity; and separating and removing the organic sulfur compound from the fuel oil through the utilization of the change in the boiling point, melting point and solubility of the organic sulfur compound.(2) A method of chemically desulfurizing fuel oil according to claim 1, wherein the fuel oil is selected from among naphtha (b.p.: 301C or below), gasoline (b.p.: 30 to 2201C), kerosine (b.p.: 220 to 300'C), gas oil (b. p.: 300 to 360'C), heavy fuel oil, and crude oil.(3) A method of-chemically desulfurizing fuel oil according to claim 1, wherein the oxidizing agent is selected from among oxygen gas, air, ozone gas, chlorine gas, hydrogen peroxide, peracetic acid, a mixture of aqueous hydrogen peroxide with an acid, performic acid, a mixture of aqueous hydrogen peroxide with formic acid, perbenzoic acid, a mixture of - 21 the range of from 0 to 140C while agitating, separating an oil phase from the reaction mixture after the reaction, adding an aqueous alkaline solution to the oil to wash the oil, washing the oil further with water, drying the washed oil, and separating the resultant sulfur oxide from the oil.(6) A method of chemically desulfurizing fuel oil according to claim 1, which comprises reacting fuel oil with a:gaseous oxidizing agent at a temperature in the range of from -20 to 50C in such a manner that the gaseous oxidizing agent is bubbled through the reaction system, adding a reducing agent to the reaction mixture for washing, washing the oil further with water, drying the washed oil, and separating the resultant sulfur oxide from the oil.(7) A method of chemically desulfurizing a fuel oil according to claim 1, which comprises reacting a fuel oil with a gaseous oxidizing agent at a temperature in the range of from -20 to 500C in the presence of a photosensitizer in such a manner that the gaseous oxidizing agent is bubbled through the reaction system while irradiating the reaction system with light, adding a reducing agent to the reaction mixture for washing, washing the oil further with water, drying the washed oil, and separating the resultant sulfur oxide from the oil.(8) A method of chemically desulfurizing fuel oil according to claim 1, which comprises treating fuel oil with an oxidizing agent and distilling the treated fuel oil in the boiling point range of the fuel oil before the treatment through the use of a rectifier to separate an organic sulfur compound as distillation residue.(9) A method of chemically desulfurizing fuel oil according to claim 1, which comprises treating fuel oil with an oxidizing agent, distilling the treated fuel oil in the boiling point range of the fuel oil before the treatment through the use of a rectifier, and passing the resultant distillate through a column packed with an adsorbant selected from among activated carbon, silica gel and alumina or a combination of two or more of the adsorbents to adsorb a sulfur component.(10) A method of chemically desulfurizing fuel oil according to claim 1, which comprises treating fuel oil with an oxidizing agent, cooling the treated fuel oil to such a temperature that insoluble components precipitate, allowing the cooled fuel oil to stand, separating an oil component by means of a filter or a separator, and distilling the oil component in the boil ng point range of the fuel oil before the treatment through the use of a rectifier to separate an organic sulfur compound as a lowtemperature insoluble and a distillation residue.(11) A method of chemically desulfurizing fuel oil according to claim 1, which comprises treating a fuel oil with an oxidizing agent, cooling the treated fuel oil to such a temperature that insoluble components precipitate, allowing the cooled fuel oil to stand, separating an oil component by means of a filter or a-separator, distilling the oil component in the boiling point range of the fuel oil before the treatment through the use of a rectifier, and passing the resultant distillate through a column packed with an adsorbant selected from among activated carbon, silica gel and alu:mina or a combination of two or more of the adsorbents to adsorb a sulfur component remaining in the distillate, thereby refining the fuel oil.(12) A method of chemically desulfurizing fue-7 oil according to claim 1, wherein the organic sulfur compound contained in the fuel oil is a chemically stable thiophene compound having a divalent sulfur atom, and the divalent sulfur atom of the thiophene compound is combined with oxygen by oxidation to It l convert the thiophene compound into a sulfoxide, a sulfone and a sulfonic acid containing a sulfur atom having a higher valency.13. A method of chemically desulfurizing fuel oil substantially as hereinbefore described in the Examples. - - 26
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14239290A JPH0472387A (en) | 1990-05-30 | 1990-05-30 | Removal of sulfur content from fuel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9127542D0 GB9127542D0 (en) | 1992-02-19 |
| GB2262942A true GB2262942A (en) | 1993-07-07 |
Family
ID=15314296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9127542A Withdrawn GB2262942A (en) | 1990-05-30 | 1991-12-31 | Method of desulfurizing fuel oil |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0472387A (en) |
| DE (1) | DE4200376A1 (en) |
| GB (1) | GB2262942A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995001411A1 (en) * | 1993-06-30 | 1995-01-12 | Horst Kief | Fuel for internal combustion engines and turbines |
| WO1997005217A1 (en) * | 1995-07-27 | 1997-02-13 | Horst Kief | Method of producing a homogeneous catalyst for fuels |
| GB2366803A (en) * | 2000-08-14 | 2002-03-20 | Ici Plc | Sulphur removal from a hydrocarbon stream |
| WO2002081597A1 (en) * | 2001-03-30 | 2002-10-17 | Ohtix Inc. | Method and device for separating sulfuric compound contained in oil |
| US6827845B2 (en) * | 2001-02-08 | 2004-12-07 | Bp Corporation North America Inc. | Preparation of components for refinery blending of transportation fuels |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2159785C (en) | 1994-11-11 | 2003-04-08 | Tetsuo Aida | Process for recovering organic sulfur compounds from fuel oil and equipment therefor |
| US7018531B2 (en) | 2001-05-30 | 2006-03-28 | Honeywell International Inc. | Additive dispensing cartridge for an oil filter, and oil filter incorporating same |
| US7182863B2 (en) | 2000-05-08 | 2007-02-27 | Honeywell International, Inc. | Additive dispersing filter and method of making |
| US6673230B2 (en) * | 2001-02-08 | 2004-01-06 | Bp Corporation North America Inc. | Process for oxygenation of components for refinery blending of transportation fuels |
| JP2002322482A (en) * | 2001-04-24 | 2002-11-08 | Idemitsu Kosan Co Ltd | Method for desulfurizing liquid oil containing organic sulfur compounds |
| JP2002322483A (en) * | 2001-04-24 | 2002-11-08 | Idemitsu Kosan Co Ltd | Method for desulfurizing liquid oil containing organic sulfur compounds |
| US6887381B2 (en) | 2001-10-11 | 2005-05-03 | Honeywell International, Inc. | Filter apparatus for removing sulfur-containing compounds from liquid fuels, and methods of using same |
| JP4594602B2 (en) * | 2003-06-24 | 2010-12-08 | 三井造船株式会社 | Method for oxidative desulfurization of liquid petroleum products |
| US20050109678A1 (en) * | 2003-11-21 | 2005-05-26 | Ketley Graham W. | Preparation of components for refinery blending of transportation fuels |
| US7931817B2 (en) | 2008-02-15 | 2011-04-26 | Honeywell International Inc. | Additive dispensing device and a thermally activated additive dispensing filter having the additive dispensing device |
| EP2436664A4 (en) * | 2009-05-12 | 2012-10-31 | Wako Pure Chem Ind Ltd | Method for purifying organic solvent |
| WO2013035200A1 (en) * | 2011-09-09 | 2013-03-14 | Aida Tetsuo | Method for producing ultra-low sulfur fuel oil |
| US9623350B2 (en) | 2013-03-01 | 2017-04-18 | Fram Group Ip Llc | Extended-life oil management system and method of using same |
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| GB404571A (en) * | 1933-08-04 | 1934-01-18 | Louis Boulanger | Process of cracking tar and bituminous schist oils with recovery of by-products |
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- 1990-05-30 JP JP14239290A patent/JPH0472387A/en active Pending
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- 1991-12-31 GB GB9127542A patent/GB2262942A/en not_active Withdrawn
-
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- 1992-01-09 DE DE19924200376 patent/DE4200376A1/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB282738A (en) * | 1926-12-27 | 1929-03-11 | Axtell Research Laboratories, Inc. | |
| GB424564A (en) * | 1933-07-18 | 1935-02-18 | Jean Herzenberg | Improvements in refining gasoline, mineral oils and tar oils |
| GB404571A (en) * | 1933-08-04 | 1934-01-18 | Louis Boulanger | Process of cracking tar and bituminous schist oils with recovery of by-products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995001411A1 (en) * | 1993-06-30 | 1995-01-12 | Horst Kief | Fuel for internal combustion engines and turbines |
| US5762655A (en) * | 1993-06-30 | 1998-06-09 | Kief; Horst | Fuel for internal combustion engines and turbines containing ozonization products |
| WO1997005217A1 (en) * | 1995-07-27 | 1997-02-13 | Horst Kief | Method of producing a homogeneous catalyst for fuels |
| GB2366803A (en) * | 2000-08-14 | 2002-03-20 | Ici Plc | Sulphur removal from a hydrocarbon stream |
| US6827845B2 (en) * | 2001-02-08 | 2004-12-07 | Bp Corporation North America Inc. | Preparation of components for refinery blending of transportation fuels |
| WO2002081597A1 (en) * | 2001-03-30 | 2002-10-17 | Ohtix Inc. | Method and device for separating sulfuric compound contained in oil |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9127542D0 (en) | 1992-02-19 |
| DE4200376A1 (en) | 1993-07-15 |
| JPH0472387A (en) | 1992-03-06 |
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