EP0236021A2 - Procédé de valorisation d'huiles diesel - Google Patents

Procédé de valorisation d'huiles diesel Download PDF

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Publication number
EP0236021A2
EP0236021A2 EP87301467A EP87301467A EP0236021A2 EP 0236021 A2 EP0236021 A2 EP 0236021A2 EP 87301467 A EP87301467 A EP 87301467A EP 87301467 A EP87301467 A EP 87301467A EP 0236021 A2 EP0236021 A2 EP 0236021A2
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EP
European Patent Office
Prior art keywords
diesel oil
oxidant
oil
diesel
weight
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EP87301467A
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German (de)
English (en)
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EP0236021A3 (fr
Inventor
James R. Kittrel
Saeed T. Darian
Patrick S. Tam
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ENSR CORPORATION (A DELAWARE CORPORATION)
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ENSR Corp (a Delaware Corporation)
ENVIRONMENTAL RES AND Technology
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Publication of EP0236021A2 publication Critical patent/EP0236021A2/fr
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    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • This invention relates to a process for upgrading the cetane rating of diesel oils. More particularly, the invention relates to a process for upgrading the cetane rating of diesel fuels while also removing compounds containing heteroatomic sulfur impurities, and selectively removing instability-causing organic compounds from the oil. Specifically, this invention relates to a process for upgrading middle distillates containing such impurities by contacting the oils with ozone, nitrogen oxides, nitrous acid or nitric acid under conditions enhancing removal of impurities by solvents in solvent extraction, solvent extracting the oil using selected solvents to remove the organic impurities, and then separating the oil from the solvents employed for extraction.
  • diesel fuels In addition to sulfur content, other important distillate fuel specifications are feedstock-dependent.
  • the important properties of diesel fuels include ignition quality, oxidation stability, and Ramsbottom carbon in addition to sulfur content.
  • cetane number is a limiting specification for diesel fuels.
  • No. 1 diesel fuel In order to be suitable for automotive use, No. 1 diesel fuel is generally made from virgin stocks having cetane numbers of about 45.
  • Railroad diesel fuels are similar to the automotive diesel fuels, but can have somewhat lower cetane numbers of about 40.
  • hydrotreating is effective in desulfurization and in improving stability, it is a costly method of improving cetane and stability, requiring a high capital investment, use of hydrogen which is expensive and a high utilities cost relative to other treatment methods.
  • caustic scrubbing is often employed to remove sediment precursors such as benzenthiol, mercaptan sulfur, H 2 S, acids and phenols from middle distillates. Although caustic scrubbing is often effective, it removes little sulfur, it does not improve cetane rating, and it cannot produce a stable product in all cases, and cannot, for example, remove pyrrolic nitrogen impurities.
  • the disadvantages of caustic treating include cost of maintaining caustic strength, disposal of spent caustic and loss of product by extraction.
  • Stabilizers generally provide basicity without initially entering into an organic acid-base reaction to form a salt.
  • Antioxidants perform the same function with thermally derived distillates as they do for gasolines. Unsaturates provide free radical precursors that can enter into any of several sediment forming reactions, but these reactions are interrupted by the presence of an antioxidant. Once sediment starts to form, however, stabilizers are less effective and dispersant type additives are used, which cause disassociation of agglomerated sediment particles as well as preventing agglomeration.
  • solvent extractions have often been used to remove sulfur and/or nitrogen compounds from petroleum distillates and synfuels, the extract oil and solvent then being separated by distillation.
  • solvent extraction of petroleum products to remove sulfur involves a large loss of oil yield and high solvent-to-oil ratio, and provides only limited sulfur removal.
  • cetane characteristics of a fuel composition containing. both aromatic and paraffinic constituents can be improved by removing the aromatic component to increase the concentration of paraffins, e.g., by solvent extraction.
  • the cetane number of diesel fuels can be improved either by adding a nitrogen-containing fuel additive, or by nitrogenation with a nitrogenous oxidizing agent.
  • Fuel oils in the diesel range having the proper physical characteristics such as pour point, cloud point, viscosity and volatility can be obtained by nitrogenating the diesel fraction in order to increase the cetane number.
  • the nitrogenation of such fuel oils tends to increase the Ramsbottom carbon content and to decrease the stability of the oils by forming an insoluble sediment, which produces a haze and eventually a deposit while the fuel oils are in storage.
  • the invention described and claimed herein is directed to a process for upgrading a diesel fuel by removing sulfur-containing organic compounds, increasing cetane rating, reducing Ramsbottom carbon and instability-causing compounds using an oxidation/extraction/separation approach in contrast to the generally used catalytic hydrogenation, caustic scrubbing and chemical additive approaches conventionally practiced.
  • U.S. Patent No. 1,933,748 describes using nitrogen oxides to remove sulfur compounds from cracked petroleum stocks at 150 to 350°F followed by the use of sulfuric acid for extraction
  • U.S. Patent No. 1,935,207 discloses a similar process with improved results obtained by carrying out the oxidation using nitrogen oxides in the presence of sulfuric acid at a temperature below 30°C.
  • the use of nitric and acetic acid, followed by sulfuric acid, to improve color and odor and to remove sulfur from cracked distillate stocks is disclosed in U.S.
  • Patent No. 2,027,648 Although nitric acid treatment followed by sulfuric acid will remove odor and sulfur and will improve color, it will not satisfactorily reduce Ramsbottom carbon without uneconomic levels of sulfuric acid usage and cetane loss.
  • the desulfurization of petroleum fractions using sulfuric acid in combination with air and nitrosyl sulfuric acid is disclosed in U.S. Patent No. 3,294,677.
  • U.S. Patent No. 2,009,898 describes the treatment of cracked gasoline vapors with nitrogen oxides without significant olefin oxidation, followed by clay-treatment of the product to achieve a reduction in sulfur content. This process, however, requires the use of uneconomical quantities of clay to meet product specifications.
  • U.S. Patent No. 2,825,744 discloses a similar process operated in the vapor phase at temperatures less than 200°C to produce low molecular weight sulfoxides.
  • U.S. Patent No. 3,824,342 discloses oxidation of residue using a number of oxidants including nitrogen oxides, followed by thermal treating to reduce the sulfur content of the residue, in which both steps can be promoted with catalysts.
  • U.S. Patent No. 3,163,593 describes a process using a number of different oxidants, including nitrogen dioxides, to treat vacuum residues, residues from cracking processes, oil from tar sands and oil shale followed by thermal decomposition at 350°C to 400°C to produce volatile sulfur compounds and low sulfur oil.
  • an alkaline material such as dolomite or lime can be used to accelerate the process.
  • U.S. Patent No. 3,341,448 discloses a process for sweetening petroleum hydrocarbons by treating the hydrocarbon !fraction with molecular oxygen in the presence of a catalytic amount of a nitrogen oxide. Application of this process to diesel fuel results in a product of unacceptable stability and Ramsbottom carbon content.
  • U.S. Patent No. 2,004,849 discloses the use of an oxidant, hydrogen peroxide, in combination with sulfuric acid to effect sulfur removal from hydrocarbons, without substantial loss of aromatics. However, this process is ineffective for improving cetane of diesel fuel, and would not provide a yield enhancement upon extraction.
  • British Patent No. 491,648 teaches contacting a diesel fuel with a nitrating agent in order to increase its cetane number. Extraction with solvents including acetone, methyl and ethyl alcohols, ethylene dichloride and aniline is described for obtaining concentrates of nitrated petroleum components.
  • solvents including acetone, methyl and ethyl alcohols, ethylene dichloride and aniline.
  • stability is decreased and Ramsbottom carbon is increased, and poor process yields and loss of cetane rating are encountered when the product is extracted using the solvents disclosed.
  • U.S. Patent No. 3,135,680 discloses the use of oxidation by nitrogen dioxide followed by washing with water and alkali, to desulfurize diesel fuel oils and improve cetane.
  • the product obtained tends to have an objectionable color resulting from the nitrogen dioxide treatment, and subsequent sulfuric acid treatment, vacuum distillation or clay treating to completely remove materials formed during oxidation reduces or eliminates the increase in cetane number. Due to its high Ramsbottom carbon content, the product of this process forms substantial coke in the still upon distillation.
  • U.S. Patent No. 3,164,546 a process is described for producing diesel fuels having improved cetane number and odor, by treating the oil with nitrogen dioxide, washing with aqueous caustic and/or solvent extraction, followed by a water wash.
  • Solvents disclosed as suitable for the solvent extraction step are nitromethane, dimethylformamide, pyridine, acetonitrile, glycolonitrile, ethylene glycol, ethanolamine and phenol. No reference is made, however, to the important stability and Ramsbottom carbon content specifications, which are by far the most difficult product specifications to meet when employing nitrogenous treating agents. The process is exemplified only at low cetane enhancement levels, which is disadvantageous.
  • U.S. Patent No. 2,083,253 discloses the use of a bichromate oxidizing agent followed by a sulfuric acid treatment to remove polymers and gums. This process does not enhance cetane rating, and the product does not have the instability characteristics of nitrated products which are improved by the extraction step of the present invention.
  • U.S. Patent No. 2,333,817 discloses oxidation of diesel fuel oils by nitrogenous compounds followed by hexane dilution and filtering to improve cetane and prevent sediment formation. Such a product does not pass present-day industry standards for stability (although haze formation is reduced) and it does not meet Ramsbottom carbon specifications.
  • U.S. Patent No. 2,114,852 discloses a process comprising heating high boiling hydrocarbon oils or shale containing objectionable sulfur compounds as an impurity to obtain hydrocarbon fractions, extracting the product obtained with solvents to remove high boiling sulfur compounds in the presence of unsaturated hydrocarbons, followed by oxidizing the extract.
  • U.S. Patent No. 2,114,852 discloses a preference for solvents with boiling points no more than 80°C below the boiling range of the initial hydrocarbonaceous oil mixture to improve fractionation.
  • I.N. Diyarov, Khim. Tekhnol. Topl. Masel, (5), pages 14-16 (1978) discloses treatment of diesel fuel with ethylene chlorohydrin mixed with water
  • Yu. E. Nikitin, Neftekhimiva, 16, (6), pages 917-920 (1976) describes a comparison of extraction of sulfoxides from diesel fuel using citric and tartaric acids with citric acid being found five times more efficient than tartaric acid in the extraction of sulfoxides.
  • U.S. Patent No. 2,608,519 discloses dimethyl formamide (with less than 25% water) for extraction to remove sulfur and aromatics from highly olefinic naphthas, without extracting olefins.
  • J.S. Patent No. 2,361,080 describes the use of nitromethane, nitroparaffin-SO 2 , benzol-acetone, furfural, methyl ethyl ketone, liquified sulfur iioxide, benzol-SO 2 and chlorex as suitable solvents to extract aromatics from catalytic cycle stock, to thereby improve cetane rating.
  • the yields from this process are uneconomically low, and there is no iisclosure of the yield enhancement obtained by nitrogenous oxidation, coupled with specific solvents which also control other important properties, such as 3 tability and Ramsbottom carbon, not normally controlled with nitrogenous oxidation.
  • U.S. Patent No. 3,317,423 discloses preparation of i carbon black feedstock by aromatics extraction of a l eavy (500°F+) hydrocarbon using a dual solvent of furfural and a paraffinic hydrocarbon. Preparation of in aromatic carbon black feedstock in a two-stage solvent extraction process using furfural, phenol, Liquid sulfur dioxide or glycol ethers is disclosed in J.S. Patent No. 3,349,028, in which Ramsbottom carbon Ls also extracted.
  • U.S. Patent No. 3,415,743 discloses :he extraction of heavy aromatics and heavy aliphatics from cycle oil in a two-stage process using dimethyl formamide (5 to 18% water) and xylene in the first stage.
  • Patent No. 3,546,108 discloses a fur- fural/dimethyl formamide/water mixed solvent used for the extraction of aromatics from gas oils and U.S. Patent No. 2,137,206 also relates to a method for dewaxing oils using furfural. These patents all fail to appreciate the importance of treatment prior to solvent extraction, and the surprising yield enhancement obtained thereby, or the control of other important product properties, such as stability and Ramsbottom carbon, obtained by the combined use of nitrogen treatment and extraction with selected solvents in the present invention.
  • U.S. Patent No. 3,539,504 describes production of a middle distillate fuel such as kerosene with improved burning and color characteristics by a temperature graduated furfural extraction to remove aromatics and olefins.
  • U.S. Patent No. 4,485,007 discloses a process for purifying hydrocarbonaceous oils containing both heteroatom sulfur and heteroatom nitrogen compound impurities, such as shale oils, by first reacting the hydrocarbonaceous oil with an oxidizing gas containing nitrogen oxides while limiting the molar ratio of the nitrogen oxide to the total sulfur heteroatom content and nitrogen heteroatom content and limiting the conversion of sulfur heteroatom content into gaseous sulfur oxides to about 60% or less on a weight basis, followed by extracting the oxidized oil in one step with an amine selected from the group consisting of ethylene diamine, monoethanolamine, diethanolamine and mixtures thereof, and a second extracting step using formic acid as an extracting solvent. It is disclosed that the amine extracting solvent acts to remove sulfur compound impurities and the formic acid extracting solvent acts to remove nitrogen impurities.
  • a process for producing a fuel composition by oxidizing a hydrocarbon oil with aqueous nitric acid, followed by extraction with acetone, methyl ethyl ketone, cyclohexanone, methanol, ethanol, normal propanol, isopropanol, ethyl acetate, tetrahydrofuran, dioxane, or a combination of an alcohol and a ketone, an alcohol and water, a ketone and water or a combination of alcohols is disclosed in U.S. Patent No. 4,280,818.
  • the methods described above basically have the disadvantages that (a) the solvents selected are suitable only for specific selected oils; (b) the solvents result in poor extraction yields or they do not provide sufficient phase separation to make solvent extraction possible; (c) unacceptably high solvent-to-oil ratios are required, decreasing oil yield and making the processes uneconomical; (d) they require expensive catalysts or extremely severe oxidizing conditions to provide sufficient sulfur removal; or (e) oxidative desulfurization methods involving nitrogenous oxidizing agents result in increased gum and sedimentation, and reduce the stability of the fuels produced.
  • One object of the present invention is a process for improving the cetane number of diesel oil without decreasing stability or increasing Ramsbottom carbon content.
  • a second object of the present invention is a process for upgrading diesel oil by decreasing sulfur content and improving stability.
  • Another object of the present invention is a process for upgrading diesel oil employing solvent extraction with a high solvent extraction efficiency and correspondingly high yield.
  • An additional object of the present invention is a process for producing a blended diesel fuel from off-specification diesel oils meeting industrial specifications for cetane, sulfur content, Ramsbottom carbon, product stability and pour point.
  • a diesel oil can be improved, and the production of diesel fuels from substandard or blended stocks made possible, by a simple and economical process of first contacting the diesel oil with an oxidant selected from the group consisting of ozone, gaseous nitrogen oxides, nitric acid and nitrous acid, followed by selective solvent extraction.
  • an oxidant selected from the group consisting of ozone, gaseous nitrogen oxides, nitric acid and nitrous acid, followed by selective solvent extraction.
  • the process according to the invention permits the simultaneous desulfurization and cetane improvement of diesel fuels with remarkably improved stability on storage and enhanced handling characteristics.
  • one embodiment of the present invention provides a process for upgrading diesel oil to produce an upgraded diesel fuel comprising the steps of:
  • this invention provides a process for upgrading petroleum derived diesel fuel oils having a boiling point at normal pressure of about 300°F to about 700°F, including those containing heteroatom sulfur compounds, to produce a cetane number increase of at least about 5 of the reacted product of step (a) over the diesel oil feed to step (a) while meeting stability requirements.
  • the process of this invention is applicable to the upgrading of diesel oil which can be derived from any source, for example, a conventional petroleum crude oil or crude oil fraction containing sulfur, aromatic, olefinic and napthenic compounds as impurities.
  • diesel oil as used herein is broadly defined to include any hydrocarbon having a nominal boiling range of about 300°F to about 700°F of petroleum origin which can be upgraded by the process of this invention to meet commercial product specifications for a diesel fuel and the term “diesel fuel” is generally used to describe the upgraded product, although the terms can be used interchangeably.
  • Preferred petroleum source of diesel oils which can be used in the process of this invention are those! containing less than about 40% by weight aromatics content, those containing less than about 35% by weight olefins content and those containing both less than about 40% by weight aromatics and less than about 35% by weight olefinics content.
  • the process of this invention is basically not limited in terms of the source of the diesel oil, but is applicable to any diesel oil with the above described boiling point range from petroleum sources, including conventional crude oil, heavy crude oil and tar sands.
  • Fuel stability is measured by a number of accelerated tests, one of which is the Nalco 300°F test.
  • a transportation fuel must exhibit a Nalco rating of about 7.0 or lower.
  • a rating of about 7.0 is the upper limit of acceptability for commercial use, although a lower level is desirable.
  • the applicable Nalco test is well known in the art, and can be simply performed, for example, by placing 50 ml of oil to be tested in a tube 3 cm in diameter, heating the tube in a 300°F bath for 90 minutes, and then cooling the oil. The oil is then filtered using a micropore filter with a number 1 filter paper, the paper and the filter are washed with heptane, and the residue remaining is compared with standard samples to determine the stability rating.
  • Desulfurization is a second generally important aspect of purification or upgrading of diesel oils.
  • Sulfur compounds present as impurities may include, for example, thiophenic sulfur, mercaptan sulfur, sulfides, thiols and disulfides. Because of the differing selectivities of various solvents in extracting different sulfur-containing impurity compounds, which can be enhanced or depressed by oxidation, depending on the particular solvent and feed characteristics, selection of an appropriate solvent for desulfurization is empirical and selection generally is not possible on the basis of theory.
  • cetane number is an important quality characteristic of diesel fuels, cetane enhancement obtained by oxidation is poorly understood.
  • increasing oxidizer nitrogen is related to increased cetane and it is known that aromatics extraction contributes to cetane improvement, raffinate nitrogen is not well correlated with cetane improvement, and aromatics removal alone cannot account for the cetane response obtained at the high yields observed in this invention.
  • Oxidation with non-nitrogen containing oxidants such as ozone as in this invention increases cetane although nitrogen is not added by the oxidant.
  • Ramsbottom carbon content is an important quality specification for diesel fuels, since fuels high in Ramsbottom carbon cause fouling problems when used in diesel engines.
  • the Ramsbottom carbon content is preferably less than about 0.3 weight percent, as determined by the method disclosed in ASTM D 524.
  • the complex process according to the present invention for upgrading diesel oils by oxidation and extraction probably involves nitrogen addition to paraffins, olefins, naphthenes and aromatics to form nitrates, esters, amines, azides, indoles and the like.
  • the choice of an appropriate extracting solvent with a high selectivity for the compounds formed with oxidation permits selective removal of cetane-neutral or cetane-depressing compounds in extraction.
  • sulfur-containing and instability-causing compounds can be simultaneously extracted by the choice of an appropriate solvent.
  • Atmospheric gas oil is a fraction derived from petroleum crude sources. Atmospheric gas oil is one component used in diesel oil blending, and may contain an off-specification sulfur content for use as a diesel fuel. Typically, sulfur as a heteroatom is present as thiols, disulfides, sulfides, thiophenes, mercaptans, and nitrogen is present as substituted pyridines and pyrroles, and other compounds. Typical analyses of diesel oils which can be used in this invention are set forth in Table 1 below.
  • FIG. 1 describes schematically an embodiment of the process of this invention comprising mixing diesel oil feed at 1 and nitric acid through inlet 2 into a reactor 3.
  • the oxidized product 4 may be separated from a byproduct residue 5 and is passed into a solvent extractor 6, where it is contacted with an extracting solvent 7 and after solvent/oxidized oil separation to remove an extract phase containing solvent with impurities 8, the oxidized raffinate phase with residual solvent 9 is subjected to recovery at 10 to remove residual solvents 11 and to obtain upgraded diesel fuel 12 in accordance with this invention.
  • a diesel oil such as an atmospheric gas oil fraction
  • the feed oil can first be subjected to pretreatment, such as by washing to remove phenols or other corrosive components of the oil, filtering to remove gum or sediment, heating or treatment with H 2 S0 4 as conventionally used.
  • the oxidant can be a nitrogenous oxidizing agent or a non-nitrogenous oxidizing agent such as ozone.
  • nitrogenous oxidizing agent is used herein to mean any nitrogen-containing oxidizing compound including, e.g., an oxidizing gas containing at least one nitrogen oxide with more. than one oxygen atom for each nitrogen atom, a liquid containing at least one nitrogen oxide with more than one oxygen atom for each nitrogen atom, nitrous acid and nitric acid.
  • the oxidizing gas used can be a gas containing only such a nitrogen oxide or can be one which contains mixtures of such nitrogen oxides. Furthermore, the oxidizing gas can be one which also contains other components such as oxygen, nitrogen, lower nitrogen oxides, i.e., nitrogen oxides containing only one oxygen atom or less than one oxygen atom per nitrogen atom in the oxide. For efficiency, preferably the oxidizing gas will be one which contains only nitrogen oxides with more than one oxygen atom for each nitrogen atom but mixtures with other gases such as oxygen, nitrogen, as well as inert gases such as air, helium and helium with air can be employed if desired.
  • the oxidizing gas will contain at least 0.5% by volume of at least one nitrogen oxide with more than one oxygen atom for each nitrogen atom, but the concentration can be reduced if the flow rate of oxidant is increased for a longer time.
  • Nitrogen dioxide or its dimer N 2 0 4 can be advantageously employed, alone or in admixture with air.
  • the nitrogenous oxidizing liquid used can be a liquid nitrogen oxide as defined above, nitrous acid, or nitric acid, either acid concentrated or in a mixture with about 0 to 90% water by weight.
  • the liquid nitrogenous oxidizing agent is an aqueous solution of nitric acid containing about 50 to 90% nitric acid by weight.
  • nitric acid When used as a nitrogenous oxidizing agent in the present invention, it may advantageously be used in combination with other organic or inorganic acids.
  • Suitable inorganic acids include sulfuric and phosphoric acids, and suitable organic acids include, e.g., acetic and formic acids.
  • the organic and inorganic acid may be used alone or in combination.
  • an inorganic acid can be added to the aqueous nitric acid solution used as an oxidizing agent in an amount of from about 5 to 200% by weight of the nitric acid solution, and an organic acid can be added in an amount from about 5 to 200% by weight of the nitric acid solution.
  • Preferred combinations of nitric and auxiliary acids include nitric and sulfuric, nitric and acetic, and nitric and formic acids.
  • ozone When ozone is used as an oxidizing agent in the present invention, it is typically used as an oxidizing gas containing either ozone alone or a mixture which contains other components such as oxygen, nitrogen, as well as inert gases such as helium or helium with air.
  • the oxidizing gas will contain at least about 1% volume of ozone.
  • ozone can be used in the process according to the present invention in combination with a nitrogenous oxidizing agent as described above.
  • a diesel oil such as atmospheric gas oil is reacted with the oxidant in the f:orm of a liquid or gas.
  • the contacting of the diesel oil with the oxidant as a liquid can be accomplished by any means conventional in the art for contacting two liquid reactants, e.g., by injecting the oxidant under the surface of agitated oil contained in a reactor.
  • the oxidant gas can be contacted with the diesel oil using any conventional means for contacting a gaseous reactant with a liquid reactant.
  • Suitable examples of such means for contacting a gaseous reactant with a liquid reactant include dispersing the gas as bubbles in the liquid, trickling the liquid over an inert solid bed with gas passing also over the bed co-currently with or countercurrently to the liquid flow, the latter type flow being preferred.
  • the term "acid-to-oil ratio" refers to the weight of water-free acid (or its nitrogen equivalent based on 100% concentration nitric acid when a nitrogenous oxidizing agent such as NO 21 or N 2 0 4 is used) to the weight of diesel oil feedstock, and is from about 0.0001 to about 0.1, preferably from about 0.0005 to about 0.05.
  • the control of the treatment with a nitrogenous oxidizing agent in the first step of the process of this invention may be achieved by controlling the water content of the acid used in the reactor.
  • Treatment with a nitrogenous oxidizing agent in the first step can also be controlled and improved by the copresence of sulfuric acid or other auxiliary acid mixed with the oxidizing agent.
  • the amount of ozone is that amount sufficient to achieve about 10% or greater reduction up to about 50% reduction in the sulfur content of the reacted diesel oil obtained in step (a) over the diesel oil feed to step (a).
  • This control of the amount of nitrogenous oxidizing agent or ozone to the total amount of the diesel oil feed can be easily maintained.
  • step (a) of the process of this invention a cetane number increase of the reacted diesel oil over the diesel oil feed to step (a) of at least about 5 is achieved.
  • the amount of oxidizing agent can be determined.
  • Conventional means for metering gaseous and liquid reactants can be employed.
  • the reaction of the first step of the present invention can be performed at any temperature from about -40 to about 200°C, but is preferably conducted at a temperature of about 90°C or less, most preferably about 25 to 90°C.
  • the reaction time is not particularly limited, and may include, for example, any time from about 1 minute to about 3 weeks.
  • the first step of the present invention may be conducted at atmospheric pressure or at greater or lower pressures as desired.
  • the reaction step is conducted using conventional agitation means, such as a stirrer.
  • step (a) above is conducted to the extent that an increase in cetane number of at least five cetane numbers, generally seven cetane numbers and more generally nine cetane numbers, over the diesel oil feed to step (a) is achieved.
  • a nitrogenous oxidizing agent When a nitrogenous oxidizing agent is used in the first step of the present invention, typically an increase in nitrogen compound content over that originally present in the diesel oil will be observed. While not desiring to be bound by theory, the reason for the increase in observed nitrogen compound content is believed to be that nitration of the diesel oil substrate can occur resulting in an increase in the heteroatom nitrogen compound content.
  • Contact times on the order of less than about 120 minutes and weight ratios of nitrogenous oxidizing agent to total feed of less than about 0.1 are desirable not only from the standpoint of efficiency but also from the standpoint of economics. Particularly preferably, a contact time of about 30 minutes in combination with a weight ratio of nitrogenous oxidizing agent to diesel oil of about 0.05 or less can be advantageously employed with maximum yield of diesel oil having reduced sulfur content and improved stability.
  • a preferred level of nitrogen in the diesel oil following the first step of contacting the oil with a nitrogenous oxidizing agent is from about 1500 to 2000 ppm of nitrogen.
  • oil can be subjected to acid separation step, such as decanting, alkali treatment, water wash or clay treatment.
  • a diesel oil after being subjected to the reaction described above for step (a) of the process of this invention, is then subjected to an extraction step (b) with an appropriate extracting solvent.
  • processing conditions set forth for the reaction step (a) above are controlled to improve the ability of the specific and selected extracting solvents used in the extracting step (b) of the process of this invention to enhance removal by extraction of sulfur-containing impurities, instability-causing compounds, Ramsbottom carbon, cetane-depressing compounds present originally in the diesel oil to be upgraded, and thereby to reduce their level in the ultimate diesel oil recovered and upgrading as a result of the process of this invention.
  • step (b) of the process of this invention the diesel oil obtained from step (a) of the process of this invention is contacted with an extracting solvent
  • appropriate extracting solvents having the above-described characteristics as to dipole moment, immiscibility, non-halogenation and oxidant-non-reactivity include solvents having the following functional groups therein and
  • solvents useful in the extraction step (b) of the present invention which have the required dipole moment and immiscibility and are nonhalogenated and non-amine include furfural, butyrolactone, dimethyl formamide, methyl carbitol, tetrahydrofurfuryl alcohol, dimethyl sulfoxide, sulfolane, sulfolene, acetic anhydride, dimethylacetamide, acetonitrile, I-methyl-2-pyrrolidone, nitrobenzene, and nitromethane.
  • extracting solvents can be used alone or in combination, and further each of the extracting solvents used can be used alone in admixture with or as mixture in admixture with water to the extent of up to about 50% by weight of water.
  • Water in combination with these extracting solvents can be advantageously used to increase phase separation and yields of oil recovered in extraction step (b).
  • the amount of water which can be used with any particular extracting solvent can be appropriately determined by running routine screening tests to determine for a particular diesel oil feedstock to be upgraded and under the reaction conditions employed in step (a), which of the extracting solvents, alone or in admixture with water and to what extent in admixture with water can be advantageously used.
  • routine screening tests can be simply a consideration of yield, reduction in sulfur content present, stability and cetane number, determined by routine chemical analysis, to determine which of the extracting solvents or water/extracting solvent mixtures can be most advantageously used with a given diesel oil feed.
  • step (b) of the present invention conventional extraction procedures are employed.
  • the extracting solvent is simply added to and mixed with the diesel oil processed as in step (a).
  • the length of time for contact of the extracting solvent is only that time necessary to permit a simple mass transfer of the sulfur compound impurities, instability-causing compound impurities, or Ramsbottom carbon containing components from the diesel oil phase into the extracting solvent phase, and is typically from about 1 to 30 minutes.
  • a suitable extraction time ranges from about 1 to about 10 minutes.
  • the temperature of the extracting step is controllable over wide ranges, and can be, for instance, any temperature from about 40°F to about 300°F and preferably is at room temperature, e.g., about 70°F to 90°F.
  • the solvent can be added in substantially pure form, e.g., as obtained directly from commercial sources, or can be a used solvent which is recovered and purified or a recycle stream rich solvent, with any deficiency in amount of solvent desired for extraction being made up by the addition of additional solvent.
  • the solvent extraction step (b) can be conducted, if desired, in a sequence of separate solvent extraction zones, varying, e.g., time, temperature, or solvent-to-oil ratio as desired.
  • the extracting solvent is immiscible with the diesel oil and is nonhalogenated.
  • the lack of miscibility thus permits an easy phase separation after the extraction is completed. If an emulsion is formed, it can be easily broken, e.g., by warming, for phase separation. Further, oxidant reactive amine solvents are not employed as extracting solvents in extraction step (b) of the process of this invention.
  • step (b) of the process of this invention can be generally conducted by simply adding the extracting solvent to the diesel oil, mixing such with the diesel oil, allowing phase separation of the mixture to occur and then separating the extracting solvent phase containing the sulfur impurity content or instability-causing content removed from the diesel oil substrate phase.
  • Conventional chemical engineering techniques can be employed to achieve this extraction conducted in step (b) of the process of this invention.
  • a suitable extracting solvent-to-oil ratio (S/O) by weight can range from about 0.05:1 to about 5:1, preferably 0.1:1 to 0.5:1, but these ratios are not considered to be limiting.
  • the solvent-to-oil ratio in the solvent extraction step (b) is reduced to much smaller values than those conventionally used in order to increase the overall efficiency of the reaction/extraction process of this invention.
  • the efficiency of solvent extraction of sulfur impurities can be improved by increasing the solvent-to-oil ratio in extraction even without reaction with an oxidant.
  • FIG. 2 shows the results of the extraction of an atmospheric gas oil of Table 1 by gamma-butyrolactone. For an unreacted AGO, at a solvent-to-oil ratio (S/O) of 1.0:1 by weight, the raffinate had a yield of 91% by weight but with only 22% sulfur reduction (0.93% S).
  • FIG. 3 which illustrates the effects of reaction of an atmospheric gas oil of Table 1 on gamma-butyrolactone extraction
  • an increase in solvent-to-oil ratio decreases oil yield even with reacted oils.
  • the loss in oil yield can be offset by an increase in severity of reaction.
  • a 55% sulfur removal by extraction requires a S/O ratio of about 6.0:1 for unreacted oil, an S/O ratio of more than 1.0:1 for mildly reacted AGO, a S/O ratio of less than 1.0:1 for moderately severely reacted AGO and a S/O ratio of less than 0.5:1 for severely reacted AGO, when the severity of reaction is here expressed in terms of sulfur content remaining after reaction.
  • the oil is defined as "severely reacted" when the sulfur reduction is more than about 50%.
  • the decrease in solvent-to-oil ratio is accompanied by a significant increase in oil yield, i.e., from about 75 weight percent extracted oil yield for unreacted oil to more than 90% extracted oil yield for severely reacted oil.
  • one aspect of the present invention is that surprisingly low solvent-to-oil ratios are required to obtain a desired degree of sulfur reduction for reacted as opposed to unreacted stocks.
  • nitric acid or ozone will significantly deteriorate stability and Ramsbottom carbon.
  • a weight ratio of only 0.0025 of 90% nitric acid to oil will increase Ramsbottom carbon to levels of over 1.5% and will deteriorate Nalco stability to about 20.
  • Solvent extraction by the solvents of the present invention can be used to bring stability and Ramsbottom carbon into commercially acceptable specifications, while removing sulfur, retaining cetane, and achieving high raffinate yields.
  • the results achieved depend upon solvent to oil ratio, the extracting solvent chosen, extractor stage efficiency, number of stages, and co-current or counter-current operation.
  • an oxidant treated diesel oil with a Ramsbottom carbon of 7% and a Nalco stability of 20 can be extracted to produce an upgraded diesel fuel with a Nalco stability of 7 and a Ramsbottom carbon of 0.2% at a solvent-to-oil ratio of 0.56.
  • Ramsbottom carbon contents of ⁇ .62% and 0.14% can be achieved.
  • the process according to the present invention provides substantially improved yields with substantially lower and more economic solvent-to-oil ratios than heretofore achieved.
  • the extracting solvents employed in the present invention can be used in their commercially available forms as described above or can be upgraded to remove any undesired components which might be present in the commercially available forms.
  • Step (c) of the process of this invention comprises recovery of the diesel oil substrate purified as a result of the reaction step (a) and extraction step (b) of the process of this invention.
  • Conventional purification procedures for removal of an extracting solvent from a diesel oil can be employed. These extraction procedures include distillation, fractional crystallization, water washing followed by distillation and any other appropriate conventional procedures for removing an extracting solvent from an oil substrate.
  • the process of this invention is not to be construed as limited in any way to selection of a specific diesel oil recovery and separation procedure.
  • the process of this invention described above can be advantageously used to upgrade various types of petroleum derived diesel oils containing heteroatom sulfur compound impurities and organic compounds causing instability in the diesel oil products.
  • diesel oils having a heteroatom sulfur content ranging up to about 4% by weight can be subjected to and purified in accordance with the process of this invention to yield from the process of this invention an upgraded diesel fuel having on the order of at least about 30%, preferably about 75%, sulfur impurity content removal, while simultaneously improving product stability.
  • diesel oils of relatively low initial sulfur content can be upgraded and purified in accordance with the process of this invention to yield a upgraded diesel oil having improved cetane and meeting stability, Ramsbottom carbon and sulfur product specifications with somewhat reduced sulfur content removal at higher yield, by conducting the extraction step (b) of this invention using a low solvent-to-oil ratio.
  • Diesel oils which are not of petroleum origin generally contain high levels of aromatics, olefins, or both.
  • the solvents employed in the present invention are generally ineffective for such oils, and are less effective for petroleum oils with high aromatics or olefin levels, due to the strong affinity of the solvent employed in this invention for these compounds.
  • such diesel oils will exhibit inferior yields at all solvent-to-oil ratios employed, and many of such solvents become miscible with the oil at low solvent-to-oil ratios of about 0.2 or lower.
  • step (a) of the process of this invention results in a remarkably economical and advantageous process. This is particularly true when it is compared with the high temperature and high pressure hydrodesulfurization treatments employed conventionally in the past. Further, the advantages of the process of this invention can be seen in comparison with similar upgrading processing using catalysts conventionally employed in the art since an expensive catalyst is not needed and no steps are required to separate catalyst or regenerate catalyst. Thus, the process of this invention is considered to be a marked advance over current technology for cetane improvement and upgrading diesel oils containing sulfur impurities or instability-causing impurities, and is believed to be of particular commercial significance.
  • the process of this invention can be used to purify and upgrade diesel fuel oils, to reduce sulfur content, improve stability, increase cetane number and reduce Ramsbottom carbon content.
  • diesel oils after reaction in step (a) of the present invention and having a sulfur content up to about 4% by weight, a stability as determined by the Nalco test of up to about 20 or higher, and a Ramsbottom carbon content of up to about 15% or higher can be purified and upgraded according to the process of this invention to obtain a diesel fuel having on the order of about 5-70% sulfur impurity content removal, a Nalco stability improvement including improvements to about 7 or less, a cetane number improvement for the product of the process of this invention of about 5 to about 20 cetane numbers above feed and a significant reduction in Ramsbottom carbon content including the ability to achieve a Ramsbottom carbon content of less than about 0.3%.
  • the diesel oil upgraded in accordance with the process of this invention can be used per se or as a blending stock to produce desired products, such as a diesel fuel having an improved cetane number.
  • desired products such as a diesel fuel having an improved cetane number.
  • the high-cetane, low-sulfur raffinate obtained in the process according to the invention can be blended with other diesel fuels or cycle oils which may have adequate stabilities but low cetane, or in some cases high sulfur, to obtain a diesel fuel meeting standard commercial product specifications.
  • each of the embodiments of the process of this invention described above can be advantageously conducted in a batchwise, semi-continuous or continuous manner.
  • the procedure employed, unless otherwise indicated, for reacting the oxidizing gas with the diesel oil was to charge a weighed amount of the oil, approximately 400 grams, into the reactor. From the weight of the oil charged and the chemical analysis thereof, the total moles of sulfur heteroatom compounds, nitrogen heteroatom compounds, cetane number and Ramsbottom carbon content were known.
  • the oxidant gas flow rate into the reactor was set by considering the weight ratio of oxidant to diesel gas oil and the contact time.
  • the weight ratio set forth in the examples to follow is the ratio of total weight of oxidant used for a particular contact time to the total weight of the oil charged. Control of the flow rate was achieved using a rotameter, appropriately calibrated.
  • Various contact times for reaction of 5, 15, 30 and 60 minutes, various weight ratios of oxidant to total feed weight of 0.01 to 0.14 were employed at an initial reactor temperature of 25°C unless otherwise indicated.
  • nitrogen dioxide was used as an oxidant, it was mixed with air at a volume ratio of one part nitrogen dioxide to four parts air.
  • ozone was used as an oxidant, the ozone was generated with oxygen at a volume ratio of about one part by volume ozone to ten parts by volume oxygen before being introduced into the reactor.
  • the raffinate was washed twice with water, using a water-to-raffinate ratio of 1.0 by weight for each wash, before measuring the raffinate oil yield. After washing, the final oil obtained (from which the solvent had been removed) was collected and weighed.
  • Sulfur analysis was conducted using a Princeton Gamma-Tech Model 100 chemical analyzer. Stability analysis was conducted by a standard Nalco test, i.e., by heating a tube containing the sample of oil for 90 minutes and then filtering the heated oil using a micropore filter and No. 1 filter paper, followed by washing the filter and the filter paper with heptane and comparing the residue to a standard. Determination of the cetane number of the resulting diesel fuel was determined using a diesel test engine (ASTM D613). Ramsbottom carbon content (ASTM D524) was evaluated by distilling 90% overhead and taking a portion of the bottom 10% which was burned in a Ramsbottom oven, after which the residue was weighed.
  • solvents were acetone, hexane, 2-butanone, 2-octanone, nitrobenzene, isobutylamine, diethylamine, ethyl acetate, pyridine, methylene chloride, diethyl ether, 2-propanol, trichloroethane, and trichloroethene.
  • the reaction severity was measured by the weight ratio of N0 2/ oil, which is defined as the ratio of weight of N0 2 added within the given contact time to the weight of oil charged. For this reaction, the N0 2/ oil ratio was about 0.04.
  • a 20 milliliter sample of this oxidized oil was then extracted using 20 ml of each solvent shown in Table 5 below, using the same procedures as described above in Comparative Example 1.
  • the reaction severity was measured by the weight ratio of N0 2/ oil, which is defined as the ratio of grams of N0 2 added within the given contact time to the grams of oil charged.
  • Each oxidized oil was water-washed at a water/oil weight ratio of 1.0. Sulfur removal and higher cetane number improvement in the oil were accomplished, as shown in Table 6, both increasing as the weight ratio of N0 2/ oil was increased.
  • the Ramsbottom carbon content of the reacted diesel oil was 1.52%, considerably above the commercial specification level of 0.3% for a diesel fuel. Although the Nalco stability was not measured, significant deposits formed upon storage for 20 days, indicating the stability rating would exceed 15.
  • Nitrogen is known to contribute Ramsbottom carbon and stability problems in diesel fuels. Therefore, a nitrogen removal solvent, formic acid, disclosed in U.S. Patent No. 4,485,007 as being an excellent nitrogen removal solvent, was tested.
  • a one-liter sample of atmospheric gas oil, Stock CC, as described in Table 1 was oxidized for 30 minutes using 90% HN0 3 at a weight ratio of HN0 3/ diesel oil feed of 0.01 at a temperature of 25°C in accordance with the process of the present invention.
  • the oxidant reacted oil obtained was then extracted with mixtures of dimethylformamide and water, as set forth in Table 13 below, using the extraction procedures described above for Comparative Example 1.
  • the results obtained are set forth in Table 13 below. The results show that the water content of the solvent can be adjusted to further improve the yield of the product of the present invention.
  • selected solvents of the present invention are compared to comparison solvents in Table 14.
  • the raffinates from the high dipole moment solvents have an improved sulfur level, yield, and Ramsbottom carbon, and stability compared to the raffinates obtained using comparison solvents.
  • H 2 SO 4 in the three concentrations set forth in Table 16 below was added to the 90% nitric acid.
  • the oxidized oil obtained was then extracted with gamma-butyrolactone using the extraction procedures described above in Comparative Example 1 at a solvent-to-oil ratio of 0.5.
  • Table 14 The results obtained were set forth in Table 14 below.
  • excellent cetane, Ramsbottom carbon, stability and yields were achieved where with H 2 SO 4 only (see Table 16), an inferior cetane rating was obtained.
  • Oxidized oil products from Example 3 were subjected to more extensive phase equilibria analysis. Without being limited by theory, it appears that heteroatoms are being added to the substrate material which enhance the affinity of the solvent in the extraction stage, thereby improving yields.
  • the preferential addition of heteroatoms to molecules which also contain sulfur atoms, which thereby permits the selective extraction of sulfur compounds, is a particularly surprising aspect of the process of the present invention.
  • phase lines illustrate a negative slope, showing poor selectivity in the removal of sulfur from the oxidant unreacted diesel oil.
  • the point R 1 shows that the raffinate phase contained 2% gamma-butyrolactone and 0.97% sulfur whereas the corresponding extract phase E 1 contained 91% gamma-butyrolactone and 0.48% sulfur.
  • a much higher extract phase sulfur content would be desirable.
  • the A/O ratio is defined as the ratio of weight of HN0 3 (calculated as 100% HN0 3 ) added within the contact time to the weight of oil charged.
  • each 20 milliliter sample of the oxidant reacted diesel oil sample was contacted with each solvent shown in Table 18 below using the procedures set forth in Comparative Example 2.
  • extraction of oxidant reacted diesel oil with selective solvents of this invention improves the Nalco stability and Ramsbottom carbon of the diesel oil while retaining its cetane number enhancement.
  • Table 19 shows the results obtained for the five semi-batch oxidations with the cetane number of the oxidant reacted oil.

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0252606A2 (fr) * 1986-06-09 1988-01-13 Exxon Research And Engineering Company Procédé pour augmenter l'indice de cétane d'huiles diesel
WO1995001411A1 (fr) * 1993-06-30 1995-01-12 Horst Kief Carburant pour moteurs a combustion interne et turbines
US5824207A (en) * 1996-04-30 1998-10-20 Novetek Octane Enhancement, Ltd. Method and apparatus for oxidizing an organic liquid
EP1250400A1 (fr) * 1999-12-28 2002-10-23 ExxonMobil Research and Engineering Company Procede de distillation extractive permettant de reduire les especes soufre dans des flux d'hydrocarbures
CN100404646C (zh) * 2005-02-05 2008-07-23 中国石油化工股份有限公司 一种劣质柴油馏分改质的方法
WO2009098264A1 (fr) * 2008-02-06 2009-08-13 Shell Internationale Research Maatschappij B.V. Procédé de désulfuration oxydative d'un combustible hydrocarboné
US8859833B2 (en) 2011-04-12 2014-10-14 OTG Research, LLC Methods and systems for obtaining long chain carbons from petroleum based oil
US9006504B2 (en) 2011-04-12 2015-04-14 OTG Research, LLC Methods for converting motor oil into fuel
US9365780B2 (en) 2014-02-19 2016-06-14 King Abdulaziz City For Science And Technology Cold process for removal of sulfur in straight run diesel by ozone and tert-butyl hydroperoxide
CN113061458A (zh) * 2021-03-17 2021-07-02 武汉工程大学 一种油品脱硫萃取剂及油品脱硫方法
CN113234479A (zh) * 2021-06-16 2021-08-10 河北科技大学 一种基于臭氧氧化的分相脱硫方法及其装置

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0753974A (ja) * 1993-08-06 1995-02-28 Tadashi Mochihata エマルジョン燃料の製造法
EP2542651A4 (fr) 2010-03-01 2017-08-23 Envirollea Inc. Procédé d'extraction par solvant utilisé pour stabiliser, désulfuriser et sécher de nombreux carburants diesel, les nombreux carburants diesel stabilisés obtenus et utilisations associées
CA2973210A1 (fr) 2017-07-13 2019-01-13 Louis Bertrand Procede de production de combustible liquide a partir de rejets d'hydrocarbure ou de matiere organique, systeme de gestion associe

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2521698A (en) * 1946-05-02 1950-09-12 California Research Corp Injection engine fuel
US3197400A (en) * 1962-07-10 1965-07-27 Pure Oil Co Process for removing sulfur from diesel oils
US3309309A (en) * 1965-05-27 1967-03-14 Exxon Research Engineering Co Denitrification of hydrocarbons
US4113607A (en) * 1977-03-03 1978-09-12 Chevron Research Company Denitrification process for hydrogenated distillate oils
US4280818A (en) * 1980-02-22 1981-07-28 Gulf Research & Development Company Novel compositions of matter and process for utilizing same
EP0097055A2 (fr) * 1982-06-15 1983-12-28 REI Technologies Inc. Procédé pour la purification d'huiles hydrocarbonées

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2521698A (en) * 1946-05-02 1950-09-12 California Research Corp Injection engine fuel
US3197400A (en) * 1962-07-10 1965-07-27 Pure Oil Co Process for removing sulfur from diesel oils
US3309309A (en) * 1965-05-27 1967-03-14 Exxon Research Engineering Co Denitrification of hydrocarbons
US4113607A (en) * 1977-03-03 1978-09-12 Chevron Research Company Denitrification process for hydrogenated distillate oils
US4280818A (en) * 1980-02-22 1981-07-28 Gulf Research & Development Company Novel compositions of matter and process for utilizing same
EP0097055A2 (fr) * 1982-06-15 1983-12-28 REI Technologies Inc. Procédé pour la purification d'huiles hydrocarbonées

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0252606A2 (fr) * 1986-06-09 1988-01-13 Exxon Research And Engineering Company Procédé pour augmenter l'indice de cétane d'huiles diesel
EP0252606A3 (fr) * 1986-06-09 1989-03-15 Exxon Research And Engineering Company Procédé pour augmenter l'indice de cétane d'huiles diesel
WO1995001411A1 (fr) * 1993-06-30 1995-01-12 Horst Kief Carburant pour moteurs a combustion interne et turbines
US5762655A (en) * 1993-06-30 1998-06-09 Kief; Horst Fuel for internal combustion engines and turbines containing ozonization products
US5824207A (en) * 1996-04-30 1998-10-20 Novetek Octane Enhancement, Ltd. Method and apparatus for oxidizing an organic liquid
EP1250400A1 (fr) * 1999-12-28 2002-10-23 ExxonMobil Research and Engineering Company Procede de distillation extractive permettant de reduire les especes soufre dans des flux d'hydrocarbures
EP1250400A4 (fr) * 1999-12-28 2004-08-04 Exxonmobil Res & Eng Co Procede de distillation extractive permettant de reduire les especes soufre dans des flux d'hydrocarbures
CN100404646C (zh) * 2005-02-05 2008-07-23 中国石油化工股份有限公司 一种劣质柴油馏分改质的方法
WO2009098264A1 (fr) * 2008-02-06 2009-08-13 Shell Internationale Research Maatschappij B.V. Procédé de désulfuration oxydative d'un combustible hydrocarboné
US8859833B2 (en) 2011-04-12 2014-10-14 OTG Research, LLC Methods and systems for obtaining long chain carbons from petroleum based oil
US9006504B2 (en) 2011-04-12 2015-04-14 OTG Research, LLC Methods for converting motor oil into fuel
US9499754B2 (en) 2011-04-12 2016-11-22 OTG Research, LLC Methods for converting motor oil into fuel
US9518234B2 (en) 2011-04-12 2016-12-13 OTG Research, LLC Methods and systems for converting petroleum based oil into fuel
US9365780B2 (en) 2014-02-19 2016-06-14 King Abdulaziz City For Science And Technology Cold process for removal of sulfur in straight run diesel by ozone and tert-butyl hydroperoxide
CN113061458A (zh) * 2021-03-17 2021-07-02 武汉工程大学 一种油品脱硫萃取剂及油品脱硫方法
CN113234479A (zh) * 2021-06-16 2021-08-10 河北科技大学 一种基于臭氧氧化的分相脱硫方法及其装置

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