CN100339462C - Organosulfur oxidation process - Google Patents
Organosulfur oxidation process Download PDFInfo
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- CN100339462C CN100339462C CNB2003801099391A CN200380109939A CN100339462C CN 100339462 C CN100339462 C CN 100339462C CN B2003801099391 A CNB2003801099391 A CN B2003801099391A CN 200380109939 A CN200380109939 A CN 200380109939A CN 100339462 C CN100339462 C CN 100339462C
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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
- 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
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
This invention is a method of oxidizing organosulfur impurites found in fuel streams. The method comprises reacting the organosulfur impurities with an organic hydroperoxide in the presence of a titanium-containing catalyst. The titanium-containing catalyst is obtained by impregnating a siliceous solid with a titanium halide in a hydrocarbon solvent, or a vapor stream of titanium tetrachloride, followed by calcination. The resulting sulfones are more readily removed from the fuel stream than the non-oxidized organosulfur impurities.
Description
Technical field
The present invention relates to a kind of method that is used for the contained organosulfur impurities oxidation of fuel stream.Described method comprises that organosulfur impurities reacts with organic hydroperoxide in the presence of titanium-containing catalyst.Described titanium-containing catalyst makes with following step: be used in the varsol halogenated titanium or with the vapour stream of titanium tetrachloride dipping silicon-containing solid, carry out roasting subsequently.Described catalyzer is effective especially when the contained sulfur-containing impurities oxidation of fuel.
Background technology
The hydrocarbon fraction that petroleum industry is produced is polluted by various sulfur-containing impurities usually.These hydrocarbon fractions comprise diesel oil fuel and gasoline, comprising natural gasoline, straight-run spirit and pressure gasoline.The hydrocarbon fraction of other sulfur-bearings comprises common gaseous petroleum fraction and petroleum naphtha, kerosene, rocket engine fuel, fuel wet goods.The existence of sulfocompound is undesirable, because they cause serious pollution problem.The hydrocarbon fuel that contains these impurity can discharge deleterious and mordant oxysulfide.
Federal legislation specifically is that the amendment of Clean Air sct in 1964 and 1990 and 1999 proposes more and more stricter requirement to the sulphur quantity that minimizing is discharged in the atmosphere.EPA drops to 15ppmw with the sulphur emissions standard of diesel oil from the 500ppmw of existing standard, and mid-term in 2006 came into force.For blended gasoline, the 300ppmw of existing standard has dropped to 30ppmw, and on January 1st, 2004 came into force.
Because these regulations have demand to more effective sulfur method all the time.In this specialty, the various sulfur methods that contain the hydrocarbon fraction of organic sulfide impurity are that everybody is familiar with.The most frequently used method of desulfurization of fuels is hydrogenating desulfurization, fuel and hydrogen reaction in the presence of expensive catalyst under intensification and high pressure in this method.For example, US 5985136 discloses a kind of hydrodesulfurizationprocess process that reduces sulphur content in the naphtha feed.By this reaction, organic sulfide is reduced into H
2S gas is oxidized to elementary sulfur by Kraus process then.Regrettably, the unreacted H that obtains of described method
2S is deleterious, even under the situation of small number very.Though hydrogenating desulfurization is easy to make mercaptan, thioether and disulfide to transform, other organosulfur compounds for example replace is difficult to remove with unsubstituted thiophene, thionaphthene and dibenzothiophene and reaction conditions that needs are harsher.
Because these problems relevant, so continue other sulfur methods are studied with hydrogenating desulfurization.For example, US 6402939 disclose use hydroperoxide particularly hydrogen peroxide make the ultrasonic oxidation of sulfur-containing impurities in the fossil oil.These sulfur-containing impurities through oxidation are isolated from fossil oil than unoxidized impurity is easier.Other method relates to the desulfurization of hydrocarbon materials, and cut is at first handled by the method with the hydro carbons of oxygenant oxidation sulfur-bearing in the presence of catalyzer there.For example US 3816301 disclose a kind of by in the presence of some catalyzer with organic hydroperoxide for example tert-butyl hydroperoxide oxidation at least a portion sulfur-containing impurities reduce the method for the sulphur content of sulfur-bearing hydro carbons.Described catalyzer is preferably the catalyzer that contains molybdenum.
In a word, the novel method that needs sulfur compound impurities in the oxidizing hydrocarbons cut.Particularly need the efficient oxidation to be difficult to the method for the thiophene impurities of oxidation.We have found a kind of effective ways that are used for the contained organosulfur impurity of oxygenated fuel logistics.
Summary of the invention
The present invention is a kind of method that contained organosulfur impurities in the fuel stream is oxidized to the sulfone class.Described method is included under organic hydroperoxide and the titanium-containing catalyst existence and makes the organosulfur impurities oxidation.Titanium-containing catalyst makes with such method, and described method comprises: (a) with titanium source dipping inorganic siliceous solid; (b) roasting is chosen heatable catalyst in the presence of water wantonly through the solid of dipping with (c).The titanium source can be the solution of halogenated titanium in non-oxide varsol, or is the vapour stream of titanium tetrachloride.Optional is that the Preparation of catalysts method also comprises the additional step of handling catalyzer with the silylation agent.Described catalyzer is effective especially when the contained sulfur-containing impurities of oxygenated fuel.The sulfone class can be extracted from fuel stream then, make purified fuel stream.
Embodiment
Method for oxidation of the present invention utilizes titaniferous heterogeneous catalyst, unexpectedly finds, compares with the catalyzer that uses other dipping methods to make, and described catalyzer has high oxidation susceptibility.Be used for catalyzer of the present invention by preparing with halogenated titanium dipping inorganic siliceous solid.
Impregnation steps can be by realizing with the solution impregnation inorganic siliceous solid of halogenated titanium in non-oxide varsol.Be suitable for the hydro carbons of the solvent of this purpose for those oxygen-free atoms, they are liquid at ambient temperature, and can dissolve halogenated titanium.In general, wish to select like this varsol, can reach at least 0.5% (weight) in the concentration of 25 ℃ of following halogenated titaniums in described solvent.Described varsol preferably should have suitable volatility, so that it is easy to remove from inorganic siliceous solid behind the dipping.Therefore, normal boiling point is that 25-150 ℃ solvent can utilize well.Particularly preferred hydro carbons comprises C
5-C
12Aliphatic hydrocrbon (straight chain, side chain or cyclic), C
6-C
12Aromatic hydrocarbons (comprising the aromatic hydrocarbons that alkyl replaces), C
1-C
10Halogenated aliphatic hydrocarbon and C
6-C
10Halogenated aryl hydrocarbon.Most preferably, solvent does not contain de-carbon, hydrogen and (choosing wantonly) halogen element in addition.If halogen is arranged, be preferably chlorine so in solvent.
If necessary, can use the mixture of non-oxide hydro carbons.Preferably, the solvent that is used to flood is substantially free of water (promptly anhydrous).Though oxygen containing hydro carbons for example alcohols, ethers, ester class, ketone etc. can mix existence with required non-oxide hydro carbons, in a desirable embodiment of the present invention, in steeping process, has only non-oxide hydro carbons to exist as solvent.The example of the varsol that is fit to comprises normal hexane, normal heptane, pentamethylene, methylpentane, methylcyclohexane, dimethylhexane, toluene, dimethylbenzene, methylene dichloride, chloroform, ethylene dichloride, chlorobenzene, benzyl chloride etc.
In preferred embodiments, pickling process is characterized as anhydrous basically after dipping is finished at least, and is preferably anhydrous basically later in roasting.In content of the present invention, " essentially no " is meant and deliberately do not add entry, if perhaps deliberately add, before adding halogenated titanium it is removed so.When commercial size was sold, the application that the reagent of minor amount of water and raw material arranged in such reagent and raw material usually within the scope of the invention.Preferably, in non-oxide hydro carbons, have less than 500ppm water (more preferably, less than 100ppm).
The halogenated titanium that is fit to comprises trisubstituted and quaternary titanium complex, and described title complex has 1-4 halogenide substituting group, if having, all the other substituting groups are alkoxide or amino.The halogenated titanium that is fit to comprises the mixed halide, diisopropoxy titanium dichloride, two (diethylin) titanium dichloride of titanium tetrachloride, titanium tetrafluoride, titanium tetrabromide, titanium tetra iodide, titanous chloride and Ti (III) or Ti (IV) halogenated titanium etc.Preferably, all substituting groups that are connected on the titanium all are halogenide.Most preferably, halogenated titanium is a titanium tetrachloride.
Though the concentration of halogenated titanium in varsol is inessential, the concentration of halogenated titanium is usually in 0.01-1.0 mol scope.Wishing to regulate like this concentration and the solutions employed quantity of halogenated titanium in varsol, is 0.1-15% (weight) (pressing total restatement of catalyzer with Ti) so that make the titanium content in the final catalyzer.Repeatedly dipping (centre have or do not have drying and/or roasting) can be used to the titanium content that reaches required.
Being suitable for inorganic siliceous solid of the present invention is such solid material, and their major portion is silicon oxide (silicon-dioxide), and its specific surface area is at least 50 meters
2/ gram, preferred average specific surface area is a 300-2000 rice
2/ gram.Inorganic siliceous solid is a porous, in its entire structure many ducts, cavity or space is arranged.
Major portion is that the synthesizing inorganic oxide material of silicon oxide is another kind of inorganic siliceous solid.Such material is called the infusible oxide compound, and they comprise silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silica-alumina-boron oxide and silica-alumina-magnesium oxide.Molecular sieve particularly macropore or mesoporous molecular sieve for example MCM-41, MCM-48 and M41S also can be used as inorganic siliceous solid.
Preferred inorganic siliceous solid is silicon oxide and mesoporous molecular sieve, for example MCM-41, MCM-48 and M41S.Particularly preferably be silicon oxide and MCM-41.
Very wish dry inorganic siliceous solid before dipping.For example can 100-700 ℃, preferably at least 200 ℃ down heating inorganic siliceous solid a few hours are carried out drying.In general, in order to reach enough degree of dryings, do not need to use temperature above 700 ℃.Can use vacuum or mobile dry gas (for example nitrogen) stream to quicken drying process.
Can use any conventional usefulness of using to be fit to the method for soaker dipping porosu solid.For example, halogenated titanium can be dissolved in varsol, be added to then in the inorganic siliceous solid or and make up with inorganic siliceous solid.Also inorganic siliceous solid can be added in the hydrocarbon solution of halogenated titanium.
For fear of forming slurries, use the solvent of minimum number, " beginning wetting " dipping technique also is suitable for.Before further handling, can be with the mixture ageing that generates, the optional stirring or other mixing.In general, dipping solution should be contacted for some time with inorganic siliceous solid, so that be enough to make solution to be penetrated into fully in the available pore volume of solid.Can before roasting, remove the varsol that is used to flood subsequently in medium intensification (for example 50-200 ℃) and/or the following drying of decompression (for example 1-100 mmhg).Preferred selective solvent like this removes the condition in the step, so that removes at least 80%, more preferably at least 90% varsol that is used to flood in the past in roasting.Drying step can be removed any excessive dipping solution in decant, filtration or centrifugation and carry out later on.The washing of the silicon-containing solid through flooding is unnecessary.Therefore, being characterized as of a desirable embodiment of the present invention do not have such washing step.
Be applicable to that catalyzer of the present invention also can be by preparing with vapor stream of titanium tetrachloride dipping inorganic siliceous solid.Flowing on titanium tetrachloride by gas provides described vapour stream.Vaporizing greater than under 50 ℃ and the normal pressure.Preferably, vaporization temperature greater than 80 ℃, most preferably greater than 130 ℃.On the other hand, by reducing reaction pressure, lower temperature also is possible.Preferably, described gas is rare gas element, for example nitrogen, helium, argon, carbonic acid gas etc.Then vapor stream of titanium tetrachloride is passed through on the high surface area inorganic silicon-containing solid, so that finish impregnation steps.In steeping process, inorganic siliceous solid is remained on more than 50 ℃.Preferably, dipping temperature is remained on more than 80 ℃, most preferably more than 130 ℃.
After the dipping, come the silicon-containing solid of roasting vapor phase and liquid impregnation by heating under heating up.Roasting can or more preferably be carried out in the presence of rare gas element at oxygen (for example air), and described rare gas element is substantially free of oxygen, for example is nitrogen, argon, neon, helium etc. or its mixture.In one embodiment of the invention, at first in being substantially free of the atmosphere of oxygen, carry out roasting, send into oxygen subsequently.Preferably, calcination atmosphere contains the mole oxygen less than 10000ppm.More preferably, in calcination atmosphere, exist less than the 2000ppm mole oxygen.It is desirable to, in roasting process, the concentration of oxygen is less than 500ppm.But will be appreciated that in large-scale commercial operation, the condition that is substantially free of oxygen is difficult to reach.Optional is that when existing, roasting can for example be carried out in the presence of the carbon monoxide at reducing gas as some oxygen (for example up to the 25000ppm mole).Certainly, the optimal number of reducing gas is with many factors vary of the person's character that comprises oxygen concn in the calcination atmosphere and reducing gas, but the content of reducing gas is that 0.1-10% (mole) is normally enough in the calcination atmosphere.In one embodiment of the invention, roasting is carried out in the atmosphere of one or more rare gas elementes (for example nitrogen, helium, argon, carbonic acid gas) that contain aerobic, reducing gas (preferred carbon monoxide) and choose wantonly.
Crossing with air communication in the roasting process of beds, catalyzer can be remained in the fixed bed.In order to improve the oxidation activity of catalyzer, it is important carrying out roasting under at least 500 ℃ temperature.More preferably, maturing temperature is at least 700 ℃, but is not more than 1000 ℃.Usually, about 0.1 to 24 hour roasting time is enough.
After roasting and/or in roasting process, catalyzer and water reaction.Such reaction for example can contact about 0.1 to 6 hour with water vapor down at heat up (preferably above 100 ℃, more preferably 150-650 ℃) by catalyzer and carry out.In order to reduce halogenide quantity residual in the catalyzer that makes by the halogenated titanium reactant and, to wish with the reaction of water in order to improve the hydroxy density of catalyzer.
Also can under heating up, handle catalyzer with the Organosilyl agent.Preferably after roasting, most preferably carry out later silylanizing in roasting with the water reaction.The silylanizing method of the present invention that is applicable to is disclosed among the US 3829392 and 3923843.The silylating agent that is fit to comprises organosilane, organo-halogen-silane and organic disilazane.
The organosilane that contains 1-3 organic substituent be can use, a chlorine trimethyl silane, dichlorodimethylsilane, nitrotrimethylolmethane methyl-monosilane, a chlorine triethyl silicane, a Chlorodimethyl phenyl silane etc. for example comprised.Preferred organo-halogen-silane silylating agent comprises quaternary silane, and 1-3 substituting group that is selected from chlorine, bromine and iodine wherein arranged, and remaining substituting group is methyl, ethyl, phenyl or its combination.
Organic disilazane molecular formula R
3Si-NH-SiR
3Expression, wherein the R group independently is alkyl (preferred C
1-C
4Alkyl) or hydrogen.What especially preferably use is the disilazane that six alkyl replace, for example hexamethyldisilazane.
With the processing of silylating agent can liquid phase (be that silylating agent is used for catalyzer as liquid, with silylating agent itself or be fit to solvent for example the solution in the hydro carbons use) or in gas phase (being that silylating agent contacts with catalyzer with gas form), carry out.Treatment temp is preferably about 80 to 450 ℃, uses high slightly temperature (for example 300-425 ℃) when silylating agent is organo-halogen-silane usually, and for organic disilazane, preferred low slightly temperature (for example 80-300 ℃).Silylanizing can by intermittently, semicontinuous or continuous mode carries out.
The required time portion of silylating agent and catalyst surface reaction depends on used temperature and reagent.The reaction times of the low more common needs of temperature is long more.Usually, be fit in 0.1-48 hour.
The quantity of the silylating agent that uses can change in wide region.The silylating agent quantity that is fit to can be about 1 to about 75% (weight) (by the weight of whole catalyst composition), and the quantity of 2-50% (weight) is normally preferred.Silylating agent can be used for catalyzer by primary treatment or a series of processing.
The catalyst composition that makes with above-mentioned steps is generally the composition that contains the 0.1-15% that has an appointment (weight) (preferred 1-10% (weight)) titanium (be generally the titanium oxide form, be preferably high nominal price oxidation state).Under oneself silylated occasion of catalyzer, also contain the carbon of 1-20% (weight) Organosilyl form usually.The halogenide (for example up to about 5000ppm) that in catalyzer, also has relatively small amount.
Catalyst composition can be chosen wantonly and add not interferential material and/or catalyzer promotion material, and particularly those are being the inert materials to oxidizing reaction and product chemically.Catalyzer may contain minor amounts of promoters, for example as the basic metal (for example sodium, potassium) or the alkaline-earth metal (for example barium, calcium, magnesium) of oxide compound or oxyhydroxide.Press total restatement of catalyst composition, content is that basic metal and/or the alkaline-earth metal of 0.01-5% (weight) normally is fit to.
Catalyst composition can be used by any physical form easily, for example powder, thin slice, particle, bead or pill.Inorganic siliceous solid can be such form in the past at dipping and roasting, or on the other hand, for example extrusion, granulation, grinding etc. become different physical form from a kind of formal transformation with traditional technology later on roasting at dipping.
Organic sulfide oxidation style of the present invention comprises that the fuel stream that contains organosulfur impurities contacts with organic hydroperoxide in the presence of titaniferous catalyzer.The fuel stream that is fit to comprises diesel oil fuel and gasoline, comprising natural gasoline, straight-run spirit and pressure gasoline.The hydrocarbon fraction of other sulfur-bearing comprises common gaseous petroleum fraction and petroleum naphtha, kerosene, rocket engine fuel, fuel wet goods.Diesel oil fuel is particularly preferred fuel stream.
Preferred organic hydroperoxide is C
3-C
20The hydro carbons hydroperoxide.Particularly preferably be C
3-C
15The second month in a season and tertiary hydrogen superoxide.The illustrative organic hydroperoxide that is suitable for comprises tert-butyl hydroperoxide, t-amyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide.Tert-butyl hydroperoxide is a particularly suitable.
Organic hydroperoxide is produced by corresponding oxidation of alkanes usually, produces corresponding alcohol simultaneously.For example, oxidation of isobutane generates the mixture of the tert-butyl hydroperoxide and the trimethyl carbinol.Though should use the organic hydroperoxide that contains corresponding alcohol in organic sulfide oxidation style of the present invention, preferably organo-peroxide is substantially free of alcohol before being used for oxidation style.So-called " not containing alcohol " is meant organic hydroperoxide: the mol ratio of alcohol was greater than about 25: 1.
In such oxidation style, sulfocompound: the mol ratio of hydroperoxide is particularly important not, but preferably uses about 2: 1 to about 1: 2 mol ratio.
Oxidizing reaction is carried out in liquid phase under moderate temperature and pressure.The temperature of reaction that is fit to is 0-200 ℃, but preferred 25-150 ℃.Reaction is preferably under normal pressure or be higher than under the normal pressure and carry out.Pressure is inessential accurately.Certainly, titaniferous catalyst composition has heterogeneous feature, therefore exists as solid phase in oxidising process of the present invention.Typical pressure is the 1-100 normal atmosphere.
Known any traditional structure of reactor thing carries out oxidizing reaction in available such oxidation style technology.Can use consecutive steps and step intermittently.For example, catalyzer can fixed bed or the use of slurries form.
Oxidation style of the present invention changes into the sulfone class with the organosulfur impurities of major portion.Usually, about more than 50%, preferred about more than 80% and most preferably from about organosulfur impurities more than 90% changes into the sulfone class.When oxidation proceeds to required degree, can handle product mixtures, so that from fuel stream, remove the sulfone class.Typically take off the sulfone method and comprise that for example silicon oxide, aluminum oxide, fluoropolymer resin and zeolite carry out leaching with sorbent material.On the other hand, for example methyl alcohol, dimethyl formamide, N-Methyl pyrrolidone or acetonitrile carry out liquid-liquid extraction and remove the sulfone class can to use polar solvent.The technician who is familiar with extraction polarity thing class is easy to know the spe medium of other solid and liquid.
Following examples only are used for illustrating the present invention.
Embodiment 1: Preparation of catalysts of the present invention
Catalyzer 1A: with silica support (Grace Davison DAVICAT P-732, granularity 0.6-1.4 millimeter, 300 meters of surface-area
2/ gram) under 400 ℃ air drying 4 hours.Exsiccant silicon oxide (47 gram) is put into 1 liter of round-bottomed flask.To contain diisopropyl oxidation two (Acetyl Acetone acid) titanium (IV) (15.1 grams, 75% aqueous isopropanol) and Virahol (89 restrain) then and be added in the silicon oxide, and thorough mixing.Remove at 90 ℃ of following rotary evaporations and to desolvate.With the roasting 2 hours in air under 800 ℃ of the material behind the dipping.Measure not silylated catalyzer 1A, contain 3.2% (weight) Ti and＜0.1% (weight) C.
Catalyzer 1B: the step with not silylated catalyzer 1A prepares silylated catalyzer 1B; different is that silicon oxide is dry down at 450 ℃; and restrain the silicon oxide of dryings with the solution impregnation 51 that contains diisopropyl oxidation two (Acetyl Acetone acid) titanium (IV) (16.3 gram, 75% aqueous isopropanol) and Virahol (82 gram).Make catalyzer carry out silylanizing by 500 milliliter of 3 neck round-bottomed flask that described material is packed into then, described flask is equipped with condenser, thermometer and inert gas entrance.Flask pack into not silylated catalyzer (52.9 gram) and hexamethyldisilazane (9.03 gram) and normal heptane (99 restrain).Use the oil bath heating systems, backflow (98 ℃) is 2 hours under inert atmosphere.Under inert atmosphere with system cooling, filtering catalyst, and wash with heptane (100 milliliters).In flask, flow down at 180-200 ℃ following dry 2 hours the silylanizing catalyzer 1B that makes then at rare gas element.The Ti that measures is 2.73% (weight); C is 2.0% (weight).
Catalyzer 1C: with silicon oxide (Grace Davison DAVICAT P-732) at 400 ℃ air drying 4 hours.Exsiccant silicon oxide (39.62 gram) is put into 500 milliliter of 3 neck round-bottomed flask, and described flask is equipped with inert gas entrance, pneumatic outlet and the washer of aqueous sodium hydroxide solution is housed.(solution of water＜50ppm) and titanium tetrachloride (IV) (5.02 restrain) is added in the above-mentioned flask under the exsiccant inert gas atmosphere for 84.21 grams, 99+% will to contain normal heptane.By eddy flow mixture is mixed well.Under nitrogen gas stream, under 125 ℃, came except that desolvating in 1.5 hours with the oil bath heating.
By above-mentioned materials being put into quartz tubular reactor (1 inch of the internal diameter (2.54 centimetres) that thermopair, 500 milliliter of 3 neck round-bottomed flask, heating jacket, inert gas entrance and washer (sodium hydroxide solution is housed) are housed, long 16 inches (40.64 centimetres)), make a part of above-mentioned materials (35 gram) roasting.Under exsiccant nitrogen (99.999%) stream (400 ml/min), beds is heated to 850 ℃.Bed after keeping 30 minutes under 850 ℃, is cut off the power supply of process furnace, and makes catalyzer be cooled to 400 ℃.
Make the catalyzer hydration with following step.Water (3.0 gram) is added in the 3 neck round-bottomed flasks, and arrives backflow, keep the nitrogen gas stream of 400 ml/min simultaneously with heating jacket heating flask.Water distills by beds in 30 minutes.Use heat gun heating round-bottomed flask, discharge from flask by bed to guarantee any residual water.Before the cooling, again bed was kept 2 hours down at 400 ℃.Catalyzer 1C contains 3.7% (weight) Ti.
Catalyzer 1D: by following with the further silylanizing of catalyzer 1C.
500 milliliter of 3 neck round-bottomed flask is equipped with condenser, thermometer and inert gas entrance.(39 grams, water＜50ppm), hexamethyldisilazane (3.10 gram) and catalyzer 1C (11.8 restrain) pack into heptane.Use the oil bath heating systems, can reflux at inert atmosphere (98 ℃) 2 hours, cooling then.Catalyzer is filtered and wash with heptane (100 milliliters).Then that material is following dry 2 hours at 180-200 ℃ in inert gas flow.Catalyzer 1D contains 3.5% (weight) Ti and 1.97% (weight) C.
Catalyzer 1E: with silicon oxide (Grace Davison DAVICAT P-732) at 450 ℃ air drying 2 hours.Exsiccant silicon oxide (36 gram) is put into the quartz tubular reactor (1 inch of internal diameter (2.54 centimetres), long 16 inches (40.64 centimetres)) that thermopair, 500 milliliter of 3 neck round-bottomed flask, heating jacket, inert gas entrance and washer (sodium hydroxide solution is housed) are housed.Under exsiccant nitrogen (99.999%) stream (400 ml/min), beds is heated to 300 ℃.Titanium tetrachloride (7.4 gram) is put into 3 neck round-bottomed flasks, and reflux, simultaneously nitrogen gas stream is remained on 400 ml/min with heating jacket heating flask.Titanium tetrachloride distills by beds in 1 hour.Use heat gun heating round-bottomed flask, discharge from flask by bed to guarantee any residual titanium tetrachloride.Be cooled to before 400 ℃, bed was kept 0.5 hour down at 850 ℃.
Water (3.0 gram) is added in the 3 neck round-bottomed flasks, and arrives backflow, keep the nitrogen gas stream of 400 ml/min simultaneously with heating jacket heating flask.Water distills by beds in 30 minutes.Use heat gun heating round-bottomed flask, discharge from flask by bed to guarantee any residual water.The heating of cut-out heating jacket.With the tubular reactor cool to room temperature.
The step of describing by catalyzer 1B makes the catalyzer silylanizing then, and different be to use 15 gram catalyzer, 43 gram heptane and 3.0 restrain hexamethyldisilazanes.Catalyzer 1E contains 2.6% (weight) Ti and 2.0% (weight) C.
Catalyzer 1F: can prepare the MCM-41 silica support by any known document step.For example referring to US 3556725; DiRenzo, et.al.,
Microporous Materials(1997), Vol.10,283, or Edler, et.al.,
J.Chem.Soc., Chem.Comm.(1995), 155.Before using that the MCM-41 gel that makes is dry under 180 ℃, then 550 ℃ of following roastings 14 hours.The BET surface-area of described material is 1488 meters
2/ gram.MCM-41 (4.36 gram) is put into 500 milliliter of 3 neck round-bottomed flask, and described flask is equipped with inert gas entrance, pneumatic outlet and the washer of aqueous sodium hydroxide solution is housed.(solution of water＜50ppm) and titanium tetrachloride (IV) (0.95 restrains 0.55 milliliter) is added in the above-mentioned flask under the exsiccant inert gas atmosphere for 60 grams, 99+% will to contain normal heptane.By eddy flow mixture is mixed well.Under vacuum, under 80 ℃, came except that desolvating in 1 hour with the oil bath heating.
Then by the described step of catalyzer 1C with above-mentioned material calcination that makes and hydration.Press the described step of catalyzer 1B then with the catalyzer silylanizing, different be to use 3.72 gram catalyzer, 35 gram heptane and 0.96 restrain hexamethyldisilazane.Catalyzer 1F contains 5.5% (weight) Ti and 5.1% (weight) C.
Embodiment 2. usefulness TBHP oxide compound oxidation of thiophene
Catalyzer 1A-F tests in the oxidation of various organosulfur compounds.Test-results is listed table 1 in.Charging mixes with dibenzothiophene (DBT) and Lyondell TBHP oxide compound (containing about 43% (weight) TBHP and 56% (weight) trimethyl carbinol) by toluene or ethylbenzene and prepares.Charging contains 0.175% (weight) dibenzothiophene (DBT), 0.32% (weight) trimethyl carbinol (TBA) and 0.24% (weight) tert-butyl hydroperoxide (TBHP).The mol ratio of DBT and TBHP is 2.8.
Embodiment 2A-F: the charging (28 gram) that will contain toluene in round-bottomed flask in nitrogen atmosphere and 50 ℃ heating and stirring down.Then Ti/ silicon oxide catalyst (0.2 gram, Powdered) is added, and reaction 0.5 hour under 50 ℃ and nitrogen atmosphere.With GC and HPLC analyze reaction mixture.As what measure, find that the oxidation products of thiophene is corresponding sulfoxide and sulfone with GC and GC-MS.
Embodiment 2G carries out under the identical step of embodiment 2A-F, and different is to use 0.04 to restrain pellet type catalyst 1D, and temperature of reaction is 80 ℃.
Embodiment 2H carries out under the identical step of embodiment 2G, and different is to use 4, and 6-dimethyl Dibenzothiophene (DMDBT) replaces DBT.The mol ratio of DMDBT and TBHP is 2.4.
Embodiment 2I-J carries out under the identical step of embodiment 2A-F, and different being to use contains the solution of ethylbenzene, uses 0.02 gram pellet type catalyst 1D, and temperature of reaction is that 80 ℃ and reaction times are 1 hour.For Comparative Examples 2J, do not use catalyzer.
The oxidation of Ti/ silicon oxide catalyst of table 1. organic sulfide
| Action number | Catalyzer | Catalyst amounts (gram) | Solvent | Substrate | Temperature (℃) | Transformation efficiency (%) |
| 2A * | 1A | 0.2 | Toluene | Dibenzothiophene | 50 | 31 |
| 2B * | 1B | 0.2 | Toluene | Dibenzothiophene | 50 | 39 |
| 2C | 1C | 0.2 | Toluene | Dibenzothiophene | 50 | 90 |
| 2D | 1D | 0.2 | Toluene | Dibenzothiophene | 50 | 91 |
| 2E | 1E | 0.2 | Toluene | Dibenzothiophene | 50 | 91 |
| 2F | 1F | 0.2 | Toluene | Dibenzothiophene | 50 | 97 |
| 2G | 1D | 0.04 | Toluene | Dibenzothiophene | 80 | 93 |
| 2H | 1D | 0.04 | Toluene | Dibenzothiophene | 80 | 56 |
| 2I | 1D | 0.02 | Ethylbenzene | Dimethyl Dibenzothiophene | 80 | 80 |
| 2J * | - | - | Ethylbenzene | Dibenzothiophene | 80 | 10 |
* Comparative Examples
Claims (20)
1. one kind comprises that the fuel that contains organic sulfide impurity flows the method that contacts with organic hydroperoxide in the presence of catalyzer, and described catalyzer makes with the method that may further comprise the steps:
(a) with being selected from following titanium source dipping inorganic siliceous solid:
(1) halogenated titanium is a solution in 25 ℃ to 150 ℃ the non-oxide varsol at boiling point; And
(2) vapour stream of titanium tetrachloride;
(b) roasting is through the silicon-containing solid of dipping, so that generate catalyzer; And
That (c) chooses wantonly is heatable catalyst in the presence of water;
Wherein the organosulfur impurities with major portion changes into the sulfone class.
2. according to the process of claim 1 wherein that halogenated titanium is a titanium tetrachloride.
3. according to the process of claim 1 wherein that impregnation steps (a) (1) realizes by the solution of halogenated titanium in non-oxide varsol is mixed the method for removing varsol subsequently with inorganic siliceous solid.
4. according to the process of claim 1 wherein that inorganic siliceous solid is selected from silicon oxide and MCM-41.
5. according to the process of claim 1 wherein that non-oxide varsol is selected from C
5-C
12Aliphatic hydrocrbon, C
6-C
12Aromatic hydrocarbons, C
1-C
10Halogenated aliphatic hydrocarbon, C
6-C
10Halogenated aryl hydrocarbon and composition thereof.
6. after finishing, step (b) is substantially free of water according to the process of claim 1 wherein.
7. according to the process of claim 1 wherein that the method for preparing catalyzer also is included in step (c) is handled catalyzer later on silylating agent additional step.
8. according to the process of claim 1 wherein that calcination steps (b) carries out under at least 500 ℃ temperature.
9. according to the process of claim 1 wherein that step (b) carries out in being substantially free of the atmosphere of oxygen.
10. according to the process of claim 1 wherein that organic hydroperoxide is a tert-butyl hydroperoxide.
11. according to the process of claim 1 wherein that organic hydroperoxide is substantially free of alcohol.
12. be diesel fuel stream according to the process of claim 1 wherein that fuel flows, and organic hydroperoxide is a tert-butyl hydroperoxide.
13. according to the method for claim 12, wherein impregnation steps (a) (1) realizes by the solution of halogenated titanium in non-oxide varsol is mixed the method for removing varsol subsequently with inorganic siliceous solid.
14. according to the method for claim 12, wherein inorganic siliceous solid is selected from silicon oxide and MCM-41.
15. according to the method for claim 12, wherein non-oxide varsol is selected from C
5-C
12Aliphatic hydrocrbon, C
6-C
12Aromatic hydrocarbons, C
1-C
10Halogenated aliphatic hydrocarbon, C
6-C
10Halogenated aryl hydrocarbon and composition thereof.
16., wherein after step (b) is finished, be substantially free of water according to the method for claim 12.
17. according to the method for claim 12, the method that wherein prepares catalyzer also is included in step (c) is handled catalyzer later on silylating agent additional step.
18. according to the method for claim 12, wherein calcination steps (b) carries out under at least 500 ℃ temperature.
19. according to the method for claim 12, wherein step (b) is carried out in being substantially free of the atmosphere of oxygen.
20. according to the method for claim 12, wherein tert-butyl hydroperoxide does not contain tertiary butyl alcohol substantially.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/387,849 US20040178121A1 (en) | 2003-03-13 | 2003-03-13 | Organosulfur oxidation process |
| US10/387,849 | 2003-03-13 |
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| CN100339462C true CN100339462C (en) | 2007-09-26 |
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| EP (1) | EP1601749B1 (en) |
| JP (1) | JP4209394B2 (en) |
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| CN (1) | CN100339462C (en) |
| AT (1) | ATE337386T1 (en) |
| AU (1) | AU2003300427A1 (en) |
| BR (1) | BR0318282A (en) |
| CA (1) | CA2513863A1 (en) |
| DE (1) | DE60307902T2 (en) |
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| US7744749B2 (en) | 2005-09-08 | 2010-06-29 | Saudi Arabian Oil Company | Diesel oil desulfurization by oxidation and extraction |
| US8715489B2 (en) * | 2005-09-08 | 2014-05-06 | Saudi Arabian Oil Company | Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures |
| CA2685850C (en) | 2007-05-03 | 2016-06-28 | Auterra, Inc. | Product containing monomer and polymers of titanyls and methods for making same |
| US8241490B2 (en) * | 2008-03-26 | 2012-08-14 | Auterra, Inc. | Methods for upgrading of contaminated hydrocarbon streams |
| US8197671B2 (en) * | 2008-03-26 | 2012-06-12 | Auterra, Inc. | Methods for upgrading of contaminated hydrocarbon streams |
| US8298404B2 (en) | 2010-09-22 | 2012-10-30 | Auterra, Inc. | Reaction system and products therefrom |
| US9061273B2 (en) | 2008-03-26 | 2015-06-23 | Auterra, Inc. | Sulfoxidation catalysts and methods and systems of using same |
| US8894843B2 (en) | 2008-03-26 | 2014-11-25 | Auterra, Inc. | Methods for upgrading of contaminated hydrocarbon streams |
| SG189702A1 (en) * | 2008-03-26 | 2013-05-31 | Auterra Inc | Sulfoxidation catalysts and methods and systems of using same |
| US8764973B2 (en) | 2008-03-26 | 2014-07-01 | Auterra, Inc. | Methods for upgrading of contaminated hydrocarbon streams |
| US9206359B2 (en) | 2008-03-26 | 2015-12-08 | Auterra, Inc. | Methods for upgrading of contaminated hydrocarbon streams |
| WO2012036445A2 (en) * | 2010-09-13 | 2012-03-22 | 한국화학연구원 | Catalyst for selective oxidative desulfurization and preparation method thereof |
| US9828557B2 (en) | 2010-09-22 | 2017-11-28 | Auterra, Inc. | Reaction system, methods and products therefrom |
| CN102059131A (en) * | 2010-12-14 | 2011-05-18 | 华东理工大学 | Novel titanium salt catalyst and catalytic esterification reaction thereof |
| JP6114285B2 (en) | 2011-09-27 | 2017-04-12 | サウジ アラビアン オイル カンパニー | Selective liquid-liquid extraction of oxidative desulfurization reaction products |
| KR101918775B1 (en) * | 2012-08-23 | 2018-11-15 | 에스케이이노베이션 주식회사 | Oxidative desulfurization process for hydrocarbon |
| WO2016154529A1 (en) | 2015-03-26 | 2016-09-29 | Auterra, Inc. | Adsorbents and methods of use |
| US10450516B2 (en) | 2016-03-08 | 2019-10-22 | Auterra, Inc. | Catalytic caustic desulfonylation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1302844A (en) * | 1999-10-28 | 2001-07-11 | 中国石油化工集团公司 | Process for refining gasoline or diesel oil by oxidation method |
| US6402939B1 (en) * | 2000-09-28 | 2002-06-11 | Sulphco, Inc. | Oxidative desulfurization of fossil fuels with ultrasound |
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| US3556725A (en) * | 1969-02-26 | 1971-01-19 | Sylvania Electric Prod | Process for producing low-bulk density silica |
| US3829392A (en) * | 1970-10-01 | 1974-08-13 | Shell Oil Co | Heterogeneous catalysts for olefin epoxidation |
| US3923843A (en) * | 1972-03-13 | 1975-12-02 | Shell Oil Co | Epoxidation process with improved heterogeneous catalyst |
| US3816301A (en) * | 1972-06-30 | 1974-06-11 | Atlantic Richfield Co | Process for the desulfurization of hydrocarbons |
| US5985136A (en) * | 1998-06-18 | 1999-11-16 | Exxon Research And Engineering Co. | Two stage hydrodesulfurization process |
| US6368495B1 (en) * | 1999-06-07 | 2002-04-09 | Uop Llc | Removal of sulfur-containing compounds from liquid hydrocarbon streams |
| US6114552A (en) * | 1999-09-28 | 2000-09-05 | Arco Chemical Technology, L.P. | Heterogeneous epoxidation catalyst |
| GB9925971D0 (en) * | 1999-11-03 | 1999-12-29 | Exxon Chemical Patents Inc | Reduced particulate froming distillate fuels |
| FR2802939B1 (en) * | 1999-12-28 | 2005-01-21 | Elf Antar France | PROCESS FOR THE DESULFURATION OF THIOPHENE DERIVATIVES CONTAINED IN FUELS |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1302844A (en) * | 1999-10-28 | 2001-07-11 | 中国石油化工集团公司 | Process for refining gasoline or diesel oil by oxidation method |
| US6402939B1 (en) * | 2000-09-28 | 2002-06-11 | Sulphco, Inc. | Oxidative desulfurization of fossil fuels with ultrasound |
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| ATE337386T1 (en) | 2006-09-15 |
| DE60307902D1 (en) | 2006-10-05 |
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| WO2004083345A1 (en) | 2004-09-30 |
| CA2513863A1 (en) | 2004-09-30 |
| CN1753975A (en) | 2006-03-29 |
| US20040178121A1 (en) | 2004-09-16 |
| JP4209394B2 (en) | 2009-01-14 |
| EP1601749A1 (en) | 2005-12-07 |
| JP2006514146A (en) | 2006-04-27 |
| ES2266923T3 (en) | 2007-03-01 |
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