CN101094908B - Oxidative desulfurization process - Google Patents

Oxidative desulfurization process Download PDF

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Publication number
CN101094908B
CN101094908B CN2005800453208A CN200580045320A CN101094908B CN 101094908 B CN101094908 B CN 101094908B CN 2005800453208 A CN2005800453208 A CN 2005800453208A CN 200580045320 A CN200580045320 A CN 200580045320A CN 101094908 B CN101094908 B CN 101094908B
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oxidation
fuel
sulphur
sulfur
sulfone
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CN101094908A (en
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肯尼斯·P·凯克勒
珍妮特·L·杰迪纳克
拉塞尔·R·桑普森
杰弗里·T·米勒
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BP Corp North America Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Disclosed is a process which reduces the sulfur and/or nitrogen content of a distillate feedstock to produce a refinery transportation fuel or blending components for refinery transportation fuel, by contacting the feedstock with an oxygen-containing gas in an 5 oxidation/adsorption zone at oxidation conditions in the presence of an oxidation catalyst comprising a titanium-containing composition whereby the sulfur species are converted to sulfones and/or sulfoxides which are adsorbed onto the titanium-containing composition.

Description

Oxidation desulfurizing method
Technical field
The present invention relates to the transport fuel derived from natural oil, is that the method for using component is concocted in the refining of the transport fuel of liquid under the particularly production ambient environmental conditions.More particularly, the present invention relates to prepare the method for this fuel, it is included under the existence of heterogeneous catalyst petroleum distillate is contacted with oxygen-containing gas, thereby the petroleum oxidate overhead product is with oxidation nitrogenous and/or sulfur-bearing organic impurity wherein.
Background technology
We know the last decades at 19th-century, along with the invention of oil engine has made transportation thorough change have taken place.When other people invention that comprises Benz and Gotteib Wilhelm Daimler and having developed the electrically-fired machine that uses as fuel such as gasoline, Rudolf C.K.Diesel is the fuel diesel engine that use compresses of lighting a fire automatically for using low-cost organic-fuel to invent and built.Go forward hand in hand with the exploitation of in transit improvement diesel engine and the improvement of diesel fuel composition.Modern high performance diesel needs the more fuel composition of advanced specification, but cost is still important consideration.
Present most of transport fuel is derived from natural oil.Really, oil still is used as the main source of the hydrocarbon of fuel and petrochemical material in the world.Although the composition of natural oil or crude oil is changed significantly, all crude oil all contains sulphur compound, and major part contains nitrogen compound, and these nitrogen compounds can also contain aerobic, and the oxygen level that is most of crude oil is low.Usually, in the crude oil sulphur concentration less than about 8%, the sulphur concentration of most of crude oil about 0.5% to about 1.5% scope.Nitrogen concentration still can be 1.6% height usually less than 0.2%.
Crude oil seldom uses with the form of producing from well, but changes into the fuel and the petrochemical material of wide region at refinery.Usually produce transport fuel to satisfy specific terminal use specification by the distillation fraction of processing and blending crude oil.Because today, a large amount of available most of crude oil had high sulphur, so distillation fraction must desulfurization satisfies the product of specification and/or environmental standard with production.Organic compounds containing sulfur remains the main source of environmental pollution in the fuel.When burning, they change into sulfur oxide, produce again to contain oxygen sulfuric acid, also have particulate emission.
Even in newer high performance diesel engine, the traditional fuel burning also produces cigarette in exhaust.We know the compound of oxidation and contain seldom or do not have the compound of C-C bond such as methyl alcohol and dme etc. can reduce cigarette and machine exhaust gas emission.But these compound major parts have high vapour pressure and/or be almost insoluble in diesel-fuel, and they have poor ignition quality, and are indicated as their cetane value.And, improve diesel-fuel with chemical hydrogenation and fuel lubricity reduced with other method that reduces sulphur and aromatic content.The diesel-fuel that oilness is low can make petrolift, oil thrower and other moving parts excessive wear that under high pressure contacts fuel.
Being used in the fuel in the compression-ignition engine (diesel engine) or the distillation fraction of use in fuels blending component is middle distillate, contains the sulphur of the 1 weight %～3 weight % that have an appointment usually.In the past, the ideal format of diesel-fuel is maximum value 0.5 weight %.By 1993, Europe and US-legislation were limited to 0.3 weight % with the sulphur in the diesel-fuel.To Europe in 1996 and the U.S. with to Japan in 1997, maximum sulfur in the diesel-fuel is reduced to is not more than 0.05 weight %.Must expect that this worldwide trend will proceed to lower level sulphur.
The target of Environmental Protection Agency be travelled in 2006 use in the sulphur level of diesel oil less than 15ppm.European union body specification was less than 50ppm in 2005.In addition, the world fuel charter that global car manufactures is supported proposes stricter sulphur requirement, is 5ppm～10ppm for " prosperity " national IV class A fuel A.In order to observe the regulation of these ultra-low sulfur fuel, refinery must make in this pass of refining and fuel be had even lower sulphur level.Refinery is faced with in the specified time frame of legislation authoritative department and reduces fuel, particularly this challenge of sulphur level in the diesel-fuel like this.
On the one hand, the new emission regulation of California and other compass of competency will introduce the very big concern that has promoted the catalytic waste gas processing.Because two factors are applied to diesel engine with the catalysis emission control, particularly the challenge of heavy-duty diesel engine significantly is different from spark-ignition internal combustion engine (petrol motor).At first, traditional three-way catalyst (TWC) is invalid for the NOx discharging of removing diesel engine, the second, and the demand that particulate is controlled is significantly higher than petrol motor.
Several exhaust gas treatment technologies are just appearring for diesel emission, in all parts, and the efficient of this technology of sulphur level affects in the fuel.Sulphur is the catalyzer poison that reduces catalytic activity.And, under catalysis control situation, form the sulfuric acid salt fog owing to the catalyzed oxidation of sulphur with the water reaction, so the high-sulfur in the fuel also produces the peripheral issue of particulate emission to diesel emission.This mist constitutes the part of particulate emission.
Owing to be used for causing incendiary method difference, the discharging of ignition machine is different from the discharging of spark ignition machine.Ignition requires fuel droplet to burn in the mixture of air/fuel than extreme poverty.Combustion processes stays small carbon particles, makes particulate emission be significantly higher than present petrol motor.Because poor air-fuel ratio operation, CO and carburet hydrogen discharging significantly are lower than petrol motor.But a large amount of unburned hydrocarbon are adsorbed on the carbon particulate.These hydrocarbon are called SOF (solvable organic fraction).
Can reduce particulate emission although increase temperature of combustion, because of known Zeldovitch mechanism, this will make the NOx discharging increase.Need balance particulate and NOx discharging to satisfy Abgasgesetz like this.
Available evidence advises that strongly super low sulfur fuel is to realize the important technology of catalytic treatment diesel exhaust with the control discharging.Possibly, need be lower than the fuel sulfur level of 15ppm to realize being lower than the fine grain level of 0.01g/bhp-hr.This level will be fit to the catalyst combination with the off gas treatment that occurs now very much, show the ability of the NOx discharging that reaches about 0.5g/bhp-hr.And the NOx capture systems is extremely responsive to fuel sulfur, and available evidence shows that they need be in the sulphur level that is lower than 10ppm to keep active.
In the face of the stricter sulphur specification of transport fuel, from petroleum and product, remove desulfuration in the coming years and become more and more important.
Can use traditional hydrogenating desulfurization (HDS) catalyzer to remove most of sulphur from the petroleum distillate that is used for refining transport fuel blending usefulness, but they for from as sulphur atom the polycyclic aromatic sulphur compound be invalid except that desulfuration in the sterically hindered compound.When sulfur heteroatom especially true during by dual steric hindrance (for example 4,6-dimethyl Dibenzothiophene).These sterically hindered dibenzothiophene mainly on the low-sulfur level as 50ppm～100ppm, need harsh treatment condition with desulfurization.At high temperature use traditional Hydrobon catalyst will cause loss of yield, catalyzer coking faster and quality product variation (for example color).Use high pressure to need big financial charges.
In order to satisfy stricter specification in future, such sterically hindered sulphur compound also must be removed from distillating material (distillate feedstock) and product.Press for and from overhead product and other hydrocarbon product, remove desulfuration economically.
This area has been full of to it is said it is the method for removing desulfuration from distillating material and product.A known method relates to the oxidation of the petroleum fractions (containing the petroleum fractions at the big at least quantity of material of the above ebullient of about 550 ℉) that contains the big at least quantity of material of ebullient on high boiling point hydrocarbon material, and the effluent of then handling the compound that contains oxidation at elevated temperatures is to form hydrogen sulfide (500 ℉～1350 ℉) and/or hydrotreatment to reduce the sulphur content of hydrocarbon materials.For example referring to United States Patent (USP) the 3rd, 847, No. 798 (Jin Sun Yoo etc.) and No. the 5th, 288,390, United States Patent (USP) (Vincent A.Durante).Verified these method use are limited, and this is owing to only reach the desulfurization of suitable low degree.In addition, when the enforcement of these methods,, cause a large amount of losses of value product because cracking and/or coking form.Therefore, a kind of to increase the desulfurization degree methods when cracking or coke form be favourable reducing in exploitation.
United States Patent (USP) the 6th, 087, No. 544 (Robert J.Wittenbrink etc.) relate to handles distillating material stream has the sulphur level that is lower than distillating material stream with production distillate fuel.Such fuel is produced by distillating material stream being fractionated into the lighting end and the last running that only contain about 50ppm～100ppm sulphur.This lighting end of hydrotreatment is to remove wherein all sulphur substantially.Then the lighting end and half last running of this desulfurization are concocted to produce the low-sulfur distillate fuel, for example the desulfurization lighting end of 85 weight % and the untreated last running of 15 weight % are reduced to 310ppm with the sulphur level from 663ppm.But,, only reclaim about 85% distillating material stream as low-sulfur distillate fuel product in order to obtain this low-sulfur level.
U.S. Patent Application Publication the 2002/0035306th A1 communique (Gore etc.) discloses a kind of liquid petroleum Desulphurization of fuels that makes and has also also removed the multistep method of nitrogenous compound and aromatic hydrocarbon.This method steps is the thiophene extraction; The thiophene oxidation; Thiophene oxide compound and dioxide extraction; Raffinate solvent recuperation and filtering; Extraction solvent reclaims; With the circulating solvent purifying.
The method of Gore etc. is attempted to remove in the feedstream 5%～65% thiophene material and nitrogenous compound and partially aromatic hydrocarbon before oxidation step.Although exist aromatic hydrocarbon will suppress cetane value in the diesel-fuel, the terminal use of the aromatic hydrocarbon that the method for Gore etc. need be used to extract.In addition, exist the aromatic hydrocarbon of significant quantity to work to increase the cold flowability of fuel density (Btu/gal) and raising diesel-fuel.Therefore, the excessive aromatic hydrocarbon of extraction is unthrifty.
About oxidation step, in-situ preparing or form this oxygenant in advance.Operational condition comprises H 2O 2And the mol ratio of S is between about 1:1 and 2.2:1; Acetic acid content charging about 5% and 45% between, solvent charging about 10% and 25% between and catalytic amount be less than about 5,000ppm sulfuric acid, preferably less than 1,000ppm.Gore etc. also disclose and used acid catalyst, preferably sulfuric acid in oxidation steps.Using sulfuric acid is problematic as oxidizing acid, and this is that when having water with regard to the corrosive problem is arranged, when having less water, hydrocarbon can be sulfonated.
According to Gore etc., the purpose of thiophene oxide compound and dioxide extraction step is to make benzo and dibenzothiophene oxide compound and N-oxide compound and a part of aromatic hydrocarbon that extraction solvent and more than one cosolvent are removed the various replacements more than 90% with acetic acid aqueous solution.
United States Patent (USP) 6,368,495 B1 (Kocal etc.) also disclose a kind of multistep method of removing thiophene and thiophene derivant from petroleum fractions.This method relates to step: the hydrocarbon incoming flow is contacted with oxygenant, make the oxidation step effluent contact sulfocompound with decomposing oxidation with solid decomposition catalysts then, thereby produce the liquid stream and the volatile sulfur compounds of heating.This patent disclosure use as oxygenants such as alkyl hydroperoxide, superoxide, percarboxylic acids and oxygen.
WO 02/18518 A1 (Rappas etc.) discloses a kind of two-segment desulfurizing method that uses in the downstream of hydrotreater.This method relates to aqueous formic acid base, hydrogen peroxide two phase oxidations of overhead product, thiophenic sulfur is transformed into corresponding sulfone.In oxidising process, some sulfones are extracted in the oxidizing solution.From hydrocarbon phase, remove these sulfones with phase separation step subsequently.The hydrocarbon phase that contains remaining sulfone then carries out liquid-liquid extraction or solid absorption step.
In oxidation step, use formic acid not advocate.Formic acid is more expensive than acetate.In addition, think that formic acid is " reduction " solvent, some metals of energy hydrogenation, thus weaken them.Therefore, need special alloy (exotic alloy) to handle formic acid.These expensive alloys must be used in solvent recuperation section and the storage vessel.In order to prevent the 3rd precipitated solid phase, for using formic acid also to need to use high temperature mutually from oxygenant aqueous phase separate hydrocarbons.Think because the lipophilicity of formic acid is poor, may form this disadvantageous the 3rd precipitated solid phase.Therefore at a lower temperature, formic acid can not remain on the sulfone of some extractions in the solution.
United States Patent (USP) the 6th, 171,478 B1 numbers (Cabrera etc.) disclose the rapid sulfur method of another kind of complicated multistep.Particularly, this method relates to hydrodesulfurisationstep step, oxidation step, decomposition step and separating step, wherein isolates the oxidized compound of a part of sulphur from the outflow logistics of decomposition step.The aqueous oxidizing that oxidation step uses preferably contains acetate and hydrogen peroxide.The outflow logistics contact decomposing catalyzer that makes oxidation step is to decompose hydrogen peroxide remaining in this effluent.
Carry out described separating step with the oxidized compound of extraction sulphur with selective solvent.According to the instruction of Cabrera etc., preferred selective solvent is acetonitrile, dimethyl formamide and tetramethylene sulfone.
For the sulphur compound that removes deoxidation has proposed many solvents.For example, at United States Patent (USP) the 6th, 160, No. 193 (Gore) instructed the solvent that uses in a large amount of extractions that is applicable to sulfone.Preferred solvent is dimethyl sulfoxide (DMSO) (DMSO).
Otsuki, S.; Nonaka, T.; Takashima, N.; Qian, W.; Ishihara, A; Imai, T.; Kabe, T., " Oxidative Desulfurization of Light Gas Oil and Vacuum GasOil by Oxidation and Solvent Extraction " Energy ﹠amp; Fuels 2000,14, announced the research of the similar solvent tabulation of using in the sulphur compound extraction in 1232.Below this tabulation is presented at:
N, dinethylformamide (DMF)
Methyl alcohol
Acetonitrile
Tetramethylene sulfone
Gore is set out between solvent polarity and the solvent extraction efficient and exists relation.This patent and the opinion all solvents listed in the text all ideally with the diesel oil unmixing.Their feature all is polar protic or aprotic solvent.
No. 01/32809 communique of WO discloses the method for another kind of selective oxidation distillate fuel or middle distillate.The distillate fuel of the open oxidation of described reference, thus hydroxyl and or carbonylation ground be bonded to and cause the particle of this fuel generation when burning to reduce in the fuel on the alkane molecule with respect to unoxidized fuel.The document discloses in the presence of various titaniferous silica-based zeolites, and optionally the radical of saturated aliphatic in the oxygenated fuel or ring compound make the method that forms hydroxyl or carbonyl with superoxide, ozone or hydrogen peroxide.
United States Patent (USP) the 6th, 402,939 B1 communiques (Yen etc.) disclose a kind of method of utilizing the oxidation sweetening of hyperacoustic fossil oil.In brief, the liquid fossil oil mixes with the acidic aqueous solution that comprises water and hydrogen peroxide to form multi-phase reaction mixture, and ultrasonic wave extracts so that sulfide oxidation becomes sulfone again to apply enough for a long time for then this heterogeneous reaction medium.
U.S. Patent Application Publication the 2001/0015339th A1 number (Sherman) discloses a kind of method of removing sulphur compound from diesel oil fuel, relate to and oxidizing gas is configured as the bubble of submicron-scale and these bubbles are distributed in the mobile diesel-fuel, sulphur compound is oxidized to sulfoxide and/or sulfone.
Consider top described, can be clear that needs a kind of more uncomplicated, economic overhead product or diesel fuel desulfurization method, it does not use bigger, the expensive hydrotreatment technology of hydrogen usage and uses the oxidation technology of expensive chemical oxidizing agent, and has avoided complex process and the etching problem followed.
The invention provides a kind of sulfur method of relatively simply selecting, wherein in the presence of the heterogeneous catalyst that comprises titaniferous composition, distillating material is contacted with oxygen-containing gas, thereby the sulfocompound in the distillating material is changed into the sulfone or the sulfoxide of their correspondences, and the part in them is adsorbed onto on the titaniferous composition then.
Summary of the invention
Method of the present invention relates to by at oxidation/adsorption zone raw material being contacted with oxygen-containing gas in the presence of the multi-phase oxidation catalyst that comprises titaniferous composition, under oxidizing condition, thereby make sulfocompound be transformed into sulfone and/sulfoxide, their part is adsorbed onto on the titaniferous composition subsequently, reduces the sulphur content of the distillating material that contains the sulfur-bearing organic impurity thus with production refining transport fuel or refining transport fuel blending component.Reclaim fuel or the blending component that sulphur content reduces from oxidation zone then.Can also from this catalyzer remove sulfone and/sulfoxide is used for further processing, thereby this catalyzer of regenerating is to be recycled and reused in this method.
Description of drawings
Fig. 1 represents the block diagram of one embodiment of the invention.
Fig. 2 represents the block diagram of another embodiment of the invention.
Fig. 3 represents to comprise oxygen-containing gas is added to the figure of the percentage desulfurization of the effect in the method for the present invention with respect to the production time.
Fig. 4 represents the desulphurizing activated performance with respect to the regeneration titanium silicate as the new titanium silicate catalyzer of the function of production time.
Fig. 5 represents the desulphurizing activated of according to the present invention two kinds of oxide catalysts of regenerated.
Fig. 6 represents the influence of oxygen level to the desulfurization carried out according to the present invention.
Embodiment
For best result, proper raw material generally comprises under atmospheric pressure at about 50 ℃ to about 650 ℃, preferred 150 ℃ to about 400 ℃ of scopes and more preferably ebullient refinery steams under the temperature between about 175 ℃ and about 375 ℃.These logistics are including, but not limited to, the concentrating and the embodiment of hydrotreatment separately of primary lightweight middle distillate, primary heavy middle distillate, fluid catalytic cracking process light catalytic cycle oil, coking still overhead product, hydrocracking overhead product, rocket engine fuel, vacuum overhead product and these logistics.Preferred logistics is the scheme of concentrating of fluid catalytic cracking technology light catalytic cycle oil, coking still overhead product and hydrocracking overhead product and independent hydrotreatment.
Also expection can be made up the raw material of more than one above-mentioned distillating stream as the inventive method.In many cases, refining transport fuel that is obtained by various replaceability raw materials or refining transport fuel can be similar with the performance of blending component.In these situations,, consider it to be conclusive as logistics such as the volume utilizability of logistics, the position that connects recently and short-term economy for using what logistics.
On the one hand, the invention provides the production of using blending component by the petroleum distillate production refining transport fuel or the refining transport fuel of hydrotreatment.By preparing the overhead product of such hydrotreatment with following method hydrotreatment ebullient petroleum distillation material between about 50 ℃ and about 650 ℃, described method is included under the existence of hydrogenation catalyst, makes petroleum distillate and sources of hydrogen reaction remove desulfuration and/or nitrogen to help hydrogenation from the petroleum distillate of hydrotreatment under hydroconversion condition; Randomly, the petroleum distillate of hydrotreatment is carried out fractionation, with lower boiling blending component that at least a fractions consisting by the rich single aromatic hydrocarbon of poor sulphur is provided with by the high boiling point raw material of the fractions consisting of the poor single aromatic hydrocarbon of rich sulphur by distillation.According to an embodiment of the inventive method, the overhead product of hydrotreatment or low boiling component can be as the suitable feedstock of the inventive method.
Usually, useful hydrogenation catalyst comprises at least a reactive metal that is selected from d transition element in the periodictable, and the amount that is incorporated into every kind of reactive metal on the inert support is that about 0.1 weight % of total body catalyst is to about 30 weight %.Suitable reactive metal comprises the d transition element in the periodictable with 21～30,39～48 and 72～78 atomicities.
This shortening process can be carried out under gentle relatively condition in the fixed bed of catalyzer, mobile fluidized-bed or ebullated bed.Preferably under the condition that needs to move the relative long period before the regeneration, use fixed bed or a plurality of fixed bed of catalyzer, for example average response district temperature is about 200 ℃ to about 450 ℃, preferred about 250 ℃ to about 400 ℃, for best result optimal selects about 275 ℃ to about 350 ℃, pressure at about 6 normal atmosphere to the about 160 atmospheric scopes.
In the minimized while of amount of required pressure of hydrodesulfurisationstep step and hydrogen, the particularly preferred pressure range that hydrogenation provides extraordinary sulphur to remove is in 20～60 barometric pressure range, more preferably from about 25～40 atmospheric pressure.
Hydrogen recycle than generally at about 500SCF/Bb1 to about 20, in the 000SCF/Bbl scope, preferably about 2,000SCF/Bb1 is to about 15, in the 000SCF/Bb1 scope, for best result optimal is selected in approximately 3,000SCF/Bb1 is extremely about 13, in the 000SCF/Bb1 scope.Be lower than the reaction pressure of these scopes and hydrogen recycle than causing higher catalyst deactivation rate, cause the lower desulfurization of efficient, denitrogenation and take off aromatic hydrocarbon.Too high reaction pressure increases energy and equipment cost, and the increment benefit of minimizing is provided thus.
This hydrogenation process is usually at about 0.2hr -1To about 10.0hr -1, preferably about 0.5hr -1To about 3.0h -1, for the best about 1.0hr of result optimal choosing -1To about 2.0hr -1Liquid hourly space velocity under operate.Too high air speed will cause overall hydrogenation to reduce.
For aromatic heterocycle sulfide being transformed into hydrocarbon and hydrogen sulfide (H 2S), further reducing aromatic heterocycle sulfide with hydrotreatment from the distillation petroleum fractions needs this logistics to carry out very harsh shortening.Usually, any hydrocarbon part is big more, and this sulfide of hydrogenation is difficult more.Therefore, remaining remaining organosulfur compound is bigger and most of structure sterically hindered aromatic heterocycle that is after the hydrotreatment.
When raw material was high boiling point distillation fraction derived from the refinery steams hydrogenation, refinery steams can be an ebullient material between about 200 ℃ and about 425 ℃.Preferred this refinery steams can be boiling, more preferably an ebullient material between about 275 ℃ and about 375 ℃ between about 250 ℃ and about 400 ℃.
The useful distillation fraction that is used for hydrogenation can be under the normal atmosphere at about 50 ℃ to about 650 ℃, preferred 150 ℃ to about 400 ℃ scope, more preferably any in the boiling refinery steams, several or all logistics between about 175 ℃ and about 375 ℃.Generally more advantageously be recovered in the gasoline than light hydrocarbon components in the distillage, the appearance of these more lower boiling materials is subjected to the restriction of distillate fuel flash-point specification usually in the distillate fuel.Generally more advantageously handle and change into gasoline at ebullient more than 400 ℃ than the heavy hydrocarbon component, but can use in the method for the invention as the fluid catalytic cracking charging.The appearance of heavy hydrocarbon component is subjected to the further restriction of distillate fuel end point specification in the distillate fuel.
The distillation fraction that is used for hydrogenation can comprise derived from the height of high and sweet crude oil and the original overhead product of low-sulfur, coking overhead product, catalytic cracking lightweight and heavy catalytic cycle oil with from the product of the distillation boiling range of hydrocracking and Residual oil hydrogenation factory.Usually, the coking overhead product is the highest feed composition of aromatic hydrocarbon with light, heavy catalytic cycle oil, up to 80 weight %.Most of coking overhead product and turning oil aromatic hydrocarbon occur with single aromatic hydrocarbons and two aromatic hydrocarbons, occur with three aromatic hydrocarbons than small part.Has lower aromatic content, the aromatic hydrocarbon of Chang Weigao to 20 weight % as initial materials such as high and doctor negative original overhead products.Usually, the aromatic content of blended hydrogenation factory raw material at about 5 weight % to the scope of about 80 weight %, more generally at about 10 weight % to about 70 weight %, the most normally at about 20 weight % to about 60 weight %.
Among the present invention in the useful distillation fraction sulphur concentration generally be high and the purified hydrogenation ability of sweet crude oil mixture, every barrel of former oil capacity and distill the function of the alternative configurations of hydrogenating materials component.Than doctor positive distillating material component generally be derived from high-sulfur crude oil original overhead product, coking overhead product with from the unitary catalytic cycle oil of fluid catalytic cracking of handling relative high-sulfur raw material.These distillating material components can contain the high elementary sulfur of 2 weight %, but generally at about 0.1 weight % to the elementary sulfur scope of about 0.9 weight %.
The nitrogen content of useful distillation fraction generally also is the purified hydrogenation ability of the nitrogen content of crude oil, every barrel of former oil capacity and distills the function of the alternative configurations of hydrogenating materials component among the present invention.The distillating material of higher nitrogen generally is coking overhead product and catalytic cycle oil.These distillating material components can have the high total nitrogen concentration of 2000ppm, but generally at about 5ppm extremely in about 900ppm scope.
Normally, sulphur compound is as relative non-polar aromatic heterocycle sulfide such as the thionaphthene that replaces and dibenzothiophene in the petroleum fractions.At first sight as if think, can optionally extract the aromatic heterocycle sulphur compound based on some characteristics that are attributable simply to these aromatic heterocycles.Even in these compounds sulphur atom have two pairs not Cheng Jian make its electronics that is divided into Lewis alkali, this characteristic remains inadequate for them with the Lewis acid extraction.In other words, it is poor with need be between sulfide and the hydrocarbon bigger polarity of the sulphur that obtains lower level optionally to extract the aromatic heterocycle sulphur compound.
Utilize heterogeneous catalytic oxidation of the present invention, these sulfide optionally directly can be changed into as more polar, sulphur compound Lewis alkalescence, oxidation such as sulfoxide and sulfone, they are adsorbed onto on the titania-silica then.Subsequently, reclaim the raw material of desulfurization from oxidation/adsorption zone.Think that method of the present invention also produces the oxidation and the absorption of nitrogenous substances, it can separate simultaneously with S-contained substance.
Having not equally, other compound of the electron pair of Cheng Jian comprises amine.In the identical logistics that has above-mentioned sulfide, also find heterocyclic aromatic amine.Amine is more alkaline than sulfide.Isolated electron pair serves as Bronsted-Lowry alkali (proton acceptor) and Lewis alkali (electron donor).On the atom this makes it be easy to oxidation in the mode that is similar to sulfide to electronics.
On the one hand, the invention provides a kind of refining transport fuel or the refining transport fuel production method with blending component, described method comprises: the distillating material that the mixture that comprises hydrocarbon and sulfur-bearing organic impurity is provided; In the presence of the oxide catalyst that comprises the titania-silica that also serves as sorbent material, in oxidation zone, make raw material and contact as oxygen-containing gass such as oxygen-denuded airs.Because the present invention can use oxygen-denuded air, so concentration of oxygen can be less than about 21 volume %.Preferably contain the oxygen level that oxygen flow should have at least 0.01 volume %.Effectively concentration is 0.5 volume %～10 volume %.This gas can and as need as inert diluent supplies such as nitrogen by air.As those skilled in the art will know that some composition is volatile, should select to contain the composition of oxygen flow to avoid blast area.This oxygen-containing gas can be with 200～20, the amount circulation in every barrel of scope of 000 standard cubic foot.
The pressure of oxidation/adsorption zone can be from normal pressure to 3000psig, and preferably about 100psig is to about 400psig, and more preferably from about 100psig is to about 300psig scope.
The temperature of oxidation/adsorption zone can be from about 100 ℉ to about 600 ℉, and preferred about 200 ℉ are to about 500 ℉, and most preferably from about 300 ℉ are to about 400 ℉ scopes.
Oxidation/adsorption method of the present invention is at about 0.1hr -1To about 100hr -1, preferably about 0.2hr -1To about 50hr -1, for the best about 0.5hr of result optimal choosing -1To about 10hr -1Liquid hourly space velocity under operate.Too high air speed will cause total oxidation and absorption to reduce.
Usually, oxidation/adsorption method of the present invention is from the distillating material pre-heating step.Distillating material was preheated to goal response district temperature in charging/effluent interchanger before entering the stove of last preheating.Can make distillating material with contain oxygen flow before the preheating, during and/or contact afterwards.
Because oxidizing reaction generally is heat release, so can use by between the fixed-bed reactor or the intersegmental cooling formed of the heat transfer unit (HTU) between the catalyst bed in the same reactor enclosure.The heat that can advantageously reclaim this oxidising process generation of at least a portion usually is to be used in the oxidising process.When this recovery of heat scheme not, can be by cooling off as cooling ways such as water coolant or air or by the quench stream that use is injected directly in the reactor.Two sections processes can provide the temperature exotherm of the reduction of each reactor enclosure, and oxidation reactor temperature control preferably is provided.
Usually cooling oxidation/adsorption zone effluent, and will flow out and directly guide in the tripping device to shift out the oxygen-containing gas that can loop back this process.Usually control oxygen-containing gas cleaning rate is to keep minimum or the maximum oxygen level in the gas that leads to reaction zone.The round-robin oxygen-containing gas generally compresses, and uses " replenishing " oxygen or oxygen-containing gas (preferred air) to replenish if desired, and is expelled in this process with further oxidation.
Method of the present invention can be carried out in the gas-liquid-solid reactor of any type that those skilled in the art will know that.For example, reaction zone can be made up of more than one fixed-bed reactor.Fixed-bed reactor liquid can also comprise a plurality of catalyst beds.In addition, this reaction zone can be fluid bed reactor, slurry bed or trickle-bed reactor.The use simplification that heterogeneous catalyst brought will make the range applications method of the present invention of traditional less application.For example, think that method of the present invention can be on the skid-mounted unit of terminal or front court, pipeline garage and using on the vehicle that contains board-like fuel cell of sulphur sensitization perception hydrocarbon reformer and fuel cell and carry out.
Think that heterogeneous catalytic oxidation of the present invention makes a part of sulfur-bearing organic impurity be direct oxidation into the sulfone and/or the sulfoxide of their correspondences.These sulfones and/or sulfoxide are adsorbed onto on this catalyzer then.
For disclosed purpose, term " oxide catalyst " is meant titaniferous material, for example:
1. amorphous titania-earth silicon material.These materials are described in CatalysisToday, 51,1999, among the 233-254 by in the survey article that Gao and Wachs write.Ti concentration is 0.001 atom %～50 atom %.Surface-area, pore volume arbitrarily arbitrarily.
2. titanium silicate zeolitic material.Know several in these materials in the document; TS-1, Ti-beta, Ti-ZSM-12, Ti-MCM-41, Ti-HMS, Ti-ZSM-48, TS-2, Ti-MCM-48, Ti-MSU, Ti-SBA-15, Ti-MMM, Ti-MWW, Ti-TUD-1 and Ti-HSM are some in these.These materials are described among Advances in Catalysis48 (2004) 1-169 in the survey article by the exercise question " Active sitesand reactive intermediates in titanium silicate molecular sieves " that Ratnasamy and Srinivas write.
3. the titania-silica mixed oxide that contains maximum 50% titanium dioxide.
4. carry out all above-mentioned catalytic materials that silanization is handled, in WO02/090468, describe as Schoebrechts etc.
Preferred effectively titanium-containing materials can be selected from titanium silicate, Ti-MCM and Ti-HMS.
Method of the present invention can realize desulfurization to the following level of about 10ppmw, can realize that denitrogenation is to the following level of about 10ppmw.
Usually, the effluent that in oxidation/adsorption zone oxygen-containing gas is contacted up to oxidation/adsorption zone with raw material reaches predetermined sulphur content, or shows that catalyzer has reached as the ideal capacity of sulfur materials such as sulfone or sulfoxide or penetrating of load.
Oxidation/adsorption zone stops service then, and regeneration.This oxide catalyst can be regenerated in many ways.These methods are included under the existence of oxygen-containing gas and are comprising about 500 high temperature oxidations to the condition of about 1000 ℃ temperature and about pressure of 0 to about 100psia; Comprising about 500 high temperature pyrolysis to the condition of about 1000 ℃ temperature and about pressure of 0 to about 100psia; Comprising that in the presence of hydrogen-containing gas about 500 handle to the high temperature hydrogenation of about 700 ℃ temperature and about 25 to the condition of about 40 atmospheric pressure; And solvent reclamation.
Effectively solvent is a methyl alcohol.Think and to have the similar effect that oxide catalyst is returned back to substantially its initial activity as other polar solvents such as acetonitrile, dimethyl sulfoxide (DMSO), tetramethylene sulfone, acetate.Solvent reclamation is generally comprising that about 50 carry out to about 400 ℉ temperature and about 0 to the condition of about 300psia pressure, and keeps that liquid hourly space velocity sulphur concentration in effusive extract stream is constant to show that regeneration finishes substantially with should making duration of contact of catalyzer.
In addition, can under the condition of the pressure that comprises about 100 to about 500 ℉ temperature and 0 to about 50psia, carry out pressure oscillating (pressure swing) operation with this catalyzer of regenerating.Ideally, use an oxidation/adsorption zone so that desulfurization of raw material, another oxidation/adsorption zone of after the desulfurization service, regenerating simultaneously.
In order to describe the present invention better, another preferred aspect of the present invention schematically is depicted among Fig. 1.With reference to the block diagram that Fig. 1 described, be preheated by pipeline 15 from the liquid starting material of charging stock tank 10, mix with diluent air stream 16, this airflow contains the oxygen of the 7 moles of % that have an appointment or the oxygen of preferred 3 moles of %.
The air of dilution and the preheated mixture of charging are by oxidation/adsorption zone 20.Oxidation/adsorption zone 20 can be at 325 ℉, 200psig pressure and 0.7hr -1Or preferred 1.0hr -1Liquid hourly space velocity under operate.This district can be the fixed bed downflow reactor, and wherein this fixed bed contains titania-silica.Sulfurous organic compound matter in reactor in the raw material is oxidized to the sulfone and/or the sulfoxide of their correspondences.These sulfones and/or sulfoxide are adsorbed onto on the titania-silica of oxidation/adsorption zone then.This reaction is heat release, and oxidation/adsorption zone is operated in the mode that the temperature rise of oxidation/adsorption zone preferably is no more than 25 ℉.Can design oxidation/adsorption zone, make and carry out cyclical operation in 24 hours with containing high raw material to 500ppmw sulphur, product sulphur specification is no more than 10ppmw.After 24 hours operation cycle,, oxidation/adsorption zone 20 is switched to off-line for the regenerating oxidation catalyzer.Come the outflow logistics 21 of autoxidation/adsorption zone 20 to be delivered to reactor effluent separator 30 then, wherein reclaim low sulfur product or blending component to flow 31.Circulating current 32 arrives gas-liquid separation tube (Knockout Drum) 50, reclaim other low sulfur product to flow 53 here, gas circulation stream 52 is dry in moisture eliminator 60, and (with compressor 70) compress again, is recycled to oxidation/adsorption zone after adding supplemental oxygen suitably.
Fig. 2 draws the oxidation/adsorption zone 40 of regeneration.In this case, arrive oxidation reactor 40 from fresh methanol jar 70 by stream 71 at 40 o'clock methyl alcohol of regeneration, thereby the sulfone and/or the sulfoxide of absorption carried out desorption.This regenerative process can be removed the sulfone and/or the sulfoxide of absorption more than 99%, recovers the oxidation activity and the adsorptive power of catalyzer substantially.The stream 41 that contains methyl alcohol and sulfone and/or sulfoxide is transported to useless methanol tank then, is transported to tower 90 then, reclaims methyl alcohol to flow 92 here from useless sulfone and/or sulfoxide methyl alcohol stream 91.This waste streams has relative smaller volume, and it is outer with further processing to deliver to hydrocracker, coker or distillation hydrotreater or device.This desorption and regeneration can with the uniform pressure of oxidation/absorption under carry out.Preferably desorption and regeneration carries out under the low pressure of the pressure that equals distilation steps.Methanol feed rate can be to be supplied to the identical feeding rate of oxidation/adsorption zone with hydrocarbon feed.Think need at least ten times of catalyst volumes solvent carry out desorption/regenerative process.After the desorption, can dry oxidation/adsorption zone to remove the remaining methyl alcohol of any free.After drying step, can use the catalyzer of 3% Oxygen Flow calcined oxide/adsorption zone under 800 ℉, finally return service.
For a more complete understanding of the present invention, referring now to the embodiment of explaining in more detail among the embodiment that is described below.
Embodiment 1
Be prepared as follows the titanium silicate of the present invention: the 350g tetraethyl orthosilicate is added in the 500g water as oxide catalyst and sulfone/sulfoxide sorbent material.Tetraethyl orthosilicate and water unmixing form two-layerly, and the upper strata is a tetraethyl orthosilicate: add the HC1 of 139g10%, it is dissolved in the water layer.Under agitation this two-layerly is heated to about 70 ℃.Form individual layer with the initial reaction of tetraethyl orthosilicate, this individual layer forms purple gel clearly when further heating.At room temperature dry this gel is to make solid.Wash this solid to reduce the amount of C1 with 3 premium on currency.This catalyzer is 100 ℃ of following dried overnight then.This solid can randomly be calcined 4 hours down at 500 ℃.Catalyst yield is 82g.
Analyze three kinds of titania-silica catalyzer as above-mentioned preparation, major part is amorphous, but as shown in table 1, and catalyst A and catalyzer C contain the TiO of small concentration 2The anatase octahedrite polymorphic form.
Table 1
Figure S05845320820070702D000171
With mortar and broken these the three kinds of catalyzer of sledge mill.On the Rigaku diffractometer that uses standard configuration, measure the x-ray powder pattern.In the Spex8000 mixer/mill, catalyst A is mixed with the quartzy internal standard of concentration known, measure pattern again.Use GSAS to carry out quantitative phase analysis with the Rietveld method.
Embodiment 2
Experimental installation
Use the performance of the device of pilot scale with the diesel feed evaluate catalysts that contains 350ppm sulphur.The reactor of pilot scale is made up of 316 stainless steel tubes of 10.5 inches long 0.75O.D. * 0.438 inch I.D. * 0.065 inch wall thickness.Keep temperature of reactor with three sections electrically heated reactor walls in the insulation stove case.On each reactor wall section, use the single-point thermopair, control the temperature of these sections with programmable calculator.In addition, the 0.125 inch O.D. stainless steel thermocouple sheath that passes reactor middle part from the top holds multiple spot thermopair (three multiple spot thermopairs, at interval 2 ") with the monitoring interior reaction temperature.
Pilot reactor is sized to by being filled with-and the preheating zone of the aluminum oxide fragment of 20+40 Tyler mesh hole dimension (the USS testing sieve of being produced by W.S.Tyler) is formed.The second and the 3rd heating zone filling 10cc catalyzer, this catalyst powder are broken to-20+40 Tyler mesh hole dimension (by the USS testing sieve of W.S.Tyler production).The remainder of reactor (humidity province 4) filling is sized to-20+40 Tyler mesh hole dimension (the USS testing sieve of producing by W.S.Tyler) and as the aluminum oxide fragment of cooling zone and supported catalyst.Reactor still also can be with the upper reaches constructor mainly with the downward stream mode operation.
Use the transmission of Brooks flow control meter to be diluted in 250ml/min7% oxygen in the nitrogen feed gas to reactor.The oxygen analyser that is installed in reactor downstream is measured the oxygen level of tail gas under normal pressure.
Precise injection volume pump (ISCO) transfers to reactor with liquid feeding.In the reactor preheating zone feeding preheating is arrived temperature of reaction, measure temperature with thermopair along medullary ray in each position.Come the product liquid of autoreactor to flow to refrigerative high-pressure separator/receptor, wherein use 7% oxygen in the nitrogen to keep the top hole pressure of reactor under working pressure.By the returning pressure setter of regulating from the tail gas of separator/receptor is maintained 200psig with reactor pressure.From high pressure receptor/separator expel liquid sample, with Spectro XEPOS XRF analysis device XEP01 type analysis sulphur content.Determine nitrogen with chemoluminescence method.Use capillary GC, determine the sulphur specification with the sulphur specific detectors.
For these experiments, the 10cc catalyzer is installed in the reactor.Operation charging flow velocity acquisition 1.0 and 2.0hr -1Between liquid hourly space velocity (charging standard volume (cc)/hour divided by the admission space (cc) of catalyzer).Reaction zone temperature maintains 320 ℉+/-5 ℉.
Experimental arrangement
After the reactor charge catalyzer, be forced into 200psig with 7% oxygen that is diluted in the nitrogen, gas flow is set at 250ml/min.Catalyst bed is saturated with the charging of about 50ml.Begin the feeding rate of 10～50ml/hr then.Under the situation of gas and liquid feeding establishment, reactor slowly is heated to the service temperature of 300～400 ℉.After reaching the service temperature that needs, begin test, collect product liquid with a hour interval.Analyze the sulphur content of product liquid then with Spectro XEPOSXEP01 type XRF analysis device.Continuation is reacted up to catalyst deactivation or is penetrated.
The assessment process of spent catalyst:
1～2 microliter methanol extracting solution of spent catalyst is expelled in the 30 meters * 0.32mm i.d. fused silica column (DB1) with 0.1 micron polydimethyl silicone coated by the shunting injection port under 300 ℃.Column temperature kept 2 minutes down at 40 ℃, then with the interval temperature programming to 300 of 10 ℃/min ℃.Conveyer line from the post end to mass spectrometer ion source remains on 300 ℃.Scanning speed with 0.7 second/mass decade range (mass decade) under 3000 mass resolution abilities or 1000 mass resolution abilities obtains mass spectrum.
Result and discussion:
Use diesel oil fuel as charging, experimentize with the titanium silicate catalyzer with following table 2 listed performances.When diesel feed flows through catalyst bed, when the experiment beginning, only to reactor delivery of pure nitrogen.The result of following table 4 is illustrated under the situation that does not have oxygen in the system, and the sulphur concentration in the reactor effluent reduces by 12.92%.Behind the charging several hrs, air-flow switches to the air-flow of being made up of the oxygen of 7 volume % in the nitrogen.Can clearly see from the result, make the sulphur content in the reactor effluent reduce by 74.72% thereby this catalyzer effectively utilizes gaseous molecular oxygen.These experimental results represent that clearly the titanium silicate catalyzer removes desulfuration effectively from incoming flow when gaseous oxygen appears in the feed gas.The result of the diagrammatically shown experiment operation of Fig. 3.
In addition, following table 3 expression with appear at charging in identical sulphur compound appear in the product, but concentration is lower.But,, except unreacted C1-C4 dibenzothiophene, also have sulfoxide and sulfone from the GC-MS analysis revealed of the methanol extraction hydrocarbon of spent catalyst.Because originally expect that pickling can selectively remove sulfone and sulfoxide from product, but do not remove substantially that so can obtain not having sulfoxide and sulfone in the conclusion product, they are adsorbed onto on the catalyzer.
Table 2
The distillation feed composition
Analytical test
Charging detects
XRF sulphur, ppm-w 356
Chemoluminescence (ASTM4629) nitrogen, ppm-w 233
Sulfur material
The 1-C1 thionaphthene, ppm S 0.30
The 2-C2 thionaphthene, ppm S 2.36
The 3-C3 thionaphthene, ppm S 9.56
The 4-C4 thionaphthene, ppm S 25.42
The 5-dibenzothiophene, ppm S 9.31
The 6-C1 dibenzothiophene, ppm S 79.78
The 7-C2 thionaphthene, ppm S 115.01
The 8-C3 thionaphthene, ppm S 60.47
The 9-C4 dibenzothiophene, ppm S 65.73
Total S, ppm 367.94
Table 3
Charging Product Acid-leached product
Total sulfur, ppm-w 356 90 70
Sulfur material
The 1-C1 thionaphthene, ppm S 0.30 0.00 0.00
The 2-C2 thionaphthene, ppm S 2.36 0.02 0.11
The 3-C3 thionaphthene, ppm S 9.56 1.25 1.23
The 4-C4 thionaphthene, ppm S 2,542 5.90 5.43
The 5-dibenzothiophene, ppm S 9.31 0.00 0.00
The 6-C1 dibenzothiophene, ppm S 79.78 17.80 16.14
The 7-C2 dibenzothiophene, ppm S 115.01 25.05 22.67
The 8-C3 dibenzothiophene, ppm S 60.47 16.28 14.98
The 9-C4 dibenzothiophene, ppm S 65.73 19.54 16.72
Total S, ppm 367.94 85.84 77.28
Table 4
Catalyst type Pressure p sg Wen Du ℉ LHSV Feed gas Gas flow rate, sccm Product S ppm Product Nppm Product OWt% Product TAN Acid-leached product Sppm Charging Sppm Charging Nppm Online hour Desulfurization % Denitrogenation %
Titanium silicate 200 322 1 N 2 250 310 128 356 233 6.63 1292％ 45.06％
Titanium silicate 200 322 1 N 2 250 310 174 <0.10 356 233 22.00 12.92％ 25.32％
Titanium silicate 200 323 1 7％O 2 250 180 176 <0.10 356 233 22.92 49.44％ 24.46％
Titanium silicate 200 323 1 7％O 2 250 90 137 <0.10 356 233 23.67 74.72％ 41.20％
Titanium silicate 200 322 1 7％O 2 250 120 134 <0.10 356 233 24.34 66.29％ 42.49％
Titanium silicate 200 322 1 7％O 2 250 130 138 <0.10 356 233 2509 63.48％ 4077％
Titanium silicate 200 323 1 7％O 2 250 170 143 0.10 356 233 25.84 52.25％ 38.63％
Titanium silicate 200 322 1 7％O 2 250 200 148 0.10 356 233 26.59 43.82％ 36.48％
Titanium silicate 200 322 1 7％O 2 250 230 156 0.10 356 233 27.34 35.39％ 33.05％
Titanium silicate 200 322 1 7％O 2 250 250 164 0.10 356 233 28.09 29.78％ 29.61％
No 200 305 1 7％O 2 250 346 246 0.10 0.03 253 356 233 17.00 2.81％ -558％
No 200 329 1 7％O 2 250 345 243 010 0.03 266 356 233 43.00 3.09％ -4.29％
Embodiment 3
Attempt the titanium silicate catalyzer that two kinds of diverse ways are used for regeneration of deactivated.First kind of regeneration (" A ") is included in heat treated spent catalyst in the flowing nitrogen (572 ℉), then thermal treatment several hrs at least in air (950 ℉); See the following form 5.Second kind of regeneration (" B ") method relates in closed reactor under 310 ℉ and catalyzer to be immersed in the methyl alcohol several hrs at least, then calcines several hrs at least in mobile is in 7% oxygen in the nitrogen under 800 ℉.Use these regenerated catalyzer to carry out method of the present invention then.The result is painted among Fig. 4 with illustrating, is listed in the table below in 6.
Table 5
Table 6
Figure S05845320820070702D000231
The result shows at catalyzer and can regenerate after oxidation/adsorption zone inactivation.At this moment, think that the sulphur compound of the oxidation of strong absorption is the reason that causes catalyst deactivation on the catalyst surface.Think and appear at nitrogen compound in the feed oil and the nitrogen compound (in the auxiliary oxidizing reaction of catalyzer) of oxidation also can work in catalyst deactivation.
Embodiment 3
Carry out three independent inactivation operations in the present embodiment.Table 7 shows basic all sulphur or is deposited on the catalyzer or is recovered in the product liquid.
Table 7
Figure S05845320820070702D000241
Embodiment 4
Use amorphous silicic acid titanium and Ti/MCM and Ti/HMS molecular sieve mixture to carry out other operation.Following table 8 and Fig. 5 represent the result of these operations.
Table 8
Online hour Catalyst type Pressure p sig Wen Du ℉ LHSV Feed gas Gas flow rate, sccm Product S, ppm Product N, ppm Charging S, ppm Charging N, ppm The % desulfurization
200 The Ti/MCM﹠Ti/MCM collosol and gel 200 318 1 3％O 2 250 92 203 356 233 74.16％
400 The Ti/MCM﹠Ti/MCM collosol and gel 200 318 1 3％O 2 250 166 160 356 233 53.37％
600 The Ti/MCM﹠Ti/MCM collosol and gel 200 318 1 3％O 2 250 177 163 356 233 5028％
225 Titanium silicate 200 321 1 3％O 2 250 74 44 356 233 79.21％
3.75 Titanium silicate 200 321 1 3％O 2 250 50 28 356 233 85.96％
6.00 Titanium silicate 200 321 1 3％O 2 250 106 47 356 233 70.22％
Embodiment 5
Fig. 6 represents the result of the various operations carried out according to the present invention, has wherein changed oxygen level and has changed temperature.

Claims (3)

1. one kind makes the distillating material desulfurization with production refining transport fuel or the refining transport fuel method with blending component, and wherein said raw material contains the sulfur-bearing organic impurity, and described method comprises:
(a) in the presence of the solid oxide catalyst that comprises titaniferous composition, under oxidizing condition, the described raw material that is in liquid phase is contacted with oxygen-containing gas, thereby at least a portion sulfur-bearing organic impurity is changed into sulfone and/or sulfoxide at oxidation/adsorption zone;
(b) sulfone and/or sulfoxide are adsorbed onto on the described solid oxide catalyst;
(c) has the oxidation/adsorption zone liquid efflunent of the sulfur-containing impurities of reduction from described oxidation/adsorption zone recovery; And
(d) described oxide catalyst regeneration is contained the sulfone of less absorption and/or the oxide catalyst of sulfoxide with generation.
2. the method for claim 1 wherein contacts described catalyzer under the condition that makes adsorbed sulfone and/or sulfoxide desorption and regenerates with methyl alcohol.
3. the method for claim 1, wherein said titaniferous composition is selected from titanium silicate, Ti-MCM and Ti-HMS.
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