CN101921614A - Remove the method for impurity from hydrocarbon ils - Google Patents
Remove the method for impurity from hydrocarbon ils Download PDFInfo
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- CN101921614A CN101921614A CN2010101678733A CN201010167873A CN101921614A CN 101921614 A CN101921614 A CN 101921614A CN 2010101678733 A CN2010101678733 A CN 2010101678733A CN 201010167873 A CN201010167873 A CN 201010167873A CN 101921614 A CN101921614 A CN 101921614A
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- hydrocarbon ils
- impurity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
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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
- C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
- C10G17/09—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acid salts
-
- 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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of method of removing impurity from the raw material that comprises hydrocarbon ils.Described method comprises makes raw material contact under the condition that effectively makes at least a portion oxidation of impurities with oxygen-containing gas, and make raw material and Louis silk acid effectively make in the raw material any Louis silk alkali impurity can with the condition of Louis silk acid-respons under contact.Remove any impurity of oxidation like this and/or reaction then.
Description
Background technology
Oil is the main source that is used as the hydrocarbon of fuel and petrochemical materials in the world.Owing to there is impurity, crude oil seldom uses with the form that produces in oil well, but generally changes into wide range of fuel and the petrochemical materials that is fit to its expection end-use at refinery.Though the composition of natural oil or crude oil is changed significantly, all crude oil all comprise sulphur compound.Sulphur concentration in the general crude oil is about 0.5 to about 1.5%, but can upwards depart from the highest by about 8%.When burning, sulfocompound changes into oxysulfide (SOx), it is believed that it is a kind of environmental pollutant.Therefore the catalyzed oxidation of sulphur and can cause forming sulfuric acid mist with water reaction subsequently also causes particulate emission.Therefore, this quasi-oil generally must be through desulfurization, to be met the product of performance specification and/or environmental standard.
In fact, may become more and more important from now on from petroleum and product sulphur removal.Though for example Europe, Japan and the U.S. to diesel oil fuel in the rules of sulphur recently the on-highway motor vehicle standard is reduced to 0.001 (EU) or 0.0015 (US) % weight from 0.05, have the following standard of sign can be lower than this level, and comprise cross-country motor vehicle.
Now used hydrogenating desulfurization (HDS) to remove impurity, and can remove most of sulphur from hydrocarbon ils.Yet conventional hydrodesulfurizationprocess process is not removed aromatic sulfur compound effectively, as thionaphthene and dibenzothiophene.Strengthen some hydrogenating desulfurization processing conditions, for example temperature of reaction, hourly space velocity etc. can improve and remove these more obstinate pollutents, yet strengthen the cost that processing conditions can increase strengthening process.In addition, use conventional Hydrobon catalyst can cause production loss, very fast catalyst coking and product quality to degenerate at high temperature.
Therefore, needs efficiently, more cost is effectively removed the method for sulphur compound from crude oil.These class methods that cater to the need can be removed to aromatic sulfur compound need extremely low-level in a lot of the application.
Summary of the invention
The invention provides the method that is used for removing sulphur impurity from hydrocarbon ils.Described method comprises makes hydrocarbon ils contact under the condition that effectively makes at least a portion oxidation of impurities with oxygen-containing gas.Method also comprise make hydrocarbon ils and Louis silk acid effectively make in the hydrocarbon ils any Louis silk alkali impurity can with the condition of Louis silk acid-respons under contact.Remove any impurity of oxidation like this and/or reaction from hydrocarbon ils.
The present invention also is provided for removing from hydrocarbon ils the method for sulphur impurity.Described method comprises makes hydrocarbon ils contact under the condition that effectively makes the oxidation of at least a portion sulphur impurity with the gas that comprises nitrogen peroxide or nitrogen oxide and oxygen.Make then comprise through the hydrocarbon ils of sulfur oxide impurity and Louis silk acid effectively make in the hydrocarbon ils any Louis silk alkali sulphur impurity can with the condition of Louis silk acid-respons under contact.Remove any impurity of oxidation like this and/or reaction then from hydrocarbon ils.
Description of drawings
By reading following detailed description and with reference to the accompanying drawings, these and other features of the present invention, aspect and advantage will become better understood, the similar similar element of digitized representation in whole accompanying drawings wherein, wherein:
Fig. 1 is the schema of an embodiment of illustrative the inventive method;
Fig. 2 is the schema of another embodiment of illustrative the inventive method;
Fig. 3 is the schema of another embodiment of illustrative the inventive method;
Fig. 4 is the schema of another embodiment of illustrative the inventive method;
Fig. 5 is the schema of another embodiment of illustrative the inventive method; And
Fig. 6 is the schema of an other embodiment of illustrative the inventive method.
Embodiment
Unless otherwise defined, technology used herein and scientific terminology all have the identical meanings that those skilled in the art in the invention generally understand.Term used herein " first ", " second " etc. are not represented any order, amount or importance, but are used to distinguish a key element and another key element.In addition, term " one " (a) and " one " (an) do not represent quantitative limitation, but there is at least one project of quoting in expression, unless and mention in addition, just use for convenience of description term " front portion ", " rear portion ", " bottom " and/or " top ", is not limited to arbitrary position or spatial orientation.If scope is open, the end points that then points to all scopes of identical component or character is inclusive and (for example can independently makes up, " maximum about 25% weight; or more particularly, about 5% weight is to about 20% weight " scope comprises all intermediate values of end points and " about 5% weight is to about 25% weight " scope etc.).Comprise described value interior with the qualifier " pact " of the relevant use of amount, and have by the specified meaning of context (for example, comprising and the concrete relevant degree of error of measurement amount).
The invention provides the method that is used for removing impurity from hydrocarbon ils.Described method comprises makes hydrocarbon ils contact under the condition that effectively makes at least a portion oxidation of impurities with oxygen-containing gas.The acid of hydrocarbon ils and Louis silk is contacted, so as to allow to as any impurity of Louis silk alkali can with Louis silk acid-respons.Remove any impurity of oxidation like this and/or reaction then from hydrocarbon ils.
Methods described herein can favourablely be applied to the impure any hydrocarbon ils or the mixture of one or more hydrocarbon ils.Be applicable to that exemplary hydrocarbon of the present invention includes but not limited to liquid oils, oil, resinous shale, coal and the synthetic crude that makes by gelatin liquefaction, heavy crude oil, oil distillate and the petroleum refining residual oil fraction (as bottoms or the cut that makes by crude oil normal pressure and vacuum distilling) that obtains from pitch (being commonly referred to Tar sands or oil-sand).
Hydrocarbon fuel oil can or add solvent " former state " through method of the present invention without pre-treatment.Yet, in some embodiments,, may need to add the fuel solvent in order to help processing.In this embodiment, hydrocarbon ils can be chosen wantonly with the combination of the mixture of fuel solvent or solvent and provide, and forms slurry with further liquefaction or with hydrocarbon ils, and therefore potentially helps processing.Exemplary suitable nonpolar fuel solvent includes but not limited to sherwood oil, hexane, pentane, hexanaphthene, heptane, propane, butane, these mixture etc.
Need therein in the embodiment of fuel solvent, the ratio of fuel solvent and hydrocarbon ils caters to the need is enough to make hydrocarbon ils-fuel solvent mixture to have the viscosity (from about 0.342cSt to 15.6 ℃ about 23.2cSt of 17.8 ℃) of the highest about 32.6 ° of API gravity crude oil.It is about 0.5: 1 to about 10: 1 that expection can provide the fuel solvent of required viscosity and the ratio of hydrocarbon ils, or about 1: 1 to about 2: 1.Optional used any fuel solvent can reclaim wholly or in part, and for this reason or other purposes circulations.
Also can choose the pre-treatment hydrocarbon ils wantonly, for example to remove high molecular and/or particulate contamination through before the method for the present invention.For example, can make hydrocarbon ils through centrifugal or other suitable isolation technique, to remove this type of particulate state resistates.Perhaps, can remove any particulate state resistates (perhaps vice versa) from hydrocarbon ils by filtration, decantation etc.If desired, available a certain amount of fuel solvent improves the processibility of hydrocarbon ils in any required pre-treatment step.
This pre-treatment can be removed any sedimentary at least a portion that exists in hydrocarbon ils, thereby can reduce to be deposited in the interference of oxidation and Louis silk acid complexing step.For example, hydrocarbon ils generally can comprise the heteroatomic bituminous matter that contains of different amounts, and these bituminous matters can be disturbed and remove impurity by competition oxygen-containing gas/Louis silk acid.By before oxidation or Louis silk acid are added to hydrocarbon ils, removing at least a portion bituminous matter, can improve the efficient of oxidation and/or Louis silk acid complexing.
The impurity of desirably removing from hydrocarbon ils by open method can comprise can be oxidized and/or generate oxidation or unoxidized any material of complex compound (being referred to herein as " Louis silk acid-alkali complex compound ") with the acid of Louis silk.In one embodiment of the invention, impurity can comprise one or more sulphur, nickel or vanadium, that is, that impurity can comprise is nickeliferous, any ion, salt, complex compound and/or the compound of vanadium and sulphur.Can include but not limited to vanadium porphyrin and oxide compound, for example vanadium pentoxide by the example that contains foreign matter of vanadium that method of the present invention is removed.The example that contains nickel impurity comprises nickel-porphyrin, salt etc.
In one embodiment, impurity comprises sulfur-containing organic compound, for example alkyl sulfide or aromatics sulfocompound.The example that generally can pollute the sulfur-containing organic compound of hydrocarbon ils comprises thiophene and derivative thereof.The exemplary derivative of thiophene comprises thionaphthene, dibenzothiophene, phenanthro-thiophene, benzo aphthothiophenes, thiophene sulfide of various replacements etc.Concrete impurity in the hydrocarbon ils and concentration thereof can be depending on the geographical source of hydrocarbon ils and the form and the previous processing (if the words that have) of hydrocarbon ils.
Method of the present invention comprises makes impure hydrocarbon ils contact with oxygen-containing gas.Can use any oxygen-containing gas, as long as oxygen carrier (comprises molecular oxygen (O in the gas
2)) oxidation capacity and concentration at least a portion oxidation that can reach impurity in the hydrocarbon ils enough.Those of ordinary skill in the art it should be understood that the concentration that should select used oxygen, forms to avoid blast.Effective concentration in these parameters can for about 0.01% volume (vol%) to about 21% volume, or about 0.5% volume is to about 10% volume.
For example, available air or oxygen-denuded air, ozone, nitrogen peroxide or its combination are as oxygen-containing gas.Now advantageously find, do not use catalyzer, can make up some impurity in the oxidation hydrocarbon ils at an easy rate by nitrogen oxide/air.Yet, in certain embodiments, can utilize air or oxygen-denuded air, and in these embodiments, by using catalyzer, as comprise any catalyzer of molybdenum, copper, manganese, cobalt, tungsten, iron etc., can promote at least a portion oxidation of impurity in the hydrocarbon ils.
Oxygen-containing gas comprises in those embodiments of combination of nitrogen peroxide or nitrogen oxide and for example air therein, does not need catalyzer, and efficient is provided.In these embodiments, can utilize 1% volume to 20% volume or about 4% volume aerial nitrogen oxide or the nitrogen peroxide in any gas to about 10% volumetric concentration.Oxygen-containing gas further cater to the need provide at least about 1 the crust, or about 1 the crust to about 200 the crust, or even about 10 the crust to about 30 the crust pressure.Have at least about 20 ℃ by providing, or about 20 ℃ to about 150 ℃, or even about 80 ℃ of hydrocarbon ils to about 120 ℃ of temperature, can further promote the oxidation of at least a portion impurity in the hydrocarbon ils.
In some embodiments, for example at hydrocarbon ils with before Louis silk acid/Louis silk acid solution contacts, can desirably remove the insoluble oxidation products that generates by contacting with oxygen-containing gas, this can increase the efficient that generates Louis silk acid-alkali complex compound.Can utilize any method of removing oxidation products that is applicable to, the exemplary method of removing comprises for example filtration, decantation, centrifugal etc.
Hydrocarbon ils is contacted with the acid of Louis silk.Louis silk acid can be any ion or the compound (for example oxidized or unoxidized impurity) that can accept electron pair from corresponding Louis silk alkali.Believe that a lot of impurity (being specially the impurity of sulfur-bearing, nickel and vanadium) of generally finding in hydrocarbon ils can be used as Louis silk alkali, these Louis silk alkali can generate stable complex compound with the acid of Louis silk again.Louis silk acid-alkali complex compound has low-solubility to there not being solvability in hydrocarbon ils, therefore can remove from hydrocarbon ils.
The example that is applicable to the Louis silk acid of the open method of the present invention comprises one or more positively charged ions H
+, Li
+, Na
+, Au
+, Be
2+, Mg
2+, Ca
2+, Sn
2+, Sn
4+, Al
3+, Ga
3+, In
3+, La
3+, Ce
3+, Cr
3+, Co
3+, Fe
3+, As
3+, Ir
3+, Si
4+, Ti
4+, Zr
4+, Th
4+, U
4+, Pu
4+, VO
2+, UO
2 2+, (CH
3)
2Sn
2+With metal halide, alkylide, hydride, alkoxide, for example BeMe
2, AlCl
3, GaCl
3, FeCl
3, AlH
3, BF
3, BCl
3, B (OR)
3, Al (CH
3)
3, Ga (CH
3)
3, In (CH
3)
3The silk acid of positively charged ion Louis generally can provide with the gegenion combination, and can generate any suitable gegenion of use in the metal-salt with the acid of Louis silk.
Also above listed a lot of exemplary Louis silk acid can be classified as the silk acid of Pearson Louis, these can be particularly suitable for generating complex compound with the sulphur of finding sometimes, vanadium and nickel impurity in hydrocarbon ils.Therefore, in one embodiment, Louis silk acid can comprise the silk acid of hard Pearson Louis.The feature of hard Pearson Louis silk acid is that generally they have the former subcenter of small ion radius, has higher relatively positive charge, in its valence shell, do not contain electron pair, have low electron affinity, may be by strong solventization, and have the low not occupied molecular orbital (LUMO) of high energy.The example of hard Pearson Louis silk acid is determined at R.G.Pearson.J.Am.Chem.Soc.1963,85:3533-3543; R.G.Pearson, Science, 966,151:172-177; R.G.Pearson, Chem.Br., 1967,3:103-107; And R.G.Pearson, J.Chem.Ed., 1968,45:581-587, described document all are attached to herein by reference for any and all purposes.
In one embodiment, silk acid in Louis can comprise one or more AlCl
3, GaCl
3, FeCl
3, these compounds with thiophene compound and derivative thereof generate in the complex compound effective especially, for example according to following reaction scheme:
(I)
MX wherein
n=AlCl
3, GaCl
3, FeCl
3
Louis silk acid can desirably provide as solution,, can provide Louis silk acid with suitable solvent combination that is.Solvent can cater to the need and be aprotic solvent, that is, and not with the solvent that is dissolved in exchange of substance proton wherein.Cater to the need aprotic solvent for can form the biphase solvent easily when mixing with hydrocarbon ils.In order to promote to separate, can select aprotic solvent, so that the positive charge material solvation of Louis silk acid.For example, in certain embodiments, aprotic solvent can be acetonitrile, Nitromethane 99Min., 1,2-ethylene dichloride or its combination.
When providing with relative stoichiometry, Louis silk acid can with can generate complex compound as any impurity of Louis silk alkali.Yet, owing in hydrocarbon ils, may have the competition component, in one embodiment, can favourablely provide stoichiometry excessive Louis silk acid, with the possibility of basic all impurity in the raising hydrocarbon ils and Louis silk acid complexing.For example, Louis silk acid can with respect to the impurity in the hydrocarbon ils slightly (for example 1%) stoichiometry is excessive provides, perhaps, Louis silk acid can stoichiometry be excessive provides with respect to about 300% (3 times) of impurity.
Carry out the acid of Louis silk complexing is favourable and needn't heat and pressurize.Subsequently, can choose wantonly by providing and have, or about 20 ℃ to about 50 ℃ at least about 15 ℃, or even about 20 ℃ of hydrocarbon ils to about 35 ℃ of temperature, further promoting in the hydrocarbon ils can be as the complexing of at least a portion impurity of Louis silk alkali.Just when Louis silk acid contact, hydrocarbon ils further caters to the need to be provided at least about 1 normal atmosphere, or about 1 normal atmosphere is to about 5 normal atmosphere, or even about 1 normal atmosphere about 2 atmospheric pressure extremely.
Can remove the impurity of oxidation like this and/or reaction from hydrocarbon ils then.More particularly, to move on to isolating difference mutually or begin to form isolating difference mutually with the optional fuel solvent from hydrocarbon ils and optional fuel solvent through the impurity of oxidation and/or reaction, so that form the first layer that contains hydrocarbon ils and optional fuel solvent and the second layer that contains Louis silk acid-alkali complex compound and optional aprotic solvent from hydrocarbon ils.Though pre-material mixture can separate alone, can promote that mixture separation becomes the first layer and the second layer by centrifugal or any other appropriate methodology.
After the layering, can separate, for example by decantation or pass through separating funnel by make layer at any suitable extracting process known in the art or device.Subsequently, will be transported to the use point, perhaps can for example remove any fuel solvent that is added to hydrocarbon ils at first, perhaps handle again by one or more steps of open method through further handling by the hydrocarbon ils that open method is handled.For example, after processing, remove, then can remove, as removing by evaporation by any appropriate methodology if the fuel solvent has used and catered to the need.
Contact procedure can any order or is carried out relatively simultaneously, but can favourablely carry out successively, and at first carries out oxidation step.In these embodiments of the present invention, the step that the acid of hydrocarbon ils and Louis silk contacts can remove can be as Louis silk alkali any through oxidation impurities and oxidation resistant any impurity.In these embodiments, contact procedure can act synergistically, that is, produce than removing more polymictic ability by independent step.
Also can repeat one of contact procedure or both parallel or successively, to be further purified hydrocarbon ils.For example, hydrocarbonaceous oil separating layer is contacted with in addition the Louis silk acid or the Louis silk acid solution of amount, and/or can contact any number of times with identical or different oxygen-containing gas.One skilled in the art will understand that the number of times that this process is carried out can be depending on the required purity of final hydrocarbon product, and can repeat one or more contact procedures, up to reaching required purity substantially.
Can further handle the separating layer that contains Louis silk acid, with recovery Louis silk acid, in case reusable, no matter at open method or additive method.The Louis silk acid of reclaiming if desired and circulate then can make the layer that contains Louis silk acid and can contact with the acid that the Louis silk acid of impurity complexing is competed.Can be the hydrochloric acid of about 0.001M with an example of the sour acid of competing of Louis silk to about 3.5M concentration.Preferably use the Louis silk acid in the silk acid-alkali complex compound of this acid substitution Louis, so that silk acid in Louis discharges.In case discharge, just can reclaim Louis silk acid by any usability methods (for example crystallization, distillation etc.), be used to be used further to this process or another process, perhaps store, utilize again up to needs.
Other known technologies of available ratio of the present invention (as HDS and solvent extraction, or separately oxidation or Louis silk acid complexing) are removed the substantially more impurity of a large amount.For example, disclosed method can the Louis silk acid of enough significant quantities be removed basic all sulphur impurities from having greater than the hydrocarbon ils of about 0.5% weight sulphur.In another aspect of the present invention, basic all sulphur impurity (for example, be removed to less than about 1% weight level) can be removed from having greater than the hydrocarbon ils material of 3% sulphur content by methods described herein and system.Aspect of the present invention is used in particular for gas turbine application, wherein caters to the need usually sulphur impurity content is reduced to less than about 1% weight sulphur from 4% weight sulphur (or bigger).Therefore, in one aspect, the invention provides effective cost effective method of removing sulphur impurity (for example thiophene and derivative thereof) from high sulfur content fuel.
With reference now to Fig. 1,, Fig. 1 shows an embodiment of removing the open method of impurity from hydrocarbon ils with the schema form.More particularly, Fig. 1 display packing 100 wherein provides the hydrocarbon ils that comprises impurity 101.Can comprise by the impurity that method 100 is removed can be oxidized and/or generate any material of complex compound with the acid of Louis silk, in some embodiments, can comprise one or more sulphur, nickel or foreign matter of vanadium.In a specific embodiments, impurity comprises sulfur-containing organic compound, and for example thiophene and derivative thereof comprise various thionaphthenes, dibenzothiophene, phenanthro-thiophene, benzo aphthothiophenes, sulfide (as aromatics and non-aromatics alkyl sulfur compounds) etc.
Can choose wantonly and mix hydrocarbon ils and fuel solvent, to improve its processibility, shown in step 102.Optional fuel solvent can comprise any suitable non-polar solvent, for example sherwood oil, hexane, pentane, hexanaphthene, heptane, propane, butane, any other nonpolar hydrocarbon solvents with relatively low boiling point or the combination of these solvents.In these embodiments, the ratio of fuel solvent and hydrocarbon ils can be about 0.5: 1 to about 10: 1, or about 1: 1 to about 2: 1.
In step 103 hydrocarbon ils or hydrocarbon ils/fuel solvent mixture are contacted with oxygen-containing gas.Oxygen-containing gas can be for making from hydrocarbon ils cater to the need any gas of at least a portion oxidation of impurities of removing, for example mixture of air, oxygen-denuded air, rich ozone-air, nitrogen peroxide, airborne nitrogen oxide or these gases.Can have and be used in those embodiments that oxygen-containing gas wherein comprises air or oxygen-denuded air though comprise the catalyzer of molybdenum, copper, manganese, cobalt, tungsten, iron or these combinations, oxygen-containing gas comprises the favourable catalyzer that do not need in those embodiments of nitrogen oxide or nitrogen peroxide therein.
As shown in the step 104, also make hydrocarbon ils provide or contact, so that Louis silk acid solution to be provided with the Louis silk acid of solvent combination with pure.If want maybe to need to use solvent, then also can desirably use aprotic solvent, for example acetonitrile, Nitromethane 99Min., 1,2-ethylene dichloride or its combination.Louis silk acid can for any can from corresponding Louis silk alkali (in the case for can as Louis silk alkali through oxidation and/or unoxidized impurity) accept the ion or the compound of electron pair.The Louis silk acid-alkali complex compound that obtains is easy to separate from hydrocarbon ils, specifically, provides those embodiments of Louis silk acid therein as Louis silk acid solution with aprotic solvent.Louis silk acid can desirably comprise the silk acid of the hard Louis of Pearson, in some embodiments, comprises AlCl
3, GaCl
3, FeCl
3Or its combination.Though can choose wantonly in any step 101-104 heating or pressurization, method disclosed by the invention is favourable not to need heating and pressurization to carry out oxidation or Louis silk acid complexing.
In case hydrocarbon ils and Louis silk acid solution mix, just begin in the acid of Louis silk and anyly can generate Louis silk acid-alkali complex compound between the impurity as the hydrocarbon ils of Louis silk alkali, and blended solution begins phase-splitting (fractionate), promptly form two not homophases.One comprises hydrocarbon ils (with the fuel solvent of any adding, if exist) mutually, and another comprises Louis silk acid-alkali complex compound and aprotic solvent (if use) mutually.If want or requirement, available centrifugal promotion separates.As shown in the step 105, can make then to be separated, for example by decantation or filtration,,, and the hydrocarbon ils of purifying stored or further handle by liquid-liquid extractor or separating funnel if perhaps use aprotic solvent.If add any fuel solvent to promote to handle hydrocarbon ils, then can for example remove from the hydrocarbon ils of purifying by evaporation.
In some embodiments, desirably one of repeated oxidation and/or Louis silk acid complexing step or both.One of repeated oxidation and/or Louis silk acid complexing step or both can further reduce the amount of impurity in the hydrocarbon ils, so that can access purer part, and perhaps can be from thicker rank.An embodiment like this is shown among Fig. 2, wherein in step 206, makes mixture through other oxidation and Louis silk acid complexing step.Fig. 3 shows this other embodiments, wherein in step 306 a repetition Louis silk acid complexing step.
Another embodiment is shown among Fig. 4, Fig. 4 display packing 400, and method 400 further comprises pre-treatment purification step 407, wherein can remove degranulation or other high molecular impurity from hydrocarbon ils.Hydrocarbon ils generally can comprise bituminous matter or other particles of different amounts, and these can disturb from hydrocarbon ils and remove sulfur-containing impurities.By before oxidation and/or Louis silk acid are added to hydrocarbon ils, removing at least some bituminous matters, can improve the efficient of oxidation and/or Louis silk acid complexing.
More particularly, pre-treatment purification step 407 can comprise the adding solvent, and is then that this mixture is centrifugal to improve the processibility of hydrocarbon ils, has than hydrocarbon ils more at least a portion particle or the impurity of high molecular or density with precipitation.The pre-treatment purification step also can comprise filtration, decantation or its combination.Can make then through pretreated hydrocarbon ils from precipitate and separate, and further handle according to methods described herein.
Another embodiment is shown among Fig. 5, and wherein method 500 comprises that further the mixture separation that makes phase-splitting (fractionated) becomes the hydrocarbon ils part and the part that contains Louis silk acid complex of purifying, and reclaims Louis silk acid in step 508.More particularly, step 508 can comprise and adds acid to Louis silk acid moieties, expects its regeneration Louis silk acid, then can be by the recovery of any usability methods, for example crystallization or distillation.Can store Louis silk acid then and be used for using in the future,, circulate and be reused for the step 504 of method 500 perhaps as shown in the step 509.Any acid of Louis silk acid of can regenerating all can be used for step 508, and an example that is fit to acid is to have the extremely hydrochloric acid of about 3.5M concentration of about 0.001M.
In some embodiments, with before Louis silk acid/Louis silk acid solution contacts, can remove the oxidation products that generates by contacting with oxygen-containing gas at hydrocarbon ils, this can increase the efficient that generates Louis silk acid-alkali complex compound.This embodiment is shown among Fig. 6, and wherein method 600 is included in the oxidation products that step 610 is removed generation.Can utilize any method be fit to remove oxidation products in step 610, the appropriate methodology that is used to remove oxidation products for example comprise filter, centrifugal, decantation etc.Fig. 6 also shows that embodiment of the present invention, wherein before hydrocarbon ils and oxygen-containing gas and/or the acid of Louis silk contact, hydrocarbon ils not with the fuel solvent.
Embodiment 1
4.02 grams 1% solution (simulation hydrocarbon ils) of thionaphthene (BZT) in naphthalane is weighed into the 15ml centrifuge tube.Add 5.04 gram Nitromethane 99Min.s, with the benzene extraction thiophthene.To manage and acutely shake about 2 minutes, centrifugal 10 minutes then at 2100rpm.To go up phase (supernatant liquor) suction and shift out, and measure sulphur content by XRF.5.04g about 50% sulphur in the Nitromethane 99Min. extraction naphthalane.
Embodiment 2
With 4.00 the gram 1% in naphthalane the solution of thionaphthene be weighed into the 15ml centrifuge tube, solution in being equipped with the flask of water cooled condenser by making airborne 3%NO at 75 ℃
2Used NO in 2 hours with 150sccm speed bubbling
2Anticipate.Add 5.04 gram Nitromethane 99Min.s, with benzene extraction thiophthene/NO
2Oxidation products.To manage and acutely shake about 2 minutes, centrifugal about 10 minutes then at 2100rpm.To go up phase (supernatant liquor) suction and shift out, and by XRF mensuration sulphur content wherein.About 52% sulphur in the naphthalane is extracted in the Nitromethane 99Min..
Embodiment 3
4.01 grams 1% solution of thionaphthene in naphthalane is weighed into the 15ml centrifuge tube, and solution is used NO in advance
2As processing as described in 2 among the embodiment.The Louis silk acid solution that adds 5.01 gram 0.56M iron(ic) chloride (III) in Nitromethane 99Min..To manage and acutely shake about 2 minutes, centrifugal 10 minutes then at 2100rpm.To go up to inhale mutually and shift out, and measure sulphur content by XRF.Utilize oxidation to use Louis silk acid treatment subsequently, about 88% initial sulphur in the extraction naphthalane.
Embodiment 4
4.02 grams 1% solution of thionaphthene in naphthalane is weighed into the 15ml centrifuge tube, and solution is used NO in advance
2As processing as described in 2 among the embodiment.The Louis silk acid solution that adds 2.50 gram 0.56M iron(ic) chloride (HI) in Nitromethane 99Min..To manage and acutely shake about 2 minutes, centrifugal 10 minutes then at 2100rpm.To go up phase (supernatant liquor) suction and shift out, and measure sulphur content by XRF.About 82% initial sulphur in the extraction naphthalane.Therefore, only use half Louis silk acid, at NO
2Remove most of thionaphthene mutually from naphthalane after the silk acid treatment of/Louis.
Embodiment 5
4.03 grams 1% solution of octyl group sulphur (OS) in naphthalane is weighed into the 15ml centrifuge tube, and solution is used NO in advance
2As processing as described in 2 among the embodiment.Add 4.0 gram Nitromethane 99Min.s, with extraction octyl group sulphur oxidation products.To manage and acutely shake about 2 minutes, centrifugal about 10 minutes then at 2100rpm.To go up to inhale mutually and shift out, and measure sulphur content by XRF.About 31% sulphur in the naphthalane is extracted in the Nitromethane 99Min..
Embodiment 6
4.01 grams 1% solution of octyl group sulphur in naphthalane is weighed into the 15ml centrifuge tube, and solution is used NO in advance
2As processing as described in 2 among the embodiment.The Louis silk acid solution that adds 4.01 gram 0.56M iron(ic) chloride (III) in Nitromethane 99Min..To manage and acutely shake about 2 minutes, centrifugal about 10 minutes then at 2100rpm.To go up to inhale mutually and shift out, and measure sulphur content by XRF.Remove about 82% sulphur in the naphthalane.
Embodiment 7
4.0 grams 1% solution of octyl group sulphur in sherwood oil is weighed into the 15ml centrifuge tube.The Louis silk acid solution that adds 4.01 gram 0.56M iron(ic) chloride (III) in Nitromethane 99Min..To manage and acutely shake about 2 minutes, centrifugal 10 minutes then at 2100rpm.To go up to inhale mutually and shift out, and measure sulphur content by XRF.Remove about 44% sulphur in the sherwood oil.
Embodiment 1-7 the results are summarized in the following table 1.In brief, embodiment 3 shows that oxidation is removed than neat solvent extraction (embodiment 1) and the significantly more aromatics sulphur (BZT) of independent oxidation (embodiment 2) with Louis silk acid treatment combination.Embodiment 4 shows, in addition 1/2 Louis silk acid concentration also be so, that is, compare with embodiment 3, in embodiment 4, see similar sulphur removal per-cent, although use the Louis silk acid of embodiment 3 used half strengths.Simultaneously, embodiment 6 shows the synergistic effect of using oxidation and Louis silk acid extraction to remove aliphatic sulphur, i.e. oxidation is removed more aliphatic sulphur with Louis silk acid extraction combination than independent oxidation (embodiment 5) or Louis silk acid extraction (embodiment 7).
| Embodiment | The sulphur source | Initial %S | Final %S | Δ (S that % removes) | Explain |
| 1 | BZT | 0.254 | 0.127 | 50％ | Only extraction (neither oxidation, also not Louis silk acid treatment) |
| 2 | BZT | 0.256 | 0.123 | 52％ | Oxidation+extraction |
| 3 | BZT | 0.256 | 0.031 | 88％ | Oxidation+Louis silk acid treatment |
| 4 | BZT | 0.256 | 0.046 | 82％ | Oxidation+Louis silk acid treatment is in 1/2 concentration of embodiment 3 |
| 5 | 0S | 0.139 | 0.096 | 31％ | Oxidation+extraction |
| 6 | OS | 0.139 | 0.025 | 82％ | Oxidation+Louis silk acid treatment |
| 7 | OS | 0.426 | 0.239 | 44％ | Louis silk acid treatment (not oxidation) |
Though this paper has shown and has described different embodiments of the present invention, should be understood that these embodiments only as an example, and not as restriction.Those skilled in the art can not break away from and much changes, changes under the professor of the present invention and substitute.Therefore, in the complete spirit and scope of accessory claim, explain the present invention consciously.
Component list
100 methods
101 steps
102 steps
103 steps
104 steps
105 steps
200 methods
201 steps
202 steps
203 steps
204 steps
205 steps
300 methods
301 steps
302 steps
303 steps
304 steps
305 steps
306 steps
400 methods
401 steps
402 steps
403 steps
404 steps
405 steps
407 steps
500 methods
501 steps
502 steps
503 steps
504 steps
505 steps
508 steps
509 steps
600 methods
601 steps
603 steps
604 steps
605 steps
610 steps
Claims (10)
1. method of removing impurity from hydrocarbon ils, described method comprises:
(a) hydrocarbon ils is contacted under the condition that effectively makes at least a portion oxidation of impurities with oxygen-containing gas;
(b) make hydrocarbon ils and Louis silk acid effectively make in the raw material any Louis silk alkali impurity can with the condition of Louis silk acid-respons under contact; With
(c) remove any impurity of oxidation like this and/or reaction from hydrocarbon ils.
2. the process of claim 1 wherein that oxygen-containing gas comprises air, rich ozone-air, nitrogen oxide and AIR MIXTURES, nitrogen peroxide or its combination.
3. the method for claim 2, wherein oxygen-containing gas comprises air, the condition of the efficient oxidation comprises the use catalyzer.
4. the process of claim 1 wherein that impurity comprises sulphur.
5. the method for claim 4, wherein impurity comprises and replacing and unsubstituted thionaphthene, dibenzothiophene, phenanthro-thiophene, benzo aphthothiophenes, alkyl sulfur compounds, aromatic yl sulfide or derivatives thereof.
6. the method for claim 5 wherein makes the oxidation of at least a portion sulphur impurity form sulfoxide and sulfone.
7. the process of claim 1 wherein that Louis silk acid comprises AlCl
3, GaCl
3, FeCl
3Or its combination.
8. the method for claim 7, wherein silk acid in Louis is used as the solution in the aprotic solvent.
9. the process of claim 1 wherein that at least one step repeats at least once.
10. the method for claim 1, described method further comprises pre-treatment oil fuel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/425,124 US20100264067A1 (en) | 2009-04-16 | 2009-04-16 | Method for removing impurities from hydrocarbon oils |
| US12/425124 | 2009-04-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101921614A true CN101921614A (en) | 2010-12-22 |
Family
ID=42562858
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101678733A Pending CN101921614A (en) | 2009-04-16 | 2010-04-16 | Remove the method for impurity from hydrocarbon ils |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20100264067A1 (en) |
| EP (1) | EP2241609A1 (en) |
| JP (1) | JP2010248509A (en) |
| CN (1) | CN101921614A (en) |
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| CN101892075A (en) * | 2010-07-27 | 2010-11-24 | 中国石油大学(华东) | Method for transforming, separating and processing heavy oil |
| CN111363588A (en) * | 2018-12-25 | 2020-07-03 | 中国石油化工股份有限公司 | Method and reaction system for producing low-sulfur petroleum coke |
| CN112442390A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing low-sulfur petroleum coke from residual oil |
| CN112442391A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of low-sulfur petroleum coke |
| CN112742476A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for producing low-sulfur petroleum coke |
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| CN102453524B (en) * | 2010-10-21 | 2015-01-21 | 上海欣年石化助剂有限公司 | Refining method of gasoline |
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| RU2578692C2 (en) | 2011-10-24 | 2016-03-27 | Адитиа Бирла Нуво Лимитед | Improved method for carbon ash production |
| MX350307B (en) | 2012-03-30 | 2017-09-04 | Aditya Birla Science And Tech Company Ltd | A process for obtaining carbon black powder with reduced sulfur content. |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
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| CN111363588B (en) * | 2018-12-25 | 2023-08-15 | 中国石油化工股份有限公司 | Method and reaction system for producing low-sulfur petroleum coke |
| CN112442390A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing low-sulfur petroleum coke from residual oil |
| CN112442391A (en) * | 2019-08-28 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of low-sulfur petroleum coke |
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| CN112742476B (en) * | 2019-10-29 | 2023-09-05 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for producing low-sulfur petroleum coke |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2241609A1 (en) | 2010-10-20 |
| JP2010248509A (en) | 2010-11-04 |
| US20100264067A1 (en) | 2010-10-21 |
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