CN110249035A - Oxidation sweetening and the sulfone management of oil distillate are carried out using FCC - Google Patents

Oxidation sweetening and the sulfone management of oil distillate are carried out using FCC Download PDF

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Publication number
CN110249035A
CN110249035A CN201880008484.0A CN201880008484A CN110249035A CN 110249035 A CN110249035 A CN 110249035A CN 201880008484 A CN201880008484 A CN 201880008484A CN 110249035 A CN110249035 A CN 110249035A
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China
Prior art keywords
hydrocarbon
aoxidizing
stream
compound
catalytic cracking
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CN201880008484.0A
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Chinese (zh)
Inventor
奥默·里法·克赛奥卢
阿卜杜努尔·布朗
斯特凡娜·西里尔·克雷斯曼
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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Priority claimed from US15/415,294 external-priority patent/US10087377B2/en
Application filed by Saudi Arabian Oil Co filed Critical Saudi Arabian Oil Co
Publication of CN110249035A publication Critical patent/CN110249035A/en
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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
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/22—Compounds containing sulfur, selenium, or tellurium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/14—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with ozone-containing gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Embodiment provides the method and apparatus for recycling ingredient from hydrocarbon raw material.According at least one embodiment, this method includes that hydrocarbon raw material is supplied to oxidation reactor, wherein in the presence of a catalyst, hydrocarbon raw material is aoxidized under conditions of being enough sulphur compound present in selectively oxygenated hydrocarbon feedstock and nitrogen compound, by solvent extraction to hydrocarbon, sulphur compound through aoxidizing and the nitrogen compound through aoxidizing are separated, collect the residual oil stream comprising the sulphur compound through aoxidizing and the nitrogen compound through aoxidizing, residual oil stream is supplied to fluid catalytic cracking unit, and the liquid product generated by fluid catalytic cracking unit is made to be recycled to oxidation reactor, selectively to aoxidize the sulphur compound in liquid product, the liquid product of the part includes at least one of light cycle and heavy recycle stock.

Description

Oxidation sweetening and the sulfone management of oil distillate are carried out using FCC
Technical field
Embodiment is related to the method and apparatus for recycling sulphur and nitrogen from hydrocarbon raw material.More specifically, embodiment It is related to for the oxidation sweetening of hydrocarbon flow and denitrogenation and is followed by subsequent processing the resulting sulphur compound through aoxidizing and nitrogen compound Method and apparatus.
Background technique
Crude oil is the main source for being used as the hydrocarbon of fuel and petrochemical industry charging in the world.Meanwhile petroleum and petroleum-type produce Product are also the main source of current air and water pollution.In order to solve of increasing concern to be caused by petroleum and petroleum-type product Problem of environmental pollution, it is many country for oil product, especially for the spy allowed in petroleum refining operation and fuel The concentration (such as the sulphur and nitrogen content allowed in Fuel Petroleum) for determining pollutant implements stringent regulation.Although natural oil or The exact composition of crude oil is widely different, but all crude oil all include the sulphur compound of some measurable contents, and most of originals Oil also includes the nitrogen compound of some measurable contents.In addition, crude oil also may include oxygen, but the oxygen content of most of crude oil is usual It is lower.In general, sulphur concentration in crude oil is below about 5 weight % (wt%), the sulphur concentration of most of crude oil be about 0.5wt% extremely In the range of about 1.5wt%.The nitrogen concentration of most of crude oil is usually less than 0.2wt%, but may be up to 1.6wt%.In beauty State is, it is specified that the maximum total sulfur content of automobile gasoline fuel is lower than the sulphur of 10/1000000ths parts by weight (ppmw).
Crude oil is refined in oil plant to feed with production and transport fuel and petrochemical industry.In general, by process and be blended come From the distillation fraction of crude oil to meet specific final use specification, thus fuel of the production for transport.Because current usual The sulphur concentration of obtainable most of crude oil is high, so distillation fraction usually requires desulfurization to generate and can meet various performance rule The product of lattice, environmental standard or both.
Organic compounds containing sulfur present in crude oil and resulting refined fuels may be the main source of environmental pollution.It is logical Often, sulphur compound is converted into oxysulfide in combustion, this can generate sulphur oxyacid (sulfur oxyacid) simultaneously in turn Weighting particles discharge.
A kind of method for reducing particulate emission includes adding various oxygenated fuel (oxygenated fuel) blendingizations Close object, containing seldom or compound (such as methanol and dimethyl ether) without C-C bond or both.However, most of The shortcomings that these compounds, is that the vapour pressure of these fuel may be very high, is practically insoluble in diesel fuel or ignition performance (as shown in its Cetane number) is poor, or has the shortcomings that these combination.
It is handled by chemical hydrotreating or hydrogenization to reduce the sulphur of diesel fuel and arene content, however, The fuel lubricity of diesel fuel may reduce, this will lead in turn petrolift, injector and other contact combustion under high pressure The excessive wear of the movable part of material.
For example, midbarrel (that is, the fraction of nominal boiling range within the scope of about 180 DEG C to 370 DEG C) may be used as fuel, or Person selectively, may be used as the mixture components of fuel used in compression ignition engine (i.e. diesel engine).Midbarrel is usual Sulphur comprising about 1wt% to 3wt%.Europe and the U.S., since nineteen ninety-three, the sulphur concentration allowed in midbarrel from The level of 3000ppmw is reduced to the level of 5ppmw to 50ppmw.
In order to defer to the regulation of increasingly strict ultra-low sulfur fuel, oil plant must make oil plant dispatch from the factory (refinery gate) fuel has lower sulfur content, to can satisfy specification after blending.
Low pressure conventional hydrodesulfurization (HDS) method can be used for removing most of sulphur from petroleum distillate, for refining oil The blending of factory's transport fuel.However, in a mild condition (that is, the pressure for being up to about 30 bars), when sulphur atom is by steric hindrance When (such as in the case where Ppolynuclear aromatic sulphur compound), these units cannot effectively from compound remove desulfuration.Work as thia Atom is especially true when being hindered by two alkyl (for example, 4,6- dimethyl Dibenzothiophenes).Due to being difficult to remove, thus in example As 50ppmw to 100ppmw etc low sulfur content when, with steric hindrance dibenzothiophenes be main component.It must use harsh Service condition (for example, high hydrogen partial pressure, high temperature or high catalyst volume) with the desulfurization from these intractable sulphur compounds. The raising of hydrogen partial pressure can only be realized by improving recyclegas purity or must design new base unit, this may be generation The very high selection of valence.Normally result in that yield reduces, catalyst life cycles are shorter and product matter using harsh service condition (for example, color) deterioration is measured, therefore should usually be avoided as far as possible.
However, for petroleum upgrading conventional method have the shortcomings that various limitations and.For example, method for hydrogenation usually require by External source supplies a large amount of hydrogen, to realize required upgrading and conversion.These methods are also possible that the too early of catalyst Or rapid deactivation, this be usually in the hydrotreating of heavy feedstocks or the case where during the hydrotreating under critical conditions, because This needs to make catalyst regeneration or adds new catalyst, this will lead to processing unit shutdown in turn.Heat treatment method often by It is trapped in a large amount of coke generated as by-product and the limited ability for removing impurity (such as sulphur and nitrogen).In addition, heat treatment side Method needs the special equipment suitable for critical conditions (for example, high temperature and high pressure), and needs to input big energy, so as to cause Complexity and cost improve.
It is needed accordingly, there exist such, that is, the method for carrying out upgrading to hydrocarbon raw material is provided, especially such method: made Desulfurization, denitrogenation or desulfurization and denitrogenation are carried out to hydro carbons with low harsh degree condition；It can also provide to available sulphur compound or nitrogen The means that compound is recycled and handled；Or it carries out both above-mentioned.
Summary of the invention
Embodiment is provided for carrying out upgrading to hydrocarbon raw material to remove existing most of sulphur and nitrogen and and then in phase Close the method and apparatus that these compounds are utilized in technique.
According at least one embodiment, a kind of method that ingredient is recycled from hydrocarbon raw material is provided, wherein this method packet It includes: hydrocarbon raw material being supplied to oxidation reactor, wherein the hydrocarbon raw material packet sulphur compound and nitrogen compound；And in oxidation reactor In, under conditions of being enough sulphur compound present in selectively oxygenated hydrocarbon feedstock and nitrogen compound, make hydrocarbon raw material and oxidation Agent contact, to generate the hydrocarbon flow through aoxidizing comprising hydrocarbon, the sulphur compound through aoxidizing and the nitrogen compound through aoxidizing.This method It further include carrying out solvent extraction by using polar solvent to the hydrocarbon in the hydrocarbon flow through aoxidizing, the sulphur compound through aoxidizing It is separated with the nitrogen compound through aoxidizing, to generate extracted hydrocarbon flow and mixture flow, which includes polarity Solvent, the sulphur compound through aoxidizing and the nitrogen compound through aoxidizing, wherein the sulphur compound and nitrification of extracted hydrocarbon flow The concentration of object is lower than the sulphur compound of hydrocarbon raw material and the concentration of nitrogen compound.This method further include: use destilling tower by mixture The polar solvent stream and the first residual oil (residue) stream that flow separation is recycled at first, wherein the first residual oil stream includes warp The sulphur compound of oxidation and nitrogen compound through aoxidizing；And the first residual oil stream is supplied to fluid catalytic cracking unit, In the fluid catalytic cracking unit can sulphur of the catalytic cracking through aoxidizing and the nitrogen through aoxidizing, to generate regenerated catalyst and gas State product and liquid product, and hydrocarbon can be recycled from the first residual oil stream.In addition, this method is at least part of including making Liquid product is recycled to oxidation reactor, selectively to aoxidize the sulphur compound in liquid product, the wherein liquid of the part State product includes at least one of light cycle and heavy recycle stock.
According at least one embodiment, this method further include: extracted hydrocarbon flow is supplied to stripper, to generate Second recycling polar solvent stream and through steam stripped hydrocarbon flow；And make the polar solvent stream and the second polarity of the first recycling Solvent stream is recycled to extraction vessel, and the extraction vessel is for separating the hydrocarbon in the hydrocarbon flow through aoxidizing, the vulcanization through aoxidizing Close object and the nitrogen compound through aoxidizing.
According at least one embodiment, this method further includes urging a part of the regenerated catalyst of a part with fluidisation Change cracked charge stream and be recycled to fluid catalytic cracking unit, wherein recycling further includes the regenerated catalyst pair using the part Fluid catalytic cracking feeding flow carries out catalytic cracking, to recycle hydrocarbon from the first residual oil stream.
According at least one embodiment, oxidant is selected from consisting of the following group: air, oxygen, peroxide, hydrogen mistake Oxide, ozone, oxynitride and their combination.
According at least one embodiment, hydrocarbon raw material is set to contact generation with oxidant in the presence of a catalyst, the catalysis Agent includes to have formula MxOyMetal oxide, wherein M is the element of group ivb selected from the periodic table of elements, VB race and group vib.
According at least one embodiment, sulphur compound include sulfide, disulphide, mercaptan, thiophene, benzothiophene, Dibenzothiophenes, the alkyl derivative of dibenzothiophenes or their combination.
According at least one embodiment, oxidation reactor is maintained at about 20 DEG C to about 350 DEG C of temperature and about 1 Ba Zhiyue Under 10 bars of pressure.
According at least one embodiment, the ratio of sulphur compound present in oxidant and hydrocarbon raw material is about 4:1 to about 10:1。
According at least one embodiment, the Hildebrand value of polar solvent is greater than about 19.
According at least one embodiment, polar solvent is selected from consisting of the following group: acetone, carbon disulfide, pyridine, two Methyl sulfoxide, normal propyl alcohol, ethyl alcohol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and their group It closes.
According at least one embodiment, polar solvent is acetonitrile.
According at least one embodiment, polar solvent is methanol.
According at least one embodiment, solvent extraction about 20 DEG C to about 60 DEG C temperature and about 1 bar to about 10 bars It is carried out under pressure.
According at least one embodiment, this method further includes by extracted hydrocarbon flow supplied to adsorption tower, wherein inhaling Attached tower is equipped with the adsorbent for being suitable for removing the compound present in extracted hydrocarbon flow through aoxidizing, and adsorption tower generates high-purity Hydrocarbon product stream and the second residual oil stream are spent, the second residual oil stream includes the compound through aoxidizing of a part.
According at least one embodiment, this method further includes that the second residual oil stream is supplied to fluid catalytic cracking list Member.
According at least one embodiment, adsorbent is selected from consisting of the following group: active carbon, silica gel, aluminium oxide, natural Clay, silica-alumina, zeolite and their combination.
According at least one embodiment, adsorbent is the carrier of polymer-coated, and wherein carrier has high surface area simultaneously And selected from the group being made of silica gel, aluminium oxide, silica-alumina, zeolite and active carbon, and polymer is selected from by following The group of composition: polysulfones, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane and their combination.
According at least one embodiment, the first residual oil stream is supplied to fluid catalytic cracking unit further include: urging In the presence of agent, contact the first residual oil stream with fluid catalytic cracking feeding flow, to carry out to fluid catalytic cracking feeding flow Catalytic cracking, to recycle hydrocarbon from the first residual oil stream.
According at least one embodiment, fluid catalytic cracking feeding flow includes vacuum gas oil (VGO), atmospheric residue (reduced crude), metal removal oil, whole crude, cracking shale oil, liquefaction coal, cracked pitches, heavy coked gas Oil, light cycle, heavy recycle stock, clarification slurry oil or their combination.
According to another embodiment, a kind of method that ingredient is recycled from hydrocarbon raw material is provided, wherein this method comprises: Hydrocarbon raw material is supplied to oxidation reactor, wherein hydrocarbon raw material includes sulphur compound and nitrogen compound；And in oxidation reactor, Under conditions of being enough sulphur compound present in selectively oxygenated hydrocarbon feedstock and nitrogen compound, connect hydrocarbon raw material with oxidant Touching, to generate the hydrocarbon flow through aoxidizing comprising hydrocarbon, the sulphur compound through aoxidizing and the nitrogen compound through aoxidizing.This method is also wrapped It includes and solvent extraction is carried out to the hydrocarbon in the hydrocarbon flow through aoxidizing, sulphur compound and warp through aoxidizing by using polar solvent The nitrogen compound of oxidation is separated, and to generate extracted hydrocarbon flow and mixture flow, wherein mixture flow includes that polarity is molten Agent, the sulphur compound through aoxidizing and the nitrogen compound through aoxidizing, and the sulphur compound of wherein extracted hydrocarbon flow and nitridation The concentration of object is closed lower than the sulphur compound of hydrocarbon raw material and the concentration of nitrogen compound.This method further include: will be mixed using destilling tower Stream is separated into the polar solvent stream and the first residual oil stream of the first recycling, wherein the first residual oil stream includes the sulphur through aoxidizing Compound and nitrogen compound through aoxidizing；First residual oil stream is supplied to fluid catalytic cracking unit, and the wherein fluidisation Catalytic cracking unit can sulphur of the catalytic cracking through aoxidizing and the nitrogen through aoxidizing, with generate regenerated catalyst and gaseous products and Liquid product, and hydrocarbon can be recycled from the first oil of dreg.In addition, this method comprises: in the presence of a catalyst, making first Residual oil stream is contacted with fluid catalytic cracking feeding flow, to carry out catalytic cracking to fluid catalytic cracking feeding flow, thus from the Hydrocarbon is recycled in one residual oil stream；And at least part of liquid product is made to be recycled to oxidation reactor, with selectively oxygen Change the sulphur compound in liquid product, wherein the liquid product of the part include in light cycle and heavy recycle stock at least One.
According at least one embodiment, this method further include: extracted hydrocarbon flow is supplied to stripper, to generate Second recycling polar solvent stream and through steam stripped hydrocarbon flow；And make the polar solvent stream and the second polarity of the first recycling Solvent stream is recycled to extraction vessel, and the extraction vessel is for separating the hydrocarbon in the hydrocarbon flow through aoxidizing, the vulcanization through aoxidizing Close object and the nitrogen compound through aoxidizing.
According at least one embodiment, this method further include make a part regenerated catalyst and fluid catalytic cracking into Stream is recycled to fluid catalytic cracking unit, wherein recycling further includes the regenerated catalyst using the part to fluid catalytic Cracked charge stream carries out catalytic cracking, to recycle hydrocarbon from the first residual oil stream.
According at least one embodiment, oxidant is selected from consisting of the following group: air, oxygen, peroxide, hydrogen mistake Oxide, ozone, nitrogen oxide compound and their combination.
According at least one embodiment, hydrocarbon raw material is set to contact generation with oxidant in the presence of a catalyst, catalyst Comprising with formula MxOyMetal oxide, wherein M is the element of group ivb selected from the periodic table of elements, VB race and group vib.
According at least one embodiment, sulphur compound includes sulfide, disulphide, mercaptan, thiophene, benzothiophene, Dibenzothiophenes, the alkyl derivative or their combination of dibenzothiophenes.
According at least one embodiment, oxidation reactor is maintained at about 20 DEG C to about 350 DEG C of temperature and about 1 Ba Zhiyue Under 10 bars of pressure.
According at least one embodiment, the ratio of sulphur compound present in oxidant and hydrocarbon raw material is about 4:1 to about 10:1。
According at least one embodiment, the Hildebrand value of polar solvent is greater than about 19.
According at least one embodiment, polar solvent is selected from consisting of the following group: acetone, carbon disulfide, pyridine, two Methyl sulfoxide, normal propyl alcohol, ethyl alcohol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and their group It closes.
According at least one embodiment, polar solvent is acetonitrile.
According at least one embodiment, polar solvent is methanol.
According at least one embodiment, solvent extraction about 20 DEG C to about 60 DEG C temperature and about 1 bar to about 10 bars It is carried out under pressure.
According at least one embodiment, this method further includes by extracted hydrocarbon flow supplied to adsorption tower, wherein inhaling Attached tower is equipped with the adsorbent for being suitable for removing the compound present in extracted hydrocarbon flow through aoxidizing, and absorption tower generates high-purity Hydrocarbon product stream and the second residual oil stream are spent, the second residual oil stream includes the compound through aoxidizing of a part.
According at least one embodiment, this method further includes that the second residual oil stream is supplied to fluid catalytic cracking list Member.
According at least one embodiment, adsorbent is selected from consisting of the following group: active carbon, silica gel, aluminium oxide, natural Clay, silica-alumina, zeolite and their combination.
According at least one embodiment, adsorbent is the carrier of polymer-coated, and wherein carrier has high surface area simultaneously And selected from the group being made of silica gel, aluminium oxide and active carbon, and polymer is selected from consisting of the following group: polysulfones, polypropylene Nitrile, polystyrene, polyester terephthalate, polyurethane, silica-alumina, zeolite and their combination.
According at least one embodiment, the first residual oil stream is deposited with fluid catalytic cracking feeding flow with following weight ratio : the weight ratio range of catalyst and the first residual oil stream and fluid catalytic cracking feeding flow is about 1 to about 15.
According at least one embodiment, fluid catalytic cracking feeding flow includes vacuum gas oil (VGO), atmospheric residue, demetalization Oil, whole crude, cracking shale oil, liquefaction coal, cracked pitches, heavy coking gas oil, light cycle, heavy recycle Oil, clarification slurry oil or their combination.
According at least one embodiment, in the presence of a catalyst, make the first residual oil stream and fluid catalytic cracking into Stream contact occurs within the temperature range of about 300 DEG C to about 650 DEG C.
According at least one embodiment, in the presence of a catalyst, make the first residual oil stream and fluid catalytic cracking into Stream contact occurred within about 0.1 second to about 10 minutes residence time.
According at least one embodiment, this method further include: by low boiling point component and catalyst granules and the first residual oil Stream and fluid catalytic cracking feed flow separation；And make at least part of regenerated catalyst particles.
According at least one embodiment, at least part of regenerated catalyst particles are made to include:
Contact the catalyst granules of the part in a fluidized bed with anhydrous oxygen-containing gas, which is generating again It is operated under conditions of raw catalyst and gaseous products and liquid product, gaseous products include carbon monoxide and titanium dioxide Carbon.
Detailed description of the invention
Therefore, the feature and advantage of disclosed method and system can be more fully understood and will become apparent The more specific description of the mode of other feature and advantage, the method and system previously summarized can be by referring to its embodiment party Case and obtain, the embodiment is shown in the attached drawing of a part to form this specification.It should be noted, however, that attached drawing only shows Different embodiments are gone out, therefore have been not construed as limiting range, because it may also comprise other effective embodiments.It is identical Number always show identical element, and primary symbols (if use) indicate in alternate embodiment or position Similar components.
Fig. 1 provides the schematic diagram that an embodiment of method for upgrading is carried out to hydrocarbon raw material.
Fig. 2 provides the schematic diagram that an embodiment of method for upgrading is carried out to hydrocarbon raw material.
Fig. 3 provides the schematic diagram that an embodiment of method for upgrading is carried out to hydrocarbon raw material.
Fig. 4 provides the schematic diagram of method described in embodiment.
Specific embodiment
Although for purposes of illustration, described further below includes many details, it is to be understood that, this field is common Technical staff will be appreciated that, many examples of following details, changes and modifications are all within the scope and spirit of this invention.Therefore, right It is described in the accompanying drawings and the different embodiments that provide is illustrated and does not lose any generality, and do not apply and wanted with right Ask relevant limitation.
Embodiment solve the problems, such as to upgrading is carried out to hydrocarbon raw material and recycles the conventional method of compound it is relevant known, The especially desulfurization, denitrogenation or desulfurization and denitrogenation and subsequent removing of hydrocarbon raw material and the available hydrocarbon of recycling.According at least one A embodiment, provide it is a kind of from sulphur compound and nitrogen compound are removed in hydrocarbon raw material and in FCC technique use through oxygen The method of the sulfur material of change and the nitrogen material through aoxidizing.
As used, term " upgrading " or " upgrading " about petroleum or hydrocarbon refer to and initial petroleum or hydrocarbon raw material Compare, have api gravity is higher, midbarrel yield is higher, sulfur content is lower, nitrogen content is lower or tenor it is lower in (that is, there is less carbon atom, such as methane, the ethane and propane) petroleum or hydrocarbon products of the relatively lightweight of at least one.
Fig. 1 provides an embodiment of hydrocarbon recycling.Hydrocarbon recovery system 100 includes oxidation reactor 104, extraction vessel 112, solvent regeneration tower 116, stripper 120 and FCC unit 130.
According at least one embodiment, one kind is provided from hydrocarbon raw material (especially comprising sulfur-containing compound and nitrogen Close object hydrocarbon raw material) in recycling ingredient method.This method includes aoxidizing hydrocarbon raw material 102 supplied to oxidation reactor 104 Hydrocarbon raw material is contacted with oxidant and catalyst in reactor 104.Oxidant can be supplied to via oxidant feed pipeline 106 Oxidation reactor 104, and new catalyst can be supplied to reactor via catalyst feed line 108.
According at least one embodiment, hydrocarbon raw material 102 can be any hydrocarbon based on petroleum, and may include various Impurity such as elemental sulfur, comprising sulphur or nitrogen compound or includes sulphur and nitrogen compound.In certain embodiments, hydrocarbon raw material 102 can be the diesel oil that boiling point is about 150 DEG C to about 400 DEG C.Selectively, the boiling point of hydrocarbon raw material 102 can be up to about 450 DEG C, or it is up to about 500 DEG C.Selectively, the boiling point of hydrocarbon raw material 102 can be about 100 DEG C to about 500 DEG C.Optionally, hydrocarbon is former The boiling point of material 102 can be up to about 600 DEG C, perhaps be up to about 700 DEG C or in certain embodiments, greater than about 700 DEG C. According at least one embodiment, residual oil will be known as with charging existing for solid state after distillation.In certain embodiments, hydrocarbon Raw material 102 may include heavy hydrocarbon.As used, " heavy hydrocarbon " refers to that boiling point is greater than about 360 DEG C of hydrocarbon, and may include Aromatic hydrocarbons and alkane and alkene.In general, in certain embodiments, hydrocarbon raw material 102 can be selected from full range (whole range) Crude oil, topped crude, the product stream from oil plant, the product stream from oil-extraction plant steam process, liquefaction coal, from The liquid product that recycles in oil or Tar sands, pitch, oil shale, asphalitine, boiling range is within the scope of about 180 DEG C to about 370 DEG C Hydrocarbon-fractions such as the vacuum gas oil (VGO) of diesel oil and boiling range within the scope of about 370 DEG C to about 520 DEG C etc. and their mixture.
Sulphur compound present in hydrocarbon raw material 102 may include sulfide, disulphide and mercaptan and aromatic molecule (methyldibenzothiophene of such as thiophene, benzothiophene, dibenzothiophenes and such as 4,6- dimethyl-dibenzothiophenes etc). Compared with the aromatic compound being generally found in compared with low-boiling fraction, the aromatic compounds in higher fraction is usually richer It is rich.
Nitrogenous compound present in hydrocarbon raw material 102 may include the compound having following structure:
The oxidation that note that sulphur is limited orientation reaction, and the oxidation of nitrogen can occur during the reaction.It is considered that having Basic nitrogen and neutral nitrogen two types.
According at least one embodiment, oxidation reactor 104 can be run in a mild condition.More specifically, exist In certain embodiments, oxidation reactor 104 may remain in about 30 DEG C to about 350 DEG C or about 45 DEG C to about 60 DEG C of temperature Under degree.The operating pressure of oxidation reactor 104 can be about 1 bar to about 30 bars or about 1 bar to about 15 bars or about 1 bar extremely About 10 bars or about 2 bars to about 3 bars.Residence time of the hydrocarbon raw material in oxidation reactor 104 can be about 1 minute to about 120 Minute or about 15 minutes to about 90 minutes or about 5 minutes to about 90 minutes or about 5 minutes to about 30 minutes or About 30 minutes to about 60 minutes, and the preferably sufficiently long time is so that any sulphur compound or nitrification present in hydrocarbon raw material Object is oxidized.According at least one embodiment, residence time of the hydrocarbon raw material in oxidation reactor 104 is about 15 minutes to about 90 minutes.
According at least one embodiment, oxidation reactor 104 can be following any reactor, it is appropriately configured with Ensure to make in the presence of a catalyst to come into full contact between hydrocarbon raw material 102 and oxidant, for aoxidizing sulfur-containing compound and containing Nitrogen compound.In oxidation reactor 104, sulphur compound present in hydrocarbon raw material 102 and nitrogen compound are oxidized to sulfone, sulfoxide With the nitrogen compound through aoxidizing, these compounds can be then removed by extracting or adsorbing.It can be used different types of Reactor.For example, reactor can for batch reactor, fixed bed reactors, fluidized bed reactor, hoisting type reactor, Fluidized-bed reactor, paste state bed reactor or their combination.The other kinds of suitable reactor that can be used is for this It is it will be apparent that and being considered as in the range of different embodiments for the technical staff of field.Suitably through aoxidizing The example of nitrogen compound may include pyridine compounds and their and azoles.Thinking nitrogen-atoms not is directly to be oxidized , but what is be actually oxidized is one or more carbon atoms beside nitrogen-atoms.Some realities of nitrogen compound through aoxidizing Example may include following compound:
Or their combination.
According at least one embodiment, oxidant is supplied to oxidation reactor 104 via oxidant feed stream 106.It closes Suitable oxidant may include air, oxygen, hydrogen peroxide, organic peroxide, hydroperoxides, organic peracid, peroxy acid, Nitrogen oxide, ozone etc. and their combination.Peroxide can be selected from hydrogen peroxide etc..Hydroperoxides can be selected from Tert-butyl hydroperoxide etc..Organic peracid can be selected from peracetic acid etc..
According at least one embodiment, the molar ratio of sulphur present in oxidant and hydrocarbon raw material can be about 1:1 to about 50:1, preferably from about 2:1 are to about 20:1, more preferably from about 4:1 to about 10:1.According at least one embodiment, oxidant and sulphur Molar feed ratio can range from about 1:1 to about 30:1.
According at least one embodiment, the molar feed ratio of oxidant and nitrogen compound can be about 4:1 to about 10:1. According at least one embodiment, charging may include nitrogen compounds more more than sulphur, such as South America crude oil, African crude oil, Russia Ross crude oil, Chinese crude oil or intermediate oil plant stream, such as coking oil, hot tearing carburetion, visbreaking oil, gas oil, FCC circulation Oil etc..
According at least one embodiment, catalyst can be supplied to oxidation reactor via catalyst charge stream 108 104.Catalyst can be homogeneous catalyst.It is M that catalyst, which may include at least one chemical formula,xOyMetal oxide, wherein M is the metal of group ivb selected from the periodic table of elements, VB race or group vib.The metal may include titanium, vanadium, chromium, molybdenum and tungsten.Molybdenum It is two kinds of particularly effective catalyst that can be used in different embodiments with tungsten.In certain embodiments, dead catalyst can To be discharged from system after oxidation container with aqueous phase (for example, when using oxidizing aqueous dose).
According at least one embodiment, the ratio of catalyst and oil is about 0.1wt% to about 10wt%, preferably from about 0.5wt% to about 5wt%.In certain embodiments, which is about 0.5wt% to about 2.5wt%.Selectively, the ratio Rate is about 2.5wt% to about 5wt%.Other suitable catalyst and oily weight rate are to those skilled in the art It will be apparent that and being considered as in the range of different embodiments.
Various sulfur-containing compounds and nitrogen in hydrocarbon raw material 102 can be improved in catalyst present in oxidation reactor 104 The oxidation rate of object is closed, the amount of oxidant needed for reducing oxidation reaction, or both.In certain embodiments, it is catalyzed Agent can have selectivity to the oxidation of sulfur material.In other embodiments, catalyst can have the oxidation of nitrogen material Selectivity.
Oxidation reactor 104 generates the hydrocarbon flow 110 through aoxidizing, and the hydrocarbon flow 110 through aoxidizing can wrap hydrocarbonaceous and warp The sulphur-containing substance of oxidation and nitrogen substance through aoxidizing.Hydrocarbon flow 110 through aoxidizing is supplied to extraction vessel 112, is being extracted In container 112, the hydrocarbon flow through aoxidizing and the sulphur-containing substance through aoxidizing and the nitrogen substance through aoxidizing and Extraction solvent stream 137 contacts.Extraction solvent 137 can be polar solvent, and in certain embodiments, the Anthony Heald cloth of Extraction solvent 137 Blue moral solubility values can be greater than about 19.In certain embodiments, when the specific polar solvent of selection is for extracting through aoxidizing Sulphur-containing substance and when nitrogen substance through aoxidizing, as non-limiting examples, can be (to a certain extent) close based on solvent Degree, boiling point, freezing point, viscosity and surface tension are selected.Polar solvent suitable for extraction step may include that acetone is (uncommon Your De Bulande value be 19.7), carbon disulfide (20.5), pyridine (21.7), dimethyl sulfoxide (DMSO) (26.4), normal propyl alcohol (24.9), ethyl alcohol (26.2), n-butanol (28.7), propylene glycol (30.7), ethylene glycol (34.9), dimethylformamide (DMF) (24.7), components or the physics such as acetonitrile (30), methanol (29.7) and the similar component of chemical property.In certain embodiments, Acetonitrile and methanol due to its low cost, volatility and polarity but it is preferred.Methanol is for the specially suitable of embodiment Solvent.In certain embodiments, the solvent comprising sulphur, nitrogen or phosphorus preferably has relatively high volatility, to ensure from hydrocarbon Sufficient solvent stripping is carried out in raw material.
According at least one embodiment, Extraction solvent is non-acid.Due to sour corrosivity and require all set It is standby specially designed to be used for corrosive environment, thus usually should be avoided using acid.In addition, sour (such as acetic acid) can be due to lotion It is formed and causes separation difficult.
According at least one embodiment, extraction vessel 112 can be at about 20 DEG C to about 60 DEG C, preferably from about 25 DEG C to about 45 DEG C, run at a temperature of even more preferably about 25 DEG C to about 35 DEG C.Extraction vessel 112 can about 1 bar to about 10 bars, preferably from about It is run under 1 bar to about 5 bars, more preferably from about 1 bar to about 2 bars of pressure.In certain embodiments, extraction vessel 112 is at about 2 bars It is run under to about 6 bars of pressure.
According at least one embodiment, the ratio of Extraction solvent and hydrocarbon raw material can be about 1:3 to about 3:1, preferably from about 1:2 is to about 2:1, more preferably from about 1:1.Time of contact between Extraction solvent and hydrocarbon flow 110 through aoxidizing can be about 1 second extremely About 60 minutes, preferably from about 1 second to about 10 minutes.In certain preferred aspects, Extraction solvent and the hydrocarbon flow through aoxidizing Time of contact between 110 is less than about 15 minutes.In certain embodiments, extraction vessel 112 may include various for prolonging The device of time of contact between long Extraction solvent and the sulfur-bearing hydrocarbon through aoxidizing and the nitrogenous hydrocarbon flow 110 through aoxidizing is used for Improve the device of the mixability of two kinds of solvents.It may include mechanical agitator or mixer, pallet etc. for mixed device Device.
According at least one embodiment, extraction vessel 112 generates mixture flow 114, which may include Extraction solvent, substance (for example, being initially present in the sulfur material and nitrogen material through aoxidizing in hydrocarbon raw material 102) and trace through aoxidizing The hydrocarbon raw material 102 of amount and extracted hydrocarbon flow 118, the extracted hydrocarbon flow 118 may include and 102 phase of hydrocarbon raw material The hydrocarbon raw material lower than sulfur content reduction and nitrogen content.
By mixture flow 114 be supplied to solvent regeneration tower 116, in solvent regeneration tower 116, can using Extraction solvent as First recovered solvent stream 117 is recycled and is separated with the first residual oil stream 123, and the first residual oil stream 123 includes through aoxidizing Sulphur compound and nitrogen compound through aoxidizing.Optionally, mixture flow 114 can be separated into recycling in solvent regeneration tower 116 Hydrocarbon flow 124, the hydrocarbon flow 124 of recycling may include hydrocarbon present in the mixture flow 114 from hydrocarbon raw material 102.Solvent Regenerator 116 can be to be configured to for mixture flow 114 to be separated into the first recovered solvent stream 117, the first residual oil stream 123 With the destilling tower of the hydrocarbon flow 124 of recycling.
Extracted hydrocarbon flow 118 can be supplied to stripper 120, which can be for designed for by hydrocarbon The containers such as the destilling tower that product stream is separated with remaining Extraction solvent.In certain embodiments, one of mixture flow 114 Stripper 120 can be supplied to via pipeline 122 by dividing, and optionally be merged with extracted hydrocarbon flow 118.In certain realities It applies in scheme, the hydrocarbon flow 124 for the recycling that can be provided to stripper 120 can be generated in solvent regeneration tower 116, in stripper In 120, the hydrocarbon flow 124 of recycling can be contacted optionally with a part of extracted hydrocarbon flow 118 or mixture flow 114, Mixture flow 114 can be supplied to stripper 120 via pipeline 122.
Stripper 120 is supplied to one of the various streams and is separated into stripped oil stream 126 and the second recovered solvent material Stream 128, compared with hydrocarbon raw material 102, the sulphur and nitrogen content of stripped oil stream 126 are reduced.
In certain embodiments, the first recovered solvent stream 117 can be closed with the second recovered solvent stream 128 And and it is recycled to extraction vessel 112.Optionally, supplementing solvent stream 132 (it may include new solvent) can be with One recovered solvent stream 117, the second recovered solvent stream 128 or the two merge, and are supplied to extraction vessel 112。
First residual oil stream 123 can be supplied to FCC unit 130, the first residual oil stream 123 includes the chemical combination through aoxidizing Object (such as sulphur compound and nitrogen compound through aoxidizing) and can also include low concentration hydrocarbonaceous material, in FCC unit 130 Recovering liquid product (including hydrocarbon) 136.According at least one embodiment, sulphur compound (such as sulfone) through aoxidizing and through aoxidizing Nitrogen compound carry under one's arms heavy hydrocarbon (as boiling spread be about 343 DEG C be about 360 DEG C to about 550 DEG C to about 524 DEG C or range Hydrocarbon) in.
Make in the presence of a catalyst according to sending the first residual oil stream 123 to the different embodiments of FCC unit 130 First residual oil stream 123 is contacted with FCC feeding flow 134, with catalytic cracking FCC feeding flow 134, thus from the first residual oil stream Recovering liquid product 136 in 123.According at least one embodiment, catalyst may include the solid zeolite active catalytic of heat Agent particle.According at least one embodiment, the weight ratio range of catalyst and FCC feeding flow 134 is about 1 to about 15, pressure Range is about 1 bar (gauge pressure) to about 200 bars, to form suspension.The ratio of other suitable catalyst and FCC feeding flow 134 With service condition will be obvious to those skilled in the art that and being considered as range in different embodiments It is interior.
According at least one embodiment, then about 300 DEG C to less than about 650 DEG C at a temperature of make suspension by mentioning Device reaction zone or drop device (not shown) are risen with catalytic cracking FCC feeding flow 134, while avoiding the heat of the feeding flow 134 Convert and provide about 0.1 second to about 10 minutes hydrocarbon residence time.
According at least one embodiment, it is then separated and recovered from low boiling point component and solid catalyst particle.It is fluidizing Regenerate at least part of solid catalyst particle isolated using anhydrous oxygen-containing gas in bed, which is generating again It is operated under conditions of raw catalyst 140 and gaseous products 138 and liquid product 136, gaseous products 138 are substantially by one Carbonoxide and carbon dioxide composition.At least part of regenerated catalyst returns and merges (not shown) with FCC feeding flow 134.
According at least one embodiment, the type of ingredient contained in FCC feeding flow 134 can be different.As Non-limiting example, FCC feeding flow 134 may include vacuum gas oil (VGO), atmospheric residue, metal removal oil, whole crude, cracking Shale oil, liquefaction coal, cracked pitches, heavy coking gas oil and FCC heavy product, such as LCO, HCO and CSO.Table 1 is shown The typical yields of FCC unit.As another example, the FCC feeding flow 134 to FCC unit 130 is sent to can have shown in table 2 Property.It can be used for being sent to other suitable compounds of the FCC feeding flow 134 of FCC unit 130 for art technology It is it will be apparent that and being considered as in the range of different embodiments for personnel.
Table 1
Yield
Product Wt%
Fuel gas 4.5
Liquefied petroleum gas (LPG) 12.2
Petroleum benzin 36.4
Heavy gasoline 11.5
Light cycle (LCO) 9.8
It clarifies slurry oil (CSO) 21.3
Coke 4.3
It is total 100.0
Table 2
Different types of catalyst can be used in FCC unit 130.According at least one embodiment, FCC catalyst Grain includes with the zeolite selected from group ivb, VI race, VII race, group VIIIB, IB race, the metal of Group IIB or their compound The catalyst granules of matrix and nominal diameter less than 200 microns.Other suitable types that can be used in FCC unit 130 Catalyst is will be obvious to those skilled in the art that and be considered as in the range of different embodiments.
According at least one embodiment, the operating parameter of FCC unit 130 can be according to sending to the FCC of FCC unit 130 The type of feeding flow 134 and change.FFC unit 130 is run within the temperature range of about 400 DEG C to about 850 DEG C.According to another Embodiment, FCC unit 130 can the operations in about 1 bar (gauge pressure) to about 200 bars (gauge pressure) of pressure limit.According to another A embodiment, FCC unit 130 can be run in about 0.1 second to about 3600 seconds residence time ranges.FCC unit 130 Other suitable operating parameters are will be obvious to those skilled in the art that and be considered as in different embodiment party In the range of case.The property of the ingredient recycled by FCC unit 130 can forming and change according to hydrocarbon FCC feeding flow 134.
Fig. 2 provides the embodiment that hydrocarbon is recycled from feeding flow.Hydrocarbon recovery system 200 includes oxidation reactor 104, extraction vessel 112, solvent regeneration tower 116, stripper 120 and FCC unit 130.
It is discussed as previously discussed with respect to embodiment shown in fig. 1, it can be mono- supplied to FCC by the first residual oil stream 123 Member 130, the first residual oil stream 123 include the compound (such as sulphur compound and nitrogen compound through aoxidizing) through aoxidizing and may be used also With the hydrocarbonaceous material comprising low concentration, the recovering liquid product (including hydrocarbon) 136 in FCC unit 130.According at least one implementation Scheme, the sulphur compound (such as sulfone) through aoxidizing and the nitrogen compound through aoxidizing carry under one's arms that (such as boiling spread is about 343 DEG C in heavy hydrocarbon The hydrocarbon for being about 360 DEG C to about 550 DEG C to about 524 DEG C or range) in.
As shown in Fig. 2, sending according to by the first residual oil stream 123 to the different embodiments of FCC unit 130, in catalyst In the presence of, contact the first residual oil stream 123 with FCC feeding flow 134, with catalytic cracking FCC feeding flow 134, thus from Recovering liquid product 136 in one residual oil stream 123.According at least one embodiment, catalyst may include the solid boiling of heat Stone active catalyst particles.According at least one embodiment, the weight ratio range of catalyst and FCC feeding flow 134 be about 1 to About 15, pressure limit is about 1 bar to about 200 bars, to form suspension.The ratio of other suitable catalyst and FCC feeding flow 134 Example and service condition are will be obvious to those skilled in the art that and be considered as model in different embodiments In enclosing.
According at least one embodiment, then make suspension by mentioning in about 300 DEG C to less than about 650 DEG C of temperature Device reaction zone or drop device (not shown) are risen with catalytic cracking FCC feeding flow 134, while avoiding the heat of the feeding flow 134 Convert and provide about 0.1 second to about 10 minutes hydrocarbon residence time.
According at least one embodiment, it is then separated and recovered from low boiling point component and solid catalyst particle.It is fluidizing Regenerate at least part of solid catalyst particle isolated using anhydrous oxygen-containing gas in bed, which is generating again It is operated under conditions of raw catalyst 140 and gaseous products 138 and liquid product 136, gaseous products 138 are substantially by one Carbonoxide and carbon dioxide composition.At least part of regenerated catalyst returns and merges (not shown) with FCC feeding flow 134.
As further shown in Figure 2, in certain embodiments, at least part of liquid product 136 is via pipeline 202 It is recirculated back to oxidation reactor 104, wherein liquid product 136 includes at least one of light cycle and heavy recycle stock. Liquid product 136 rich in sulphur and can occur in oxidation reactor 104 oxidation sweetening during desulfurization.
Different types of catalyst can be used in FCC unit 130.According at least one embodiment, FCC catalyst Grain includes with the zeolite selected from group ivb, VI race, VII race, group VIIIB, IB race, the metal of Group IIB or their compound The catalyst granules of matrix and nominal diameter less than 200 microns.Other suitable types that can be used in FCC unit 130 Catalyst is will be obvious to those skilled in the art that and be considered as in the range of different embodiments.
Fig. 3 provides the embodiment that hydrocarbon is recycled from feeding flow.Hydrocarbon recovery system 300 includes oxidation reactor 104, extraction vessel 112, solvent regeneration tower 116, stripper 120, FCC unit 130 and adsorption tower 302.
As shown in figure 3, in certain embodiments, stripped oil stream 126 can be supplied to adsorption tower 302, adsorbed In tower 302, stripped oil stream 126 can be contacted with one or more adsorbents, adsorbent be designed as removing it is one or more not With impurity, such as remain in after oxidation step and solvent extraction step sulfur-containing compound in hydrocarbon product stream, through oxygen Sulphur compound, nitrogenous compound, the nitrogen compound and metal through aoxidizing of change.
According to different embodiments, one or more adsorbents may include active carbon；Silica gel；Aluminium oxide；Natural clay； Silica-alumina；Zeolite；With to through aoxidizing sulphur compound and nitrogen compound have affinity it is new, used, (rejuvenated) catalyst and other inorganic adsorbents regenerated or restore.In certain embodiments, adsorbent can To include the polar polymer for being applied to or having coated various high surface area support materials (such as silica gel, aluminium oxide and active carbon). The example of polar polymer for coating various carrier materials may include polysulfones, polyacrylonitrile, polystyrene, gather to benzene two Formic acid esters, polyurethane, the other similar polymer material and their group that compatibility is shown to the sulfur material through aoxidizing It closes.
According at least one embodiment, adsorption tower 302 can be at about 20 DEG C to about 60 DEG C, preferably from about 25 DEG C to about 40 DEG C, run at a temperature of even more preferably about 25 DEG C to about 35 DEG C.In certain embodiments, adsorption tower can be at about 10 DEG C extremely It is run at a temperature of about 40 DEG C.In certain embodiments, adsorption tower can temperature at greater than about 20 DEG C or below about 60 DEG C The lower operation of degree.Adsorption tower 302 can be up to about 15 bars, preferably of up to about 10 bars, even more preferably about 1 bar to about 2 bars of pressure It is run under power.In certain embodiments, adsorption tower 302 can be run under about 2 bars to about 5 bars of pressure.According at least one A embodiment, adsorption tower can be run at about 25 DEG C to about 35 DEG C of temperature and about 1 bar to about 2 bars of pressure.Stripped oil The weight ratio of stream and adsorbent is about 1:1 to about 20:1；It or is about 10:1.
Charging is separated into low sulfur content very low (for example, the sulphur for being less than 15ppmw) and the very low (example of nitrogen content by adsorption tower 302 Such as, less than the nitrogen of 10ppmw) extracted hydrocarbon product stream 304 and the second residual oil stream 306.Second residual oil stream 306 packet Containing the sulfur-containing compound through aoxidizing and the nitrogenous compound through aoxidizing, and can optionally merge with the first residual oil stream 123, And it is supplied to FCC unit 130, and handled as previously described.Can by make spent sorbent and polar solvent (such as methanol or Acetonitrile) contact, so that the compound through aoxidizing of absorption is desorbed from adsorbent, to make adsorbent reactivation.In certain implementations In scheme, heat, stripping gas or the two can be used also to promote to remove the compound adsorbed.For removing absorption Other suitable methods of compound are will be obvious to those skilled in the art that and be considered as in different realities In the range of applying scheme.
Embodiment
Fig. 4 shows the process flow chart of oxidation sweetening (oxidation step and extraction step) and FCC unit.Container 10 is oxygen Change container, container 16 is extraction vessel, and container 20 is solvent recovery container, and container 25 is FCC container.
To include 500ppmw elemental sulfur, 0.28wt% organic sulfur, density be 0.85 kg/liter (Kg/l) hydrotreating Straight-run diesel oil carry out oxidation sweetening.Reaction condition is as follows:
Hydrogen peroxide: sulphur molar ratio: 4:1
Catalyst: molybdenum base Mo (VI)
Reaction time: 30 minutes
Temperature: 80 DEG C
Pressure: 1,000 grams/cm of (Kg/cm2)
Table 3- oxidation step material balance
Table 4- extraction step material balance
According at least one embodiment, FCC unit is run at 518 DEG C, and the ratio of catalyst and oil is 5, the original of acquisition Material conversion ratio is 67wt%.Other than the sulfone generated in oxidation step, depressurized using the straight run from Arabian crude Gas oil is as mixture components.Micro- carbon residual oil of the charging sulphur comprising 2.65wt% and 0.13wt%.The mid-boiling point of charging is 408 DEG C, and 95wt% boiling point is 455 DEG C.
The FCC conversion ratio of charging is calculated using following equation (1):
Conversion ratio=dry gas+LPG+ gasoline+coke (1)
Catalyst used is equilibrium catalyst, and is directly used without any processing.The surface area of the catalyst is 131 meters squared per grams (m2/g), and pore volume is 0.1878 cubic centimetre/gram (cm3/g).Nickel content is 96ppmw and vanadium Content is 407ppmw.The following product of FCC Process Production simultaneously makes deposit coke on catalyst.
The coke generated in FFC technique is the 2.5wt% of processed charging.Product yield is shown in table 5.
Table 5-FCC step material balance
According to an example, LCO is recycled to oxidation step, because LCO is identical as diesel oil used in embodiment Boiling range in boiling.It note that for purposes of illustration, FCC unit be designed as processing 10, the vacuum gas oil (VGO) of 000Kg/h. FCC unit can be designed to random capacity, and oxidation/extraction step can be designed change with handle largely into Material, it would have been obvious for a person skilled in the art and is considered as in the range of different embodiments for this.Object Material balance will be proportional to processed inlet amount.The processing step of oxidation, extraction and FCC is shown in table 6 to table 8.
Table 6- oxidation step material balance
Stream # 11 12 13 14
Ingredient stream Diesel oil H2O2 Catalyst Catalyst waste material
Kg/h Kg/h Kg/h Kg/h
Water 0 983 0 8,837
Methanol 0 0 0 0
Diesel oil 173,622 0 0 0
Organic sulfur 788 0 0 2
Acetic acid 0 0 10,747 10,747
H2O2 295 0 0
Na2WO4(kg) 0 0 4,841 4,793
Total Kgh 174,410 1,278 15,588 24,379
Table 7-extraction step material balance
8-FCC step material balance of table
It is believed that method described herein and system will be by making oxidation sweetening and denitrification process and fluid catalytic cracking unit Connection, to improve the amount of the liquid hydrocarbon from aromatic series sulphur, nitrogen compound and aromatic stream.Additionally it is believed that having without any The method of effect can be used for handling oxidation reaction by-products (that is, sulphur compound and nitrogen compound through aoxidizing).Embodiment provides Sulphur compound and nitrogen compound method without handle compound of the processing through aoxidizing.
Although different embodiments are described in detail, but it is to be understood that do not departing from the principle of the present invention and model In the case where enclosing, various changes, replacement and change can be carried out.Therefore, the scope of the present invention should by following following claims and Its legal equivalents appropriate is determined.
Unless the context clearly determines otherwise, otherwise singular " one ", "one" and "the" include plural referents.
It is optional or optionally mean that the event then described or situation may occur or may not occur.The description packet Include event or situation that the situation and event or situation that happen do not occur.
Range can be expressed as from about particular value to about another particular value.When stating such range, answer Work as understanding, another embodiment is from a particular value to all combinations in another particular value and the range.

Claims (42)

1. a kind of method that ingredient is recycled from hydrocarbon raw material, the method is characterized in that following steps:
The hydrocarbon raw material is supplied to oxidation reactor, the hydrocarbon raw material includes sulphur compound and nitrogen compound；
In the oxidation reactor, it is being enough selectively to aoxidize sulphur compound present in the hydrocarbon raw material and nitrogen compound Under conditions of, it contacts the hydrocarbon raw material with oxidant, includes hydrocarbon, the sulphur compound through aoxidizing and the nitridation through aoxidizing to generate Close the hydrocarbon flow through aoxidizing of object；
Solvent extraction is carried out to the hydrocarbon, described through aoxidizing in the hydrocarbon flow through aoxidizing by using polar solvent Sulphur compound and the nitrogen compound through aoxidizing separated, to generate extracted hydrocarbon flow and mixture flow, this is mixed Closing stream includes the polar solvent, the sulphur compound and the nitrogen compound through aoxidizing through aoxidizing, wherein the warp The concentration of the sulphur compound of the hydrocarbon flow of extraction and nitrogen compound is dense lower than the sulphur compound of the hydrocarbon raw material and nitrogen compound Degree；
The mixture flow is separated into the polar solvent stream and the first residual oil stream of the first recycling using destilling tower, this first Residual oil stream includes the sulphur compound and the nitrogen compound through aoxidizing through aoxidizing；
The first residual oil stream is supplied to fluid catalytic cracking unit, which being capable of catalytic cracking warp The sulphur of oxidation and nitrogen through aoxidizing, to generate regenerated catalyst and gaseous products and liquid product, and can be from described Hydrocarbon is recycled in one residual oil stream；And
So that at least part of liquid product is recycled to the oxidation reactor, is produced with selectively aoxidizing the liquid Sulphur compound in object, the liquid product of the part include at least one of light cycle and heavy recycle stock.
2. according to the method described in claim 1, it is further characterized in that following steps:
The extracted hydrocarbon flow is supplied to stripper, to generate the polar solvent stream of the second recycling and through steam stripped hydrocarbon Stream；And
The polar solvent stream and the second polar solvent stream for making first recycling are recycled to extraction vessel, the extraction vessel For separating the hydrocarbon in the hydrocarbon flow through aoxidizing, the sulphur compound and the nitrification through aoxidizing through aoxidizing Object.
3. method according to any one of claim 1 to 2, it is further characterized in that following steps:
The regenerated catalyst and fluid catalytic cracking feeding flow for making a part are recycled to the fluid catalytic cracking unit, Wherein the recycling is further characterized in that using the regenerated catalyst of the part to the fluid catalytic cracking feeding flow Catalytic cracking is carried out, the step of to recycle the hydrocarbon from the first residual oil stream.
4. according to the method in any one of claims 1 to 3, wherein the oxidant is selected from consisting of the following group: empty Gas, oxygen, peroxide, hydroperoxides, ozone, nitrogen oxide compound and their combination.
5. method according to claim 1 to 4, wherein described make the hydrocarbon raw material contact generation with oxidant In the presence of a catalyst, the catalyst includes to have formula MxOyMetal oxide, wherein M be selected from the periodic table of elements Group ivb, VB race and group vib element.
6. the method according to any one of claims 1 to 5, wherein the sulphur compound include sulfide, disulphide, Mercaptan, thiophene, benzothiophene, dibenzothiophenes, the alkyl derivative of dibenzothiophenes or their combination.
7. method according to any one of claim 1 to 6, wherein the oxidation reactor is maintained at about 20 DEG C of peace treaties Under the pressure between temperature and about 1 bar and about 10 bars between 350 DEG C.
8. method according to any one of claim 1 to 7, wherein sulphur present in the oxidant and the hydrocarbon raw material The ratio of compound is between about 4:1 and about 10:1.
9. method according to any one of claim 1 to 8, wherein the Hildebrand value of the polar solvent is greater than About 19.
10. method according to any one of claim 1 to 9, wherein the polar solvent is selected from consisting of the following group: Acetone, carbon disulfide, pyridine, dimethyl sulfoxide, normal propyl alcohol, ethyl alcohol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, Acetonitrile, methanol and their combination.
11. method according to any one of claim 1 to 10, wherein the polar solvent is acetonitrile.
12. method according to any one of claim 1 to 11, wherein the polar solvent is methanol.
13. method according to any one of claim 1 to 12, wherein the solvent extraction about 20 DEG C and about 60 DEG C it Between temperature and about 1 bar and about 10 bars between pressure under carry out.
14. method according to any one of claim 1 to 13, it is further characterized in that following steps:
The extracted hydrocarbon flow is supplied to adsorption tower, the adsorption tower, which is equipped with, to be suitable for removing the extracted hydrocarbon material The adsorbent of compound present in stream through aoxidizing, the adsorption tower generate high-purity hydrocarbon product stream and the second oil of dreg Stream, the second residual oil stream include the compound through aoxidizing of a part.
15. according to the method for claim 14, it is further characterized in that following steps:
The second residual oil stream is supplied to the fluid catalytic cracking unit.
16. according to the method for claim 14, wherein the adsorbent be selected from consisting of the following group: active carbon, silica gel, Aluminium oxide, natural clay, silica-alumina, zeolite and their combination.
17. according to the method for claim 14, wherein the adsorbent is the carrier of polymer-coated, wherein the carrier With high surface area and it is selected from the group being made of silica gel, aluminium oxide, silica-alumina, zeolite and active carbon, and institute State polymer be selected from consisting of the following group: polysulfones, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane and it Combination.
18. according to claim 1 to method described in any one of 17, wherein described be supplied to stream for the first residual oil stream Fluidized catalytic cracking unit is further characterized in that: in the presence of a catalyst, making the first residual oil stream and fluid catalytic cracking Feeding flow contact, to carry out catalytic cracking to the fluid catalytic cracking feeding flow, to be returned from the first residual oil stream Receive hydrocarbon.
19. according to the method for claim 18, wherein the fluid catalytic cracking feeding flow includes vacuum gas oil (VGO), normal pressure Heavy oil, metal removal oil, whole crude, cracking shale oil, liquefaction coal, cracked pitches, heavy coking gas oil, light recycle Oil, heavy recycle stock, clarification slurry oil or their combination.
20. a kind of method that ingredient is recycled from hydrocarbon raw material, the method is characterized in that following steps:
The hydrocarbon raw material is supplied to oxidation reactor, the hydrocarbon raw material includes sulphur compound and nitrogen compound；
In the oxidation reactor, it is being enough selectively to aoxidize sulphur compound present in the hydrocarbon raw material and nitrogen compound Under conditions of, it contacts the hydrocarbon raw material with oxidant, includes hydrocarbon, the sulphur compound through aoxidizing and the nitridation through aoxidizing to generate Close the hydrocarbon flow through aoxidizing of object；
Solvent extraction is carried out to the hydrocarbon, described through aoxidizing in the hydrocarbon flow through aoxidizing by using polar solvent Sulphur compound and the nitrogen compound through aoxidizing separated, to generate extracted hydrocarbon flow and mixture flow, this is mixed Closing stream includes the polar solvent, the sulphur compound and the nitrogen compound through aoxidizing through aoxidizing, wherein the warp The concentration of the sulphur compound of the hydrocarbon flow of extraction and nitrogen compound is dense lower than the sulphur compound of the hydrocarbon raw material and nitrogen compound Degree；
The mixture flow is separated into the polar solvent stream and the first residual oil stream of the first recycling using destilling tower, this first Residual oil stream includes the sulphur compound and the nitrogen compound through aoxidizing through aoxidizing；
The first residual oil stream is supplied to fluid catalytic cracking unit, which being capable of catalytic cracking warp The sulphur of oxidation and nitrogen through aoxidizing, to generate regenerated catalyst and gaseous products and liquid product, and can be from described Hydrocarbon is recycled in one residual oil stream；
In the presence of a catalyst, contact the first residual oil stream with fluid catalytic cracking feeding flow, to the fluidisation Catalytic cracking feeds stream carries out catalytic cracking, to recycle hydrocarbon from the first residual oil stream；And
So that at least part of liquid product is recycled to the oxidation reactor, is produced with selectively aoxidizing the liquid Sulphur compound in object, the liquid product of the part include at least one of light cycle and heavy recycle stock.
21. according to the method for claim 20, it is further characterized in that following steps:
The extracted hydrocarbon flow is supplied to stripper, to generate the polar solvent stream of the second recycling and through steam stripped hydrocarbon Stream；And
The polar solvent stream and the second polar solvent stream for making first recycling are recycled to extraction vessel, the extraction vessel For separating the hydrocarbon in the hydrocarbon flow through aoxidizing, the sulphur compound and the nitrification through aoxidizing through aoxidizing Object.
22. the method according to any one of claim 20 to 21, it is further characterized in that following steps:
The regenerated catalyst and the fluid catalytic cracking feeding flow for making a part are recycled to the fluid catalytic cracking Unit, wherein the recycling be further characterized in that the regenerated catalyst using the part to the fluid catalytic cracking into Stream carries out catalytic cracking, to recycle the hydrocarbon from the first residual oil stream.
23. the method according to any one of claim 20 to 22, wherein the oxidant is selected from consisting of the following group: Air, oxygen, peroxide, hydroperoxides, ozone, nitrogen oxide compound and their combination.
24. the method according to any one of claim 20 to 23, wherein described contact the hydrocarbon raw material with oxidant Occur in the presence of a catalyst, the catalyst includes to have formula MxOyMetal oxide, wherein M be selected from period of element The group ivb of table, VB race and group vib element.
25. the method according to any one of claim 20 to 24, wherein the sulphur compound includes sulfide, curing Object, mercaptan, thiophene, benzothiophene, dibenzothiophenes, the alkyl derivative of dibenzothiophenes or their combination.
26. the method according to any one of claim 20 to 25, wherein the oxidation reactor be maintained at about 20 DEG C and Under the pressure between temperature and about 1 bar and about 10 bars between about 350 DEG C.
27. the method according to any one of claim 20 to 26, wherein existing in the oxidant and the hydrocarbon raw material Sulphur compound ratio between about 4:1 and about 10:1.
28. the method according to any one of claim 20 to 27, wherein the Hildebrand value of the polar solvent Greater than about 19.
29. the method according to any one of claim 20 to 28, wherein the polar solvent is selected from consisting of the following Group: acetone, carbon disulfide, pyridine, dimethyl sulfoxide, normal propyl alcohol, ethyl alcohol, n-butanol, propylene glycol, ethylene glycol, dimethyl formyl Amine, acetonitrile, methanol and their combination.
30. the method according to any one of claim 20 to 29, wherein the polar solvent is acetonitrile.
31. the method according to any one of claim 20 to 30, wherein the polar solvent is methanol.
32. the method according to any one of claim 20 to 31, wherein the solvent extraction is in about 20 DEG C and about 60 DEG C Between temperature and about 1 bar and about 10 bars between pressure under carry out.
33. the method according to any one of claim 20 to 32, it is further characterized in that following steps:
The extracted hydrocarbon flow is supplied to adsorption tower, the adsorption tower, which is equipped with, to be suitable for removing the extracted hydrocarbon material The adsorbent of compound present in stream through aoxidizing, the adsorption tower generate high-purity hydrocarbon product stream and the second oil of dreg Stream, the second residual oil stream include the compound through aoxidizing of a part.
34. according to the method for claim 33, it is further characterized in that following steps:
The second residual oil stream is supplied to the fluid catalytic cracking unit.
35. according to the method for claim 33, wherein the adsorbent be selected from consisting of the following group: active carbon, silica gel, Aluminium oxide, natural clay, silica-alumina, zeolite and their combination.
36. according to the method for claim 33, wherein the adsorbent is the carrier of polymer-coated, wherein the carrier With high surface area and selected from the group being made of silica gel, aluminium oxide and active carbon, and the polymer is selected from by following group At group: polysulfones, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane, silica-alumina, zeolite and Their combination.
37. the method according to any one of claim 20 to 36, wherein the first residual oil stream and the fluidisation are urged Change cracked charge stream to exist with following weight ratio: the catalyst and the first residual oil stream and the fluid catalytic cracking into The weight ratio range of stream is about 1 to about 15.
38. the method according to any one of claim 20 to 37, wherein the fluid catalytic cracking feeding flow includes to subtract Press gas oil, atmospheric residue, metal removal oil, whole crude, cracking shale oil, liquefaction coal, cracked pitches, heavy coked gas Oil, light cycle, heavy recycle stock, clarification slurry oil or their combination.
39. the method according to any one of claim 20 to 38, wherein it is described in the presence of a catalyst, make described the One residual oil stream contacts generation with fluid catalytic cracking feeding flow within the temperature range of about 300 DEG C to about 650 DEG C.
40. the method according to any one of claim 20 to 39, wherein it is described in the presence of a catalyst, make described the One residual oil stream contacts generation with fluid catalytic cracking feeding flow within about 0.1 second to about 10 minutes residence time.
41. the method according to any one of claim 20 to 40, it is further characterized in that following steps:
Low boiling point component and catalyst granules and the first residual oil stream and the fluid catalytic cracking are fed into flow separation；With And
Make at least part of regenerated catalyst particles.
42. according to the method for claim 41, wherein described make at least part of regenerated catalyst particles include: Contact the catalyst granules of the part in a fluidized bed with anhydrous oxygen-containing gas, the fluidized bed is generating regeneration catalyzing It is operated under conditions of agent and gaseous products and liquid product, the gaseous products include carbon monoxide and carbon dioxide.
CN201880008484.0A 2017-01-25 2018-01-25 Oxidation sweetening and the sulfone management of oil distillate are carried out using FCC Pending CN110249035A (en)

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