CN110392728A - Using coker desulfurization and remove sulfone - Google Patents

Using coker desulfurization and remove sulfone Download PDF

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Publication number
CN110392728A
CN110392728A CN201880012795.4A CN201880012795A CN110392728A CN 110392728 A CN110392728 A CN 110392728A CN 201880012795 A CN201880012795 A CN 201880012795A CN 110392728 A CN110392728 A CN 110392728A
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China
Prior art keywords
hydrocarbon
stream
raw material
coker
aoxidizing
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CN201880012795.4A
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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·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 US15/437,271 external-priority patent/US10093871B2/en
Application filed by Saudi Arabian Oil Co filed Critical Saudi Arabian Oil Co
Publication of CN110392728A publication Critical patent/CN110392728A/en
Pending legal-status Critical Current

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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
    • 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
    • C10G55/04—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 thermal cracking step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • 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
    • 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
    • C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26
    • 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
    • C10G21/28—Recovery of used solvent
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Helmets And Other Head Coverings (AREA)
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Abstract

Embodiment provides the method and apparatus that a kind of pair of hydrocarbon raw material carries out upgrading.According at least one embodiment, this method includes (a) hydrocarbon raw material being supplied to oxidation reactor, in oxidation reactor, in the presence of a catalyst, under conditions of being enough sulphur compound present in selectively oxygenated hydrocarbon feedstock, be oxidized hydrocarbon raw material；(b) hydrocarbon and the sulphur compound through aoxidizing are separated by solvent extraction；(c) the residual oil stream comprising the sulphur compound through aoxidizing is collected；(d) residual oil stream is supplied to coker, to generate coker gas and solid coke；And (e) after the completion of sorption cycle, the spent sorbents comprising residual oil from adsorption tower are supplied to coker, to handle spent sorbents.

Description

Using coker desulfurization and remove sulfone
Technical field
Embodiment is related to the method and apparatus for making hydrocarbon raw material desulfurization.More specifically, embodiment is related to passing through The oxidation sweetening of hydrocarbon raw material and sulphur-containing substance through aoxidizing and nitrogen substance then are handled to make hydrocarbon raw material desulfurization with coker Method and apparatus.
Background technique
Crude oil is the main source for being used as the hydrocarbon of fuel and petrochemical materials 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 compared with It is low.In general, the sulphur concentration in crude oil is below about 5 weight % (wt%), the sulphur concentration of most of crude oil is in about 0.5wt% to about In the range of 1.5wt%.The nitrogen concentration of most of crude oil is usually less than 0.2wt%, but may be up to 1.6wt%.In the U.S., Provide 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 Particulate emission is aggravated.
A kind of method for reducing particulate emission includes adding various oxygenated fuels compound to be blended, containing seldom or not Compound (such as methanol and dimethyl ether) containing C-C bond or both.However, the shortcomings that these most of compounds, exists In the vapour pressure of these compounds may be very high, is practically insoluble in diesel fuel or ignition performance (such as by its Cetane number It is indicated) it is poor, or have the shortcomings that these combination.
Pass through chemical hydrotreating or the processed diesel oil to reduce sulfur content and aromatic content of hydrogenization The fuel lubricity of fuel would generally reduce, this will lead in turn petrolift, injector and other contact fuel under high pressure The excessive wear of movable part.
For example, midbarrel (that is, fraction that nominal boiling range is about 180 DEG C to 370 DEG C) may be used as fuel or optional Ground may be used as the mixture components of fuel used in compression ignition engine (i.e. diesel engine).Midbarrel generally comprises about The sulphur of 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.
It is then removed to from hydrocarbon currently, the routine techniques for removing sulphur compound and nitrogen compound usually still needs Sulfur-containing compound and nitrogenous compound recycled and/or handled.In order to defer to increasingly strict ultra-low sulfur fuel Regulation, oil plant must make oil plant factory (refinery gate) fuel have lower sulfur content, after blending Enough meet stringent specification.
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 Ppolynuclear aromatic sulphur compound), these units be not in terms of the desulfurization from compound very effectively.When thia original Son is especially true when being hindered by two alkyl (for example, 4,6- dimethyl Dibenzothiophenes).Due to being difficult to remove, thus for example When the low sulfur content of 50ppmw to 100ppmw, the dibenzothiophenes with steric hindrance is main component.Harsh operation must be used Condition (for example, high hydrogen partial pressure, high temperature or high catalyst volume) is with the desulfurization from these intractable sulphur compounds.It can only lead to It crosses and improves recyclegas purity or new base unit must be designed to realize the raising of hydrogen partial pressure, this may be that cost is very high Selection.Normally result in that yield reduces, catalyst life cycles are shorter and product quality (example using harsh operating condition Such as, color) deterioration, therefore should usually avoid 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 reach required upgrading and conversion.These methods are also possible that the too early of catalyst Or rapid deactivation, because this is in the hydrotreating of heavy feedstocks or the common feelings during the hydrotreating under critical conditions Condition, it is therefore desirable to make catalyst regeneration or add new catalyst, this will lead to processing unit shutdown in turn.Heat treatment method is logical Often suffer from 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 The special equipment suitable for critical conditions (for example, high temperature and high pressure) is needed, and needs to input big energy, so as to cause multiple Polygamy and cost improve.
It is needed accordingly, there exist such, that is, provides a kind of method of desulfurization for hydrocarbon raw material (such as by from hydrocarbon raw material Except desulfuration and nitrogen), and this method further includes the steps that making hydrocarbon raw material desulfurization and denitrogenation using low harsh degree condition；It can also mention For recycling and/or handling the device of sulfur-containing compound and nitrogenous compound；Or it carries out both above-mentioned.
Summary of the invention
Embodiment provides the major part for removing existing sulphur and nitrogen and and then utilizes these chemical combination in correlation technique Object, thus the method and apparatus for carrying out upgrading to hydrocarbon raw material.
According at least one embodiment, the method that a kind of pair of hydrocarbon raw material carries out upgrading is provided, comprising the following steps: will Hydrocarbon raw material is supplied to oxidation reactor, which includes sulfur-containing compound；And in the presence of a catalyst, in oxidation reaction In device, under conditions of being enough sulphur compound present in selectively oxygenated hydrocarbon feedstock, contact hydrocarbon raw material with oxidant, with Generate the hydrocarbon flow comprising hydrocarbon and the sulfur-containing compound through aoxidizing.This method further include: hydrocarbon flow is supplied to extraction vessel, and Hydrocarbon flow is extracted by using polar solvent, so that hydrocarbon flow be separated into extracted hydrocarbon flow and mixture flow, wherein mixing Closing stream includes polar solvent and the sulfur-containing compound through aoxidizing, and the sulfur-containing compound of wherein extracted hydrocarbon flow is dense Concentration of the degree lower than the sulfur-containing compound of hydrocarbon raw material.In addition, this method comprises: mixture flow is separated into first using destilling tower The polar solvent stream of recycling and the first residual oil stream；First residual oil stream is supplied to coker, to generate volatile component Stream；And after the completion of sorption cycle, the spent sorbents comprising residual oil from adsorption tower are supplied to coker, to useless Adsorbent is handled.
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, to divide the hydrocarbon in the hydrocarbon flow through aoxidizing and the sulfur-containing compound through aoxidizing From.
According at least one embodiment, oxidant is selected from consisting of the following group: air, oxygen, nitrogen oxide, mistake Oxide, hydroperoxides, organic peracid and their combination.
According at least one embodiment, the catalyst of oxidation reactor is with formula MxOyMetal oxide, wherein M For the element of group ivb, VB race and group vib selected from the periodic table of elements.
According at least one embodiment, the temperature for making oxidation reactor be maintained at about 20 DEG C to 150 DEG C and about 1 bar to 10 Bar pressure under.
According at least one embodiment, the ratio of sulphur compound present in oxidant and hydrocarbon raw material is about 4:1 to 10: 1。
According at least one embodiment, the Hildebrand value (Hildebrandt 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 is in about 20 DEG C to 60 DEG C of temperature and about 1 bar to 10 bars of pressure Lower progress.
According at least one embodiment, hydrocarbon raw material also includes nitrogenous compound, so that making hydrocarbon in the presence of a catalyst The step of raw material and oxidant contact aoxidizes at least part nitrogenous compound, and is wherein supplied to the residual oil stream of coker Include the nitrogenous compound through aoxidizing.
According at least one embodiment, this method further include: extracted hydrocarbon flow is supplied to adsorption tower, wherein inhaling Attached tower is equipped with adsorbent, which is suitable for removing the compound present in extracted hydrocarbon flow through aoxidizing, and its Middle adsorption tower generates high-purity hydrocarbon product stream and the second residual oil stream, and the second residual oil stream includes one of the compound through aoxidizing Part.
According at least one embodiment, this method further includes that the second residual oil stream is supplied to coker.
According at least one embodiment, adsorbent is selected from consisting of the following group: active carbon, silica gel, aluminium oxide, natural Clay 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 and their combination.
According at least one embodiment, spent sorbents stream is continually or intermittently to be supplied in the stream of coker One kind.
According at least one embodiment, adsorbent includes one of carbon-based adsorbent or non-carbon base adsorbent.
According at least one embodiment, when adsorbent is carbon-based adsorbent, coker generates ash free volatility Component stream.
According at least one embodiment, when adsorbent is non-carbon base adsorbent, spent sorbents be used as slag material with The reactor wall of cooling coker, and coker generates the volatile component stream containing ash content.
According to another embodiment, a kind of method that upgrading is carried out to the hydrocarbon raw material comprising sulfur-containing compound is provided. The method for carrying out upgrading to hydrocarbon raw material includes: by about 500 DEG C of boils up till of hydrocarbon raw material supplied to reaction zone, in the reaction zone In, in the presence of a catalyst, contact hydrocarbon raw material with oxidant, at least part sulfur-containing compound in oxygenated hydrocarbon feedstock And generate the intermediate product stream comprising hydrocarbon and the sulfur-containing compound through aoxidizing.This method further include: will be comprising hydrocarbon and through aoxidizing The intermediate product stream of sulfur-containing compound keep intermediate product stream and polarity molten in extraction vessel supplied to extraction vessel Agent contact, and wherein polar solvent selectively extracts the sulfur-containing compound through aoxidizing from intermediate product stream, to generate First hydrocarbon product stream and mixture flow, the first hydrocarbon product stream include hydrocarbon and the concentration of sulfur-containing compound that has lower than hydrocarbon The concentration of the sulfur-containing compound of raw material, mixture flow include polar solvent and the sulfur-containing compound through aoxidizing extracted.In addition, This method comprises: being separated by distillation mixture flow to generate the polar solvent stream of recycling and residual oil stream, the polarity of recycling Solvent stream includes the major part of polar solvent, and residual oil stream includes the sulfur-containing compound through aoxidizing；And residual oil stream is supplied Should to coker, to generate the hydrocarbon product stream of recycling, the hydrocarbon product stream of recycling include condensation coker steam and watt This oil and solid coke, wherein coker includes coking furnace and coking tower, and wherein temperature of the coking furnace at least about 400 DEG C Lower operation, and run under pressure of coking tower in the range of at least about 425 DEG C of temperature and about 1 bar to 50 bars.This method It further include the spent sorbents comprising residual oil from adsorption tower being supplied to coker, to useless suction after the completion of sorption cycle Attached dose is handled.
According at least one embodiment, this method further includes the polar solvent stream recycling for recycling at least part To extraction vessel, wherein the polar solvent stream of at least part recycling is merged with polar solvent.
According at least one embodiment, the step of at least part of sulfur-containing compound includes: In in oxygenated hydrocarbon feedstock In oxidation reaction, contact hydrocarbon raw material with oxidant and catalyst, wherein oxidation reactor is maintained at about 20 DEG C to 150 DEG C of temperature Under degree and about 1 bar to 20 bars of pressure, time of contact is about 5 minutes to 60 minutes.
According at least one embodiment, the ratio of catalyst and oil is about 0.1 weight % to 10 weight %.
According at least one embodiment, the Hildebrand Solubility value of polar solvent is greater than about 19.
According at least one embodiment, extraction vessel is maintained at about 20 DEG C to 60 DEG C of temperature.
According at least one embodiment, hydrocarbon raw material also includes nitrogenous compound, so that supplying in the presence of a catalyst The step of hydrocarbon raw material with oxidant to contact aoxidizes at least part nitrogenous compound, and is supplied to the residual oil stream of coker Include the nitrogenous compound through aoxidizing.
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 Various 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 if you are using, main symbol indicates in optional embodiment or optional Similar component at position.
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.
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 solves the problems, such as related to following methods: the conventional method of upgrading is carried out to hydrocarbon raw material, especially Desulfurization and denitrogenation and subsequent side that sulfur-containing compound and nitrogenous compound are recycled, removed and handled for hydrocarbon raw material Method.In certain embodiments, embodiment can be found removes various sulfur-containing compounds and nitrogenous compound from hydrocarbon raw material Purposes.Therefore, according at least one embodiment, a kind of desulfurization from hydrocarbon raw material is provided and then by the sulphur object through aoxidizing Matter is supplied to method of the delay coking device to generate gas oil and coke.
As used, term " upgrading " or " upgrading " about petroleum or hydrocarbon refer to and initial petroleum or hydrocarbon raw material It compares, it is (that is, have less carbon atom, such as methane, ethane and propane) of relatively lightweight, api gravity with higher, higher The petroleum or hydrocarbon products of one of midbarrel yield, lower sulfur content, lower nitrogen content or lower tenor.
Fig. 1 provides the embodiment for carrying out upgrading to hydrocarbon.Hydrocarbon upgrading system 100 includes oxidation reactor 104, extracts and hold Device 112, solvent regeneration tower 116, stripper 120 and coker 130.
According at least one embodiment, a kind of pair of hydrocarbon raw material is provided (especially comprising sulfur-containing compound or nitrogen Close the hydrocarbon raw material of object or above two compound) method that carries out upgrading.This method includes that hydrocarbon raw material 102 is anti-supplied to oxidation Device 104 is answered, wherein contacting hydrocarbon raw material with oxidant and catalyst.Sulfur-containing compound and nitrogenous compound preferably with oxidant It is oxidized when with catalyst contact.Oxidant can be supplied to oxidation reactor 104 via oxidant feed pipeline 106, 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 petroleum base hydrocarbon, and may include various miscellaneous Matter 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.Optionally, 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.In certain embodiments, hydrocarbon raw material 102 can be the diesel oil that boiling point is about 150 DEG C to 370 DEG C.In In certain embodiments, hydrocarbon raw material 102 can be the vacuum gas oil (VGO) that boiling point is about 370 DEG C to 520 DEG C.Optionally, hydrocarbon raw material 102 boiling point can be up to about 450 DEG C, or be up to about 500 DEG C.Optionally, the boiling point of hydrocarbon raw material 102 can be about 100 DEG C To 500 DEG C.Optionally, the boiling point of hydrocarbon raw material 102 can be up to about 600 DEG C, perhaps be up to about 700 DEG C or in certain implementations In scheme, greater than about 700 DEG C.In certain embodiments, hydrocarbon raw material 102 may include heavy hydrocarbon.As non-limiting examples, Heavy hydrocarbon refers to that boiling point is greater than about 360 DEG C of hydrocarbon, and may include aromatic hydrocarbons and alkane, alkene and cycloalkane.
In general, in certain embodiments, hydrocarbon raw material 102 can be former selected from full range (wholerange) crude oil, topping Oil, the product stream from oil plant, the product stream from oil-extraction plant steam process, liquefaction coal, from oil or Tar sands Liquid product, pitch, oil shale, asphalitine of middle recycling 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 alkalinity and neutral nitrogen compound, including indoles, carbazole, Aniline, quinoline, acridine etc. and their mixture.
According at least one embodiment, relative to commonly used in the item in the conventional hydrodesulfurization method of diesel-type raw material Part, oxidation reactor 104 can be run in a mild condition.More specifically, in certain embodiments, oxidation reactor 104 may remain in about 20 DEG C to about 150 DEG C or about 30 DEG C to about 150 DEG C or about 30 DEG C to about 90 DEG C or about 90 DEG C at a temperature of about 150 DEG C.In certain embodiments, which is preferably from about 30 DEG C to about 75 DEG C, and even more preferably about 45 DEG C to 60 DEG C.The operating pressure of oxidation reactor 104 can be about 1 bar to 80 bars or about 1 bar to 30 bars or about 1 bar extremely 15 bars, and preferably from about 2 bars to 3 bars.Residence time of the hydrocarbon raw material in oxidation reactor 102 can be about 1 minute to 180 Minute or about 15 minutes to 180 minutes or about 15 minutes to 90 minutes or about 5 minutes to 60 minutes or about 60 Minute was to 120 minutes or about 120 minutes to 180 minutes, and the preferably sufficiently long time present in hydrocarbon raw material so as to appoint What sulphur compound or nitrogen compound are oxidized.In one embodiment, residence time of the hydrocarbon raw material in oxidation reactor 104 It is about 15 minutes to 45 minutes.In contrast, the conventional hydrodesulfurization of diesel-type raw material usually carries out under conditions of more harsh, For example, temperature is about 330 DEG C to 380 DEG C, pressure is about 50 bars to 80 bars and liquid hourly space velocity (LHSV) (LHSV) is about 0.5h-1To 2h-1。
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.Suitable reactor for oxidation reactor 104 may include (for example) batch reactor, fixed bed reaction Device, fluidized bed reactor, hoisting type reactor, fluidized-bed reactor, paste state bed reactor etc..Sulphur present in hydrocarbon raw material 102 Compound and nitrogen compound can be oxidized to sulfone, sulfoxide and the nitrogen compound through aoxidizing in oxidation reactor 104, these changes Closing object can be then removed by extracting or adsorbing.Nitrogen compound through aoxidizing may include (for example) pyridinyl compounds and - two furan compound of pyrrolyl compound or pyridine.In general, nitrogen-atoms itself is not oxidized during oxidation, but compound It is oxidized to the compound for being easy to separate with remaining compound.
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 oxides, 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..
In certain embodiments, for example sulphur concentration is higher than the hydrocarbon raw material of nitrogen concentration, then exists in oxidant and hydrocarbon raw material The molar ratio of sulphur can be about 1:1 to 50:1, preferably from about 2:1 to 20:1, more preferably from about 4:1 to 10:1.
In certain other embodiments, for example, nitrogen concentration be higher than sulphur concentration hydrocarbon raw material (for example, certain South America crude oil, Certain Africa crude oil, certain Russian oils, certain Chinese crude oils and such as coking oil, hot tearing carburetion, visbreaking oil, FCC Certain intermediate oil plant streams such as recycle oil), the molar ratio of oxidant and nitrogen present in hydrocarbon raw material can be about 1:1 to 50: 1, preferably from about 2:1 to 20:1, more preferably from about 4:1 to 10:1.
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.Metal may include titanium, vanadium, chromium, molybdenum and tungsten.Molybdenum and Tungsten can be used for two kinds of particularly effective catalyst of various embodiments.In certain embodiments, dead catalyst can be with It is being 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 0.1 weight % to about 10 weight %, preferably from about 0.5 weight % to about 5 weight %.In certain embodiments, which is about 0.5 weight % to about 2.5 weight %.It is optional Ground, the ratio are about 2.5 weight % to about 5 weight %.The weight rate of other suitable catalyst and oil is for this field skill It is it will be apparent that and being considered as in the range of various embodiments for art personnel.
Various sulfur-containing compounds in hydrocarbon raw material 102 and nitrogenous can be improved in catalyst present in oxidation reactor 104 The oxidation rate of compound, to realize reaction and the oxygen for being completed in a relatively short time sulfur-containing compound and nitrogenous compound Change, and reduces the amount of oxidant needed for the oxidation for realizing sulfur-containing compound and nitrogenous compound.In certain embodiments, it urges Agent can have the selectivity of raising to the oxidation of sulphur-containing substance or nitrogen substance or both substances.In other embodiments In, catalyst minimizes with selectivity the oxidation for making aromatic hydrocarbons.
According at least one embodiment, oxidation reactor 104 generates the hydrocarbon material containing the sulphur through aoxidizing and the nitrogen through aoxidizing Stream 110, which may include the hydrocarbons containing the sulphur through aoxidizing and the nitrogen through aoxidizing.Oxidation reaction by-products base Change in initial oxidant.For example, will form the pair as oxidation reaction in the embodiment that oxidant is hydrogen peroxide The water of product.In the embodiment that oxidant is organic peroxide, the alcohol of the by-product as oxidation reaction will form.It is secondary Product is usually being extracted and is being removed in solvent recovery step.
Hydrocarbon flow 110 containing the sulphur through aoxidizing and the nitrogen through aoxidizing is supplied to extraction vessel 112, in extraction vessel 112 In, the hydrocarbons containing the sulphur through aoxidizing and the nitrogen through aoxidizing can be contacted with Extraction solvent stream 137.Extraction solvent 137 can Think polar solvent, and in certain embodiments, the Hildebrand Solubility value of Extraction solvent 137 can be greater than about 19.In certain embodiments, when the specific polar solvent of selection is for extracting containing the sulphur through aoxidizing and the nitrogen material through aoxidizing When, as non-limiting example, it can be based on solvent density, boiling point, freezing point, viscosity and surface tension (to a certain extent) It is selected.Polar solvent suitable for extraction step may include acetone (Hildebrand value 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), acetonitrile (30), methanol (29.7) Etc. components or physics and the similar component of chemical property.In certain embodiments, acetonitrile and methanol are due to its low cost, volatilization Property and polarity but it is preferred.Methanol is the especially suitable solvent that can be used for these embodiments.In certain embodiments, Solvent comprising sulphur, nitrogen or phosphorus preferably has relatively high volatility, to ensure to carry out sufficient solvent vapour from hydrocarbon raw material It mentions.
According at least one embodiment, Extraction solvent is non-acid, and extraction step carries out in no acid environment. Due to sour general corrosion and require all devices specially designed to be used to corrosive environment, thus usually should be avoided make With acid.In addition, the acid of such as acetic acid etc can due to lotion formation and cause 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 be in about 1 bar to 10 bars, preferably from about 1 Bar to running under 5 bars, more preferably from about 1 bar to 2 bars of pressure.In certain embodiments, extraction vessel 112 is at about 2 bars to 6 bars Pressure under run.
According at least one embodiment, the ratio of Extraction solvent and hydrocarbon raw material can be about 1:3 to 3:1, preferably from about 1:2 To 2:1, more preferably from about 1:1.Extraction solvent and containing the time of contact between the sulphur through aoxidizing and the hydrocarbon flow 110 of the nitrogen through aoxidizing It can be about 1 second to 60 minutes, preferably from about 1 second to about 10 minutes.In certain embodiments, Extraction solvent with containing being aoxidized Time of contact between sulphur and the hydrocarbon flow 110 of the nitrogen through aoxidizing is less than about 15 minutes.In certain embodiments, extraction vessel 112 may include various for extending Extraction solvent and containing connecing between the sulphur through aoxidizing and the hydrocarbon flow 110 of the nitrogen through aoxidizing Touch the device of time or the device of the mixability for improving two kinds of solvents.It may include that machinery stirs for mixed device Mix the devices such as device or mixer, pallet.
According at least one embodiment, extraction vessel 112 generates mixture flow 114, which may include Extraction solvent, the substance (for example, being initially present in the hydrocarbons containing sulphur and nitrogen through aoxidizing in hydrocarbon raw material 102) through aoxidizing With hydrocarbon raw material and extracted hydrocarbon flow 118, which may include the sulfur-bearing compared with hydrocarbon raw material 102 The hydrocarbon raw material that the concentration of hydro carbons and nitrogenous hydro carbons reduces.In general, hydrocarbon raw material is only present in mixture flow 114 with trace.
Mixture flow 114 can be supplied to solvent regeneration tower 116 can be by Extraction solvent in solvent regeneration tower 116 It recycles as the first recovered solvent stream 117 and is separated with the first residual oil stream 123, the first residual oil stream 123 includes containing warp The sulphur of oxidation and the hydrocarbon compound of nitrogen.Optionally, mixture flow 114 can be separated into recycling in solvent regeneration tower 116 The hydrocarbon flow 124 of hydrocarbon flow 124, recycling may include hydrocarbon present in the mixture flow 114 from hydrocarbon raw material 102.Solvent is again Raw tower 116 can be to be configured to for mixture flow 114 to be separated into the first recovered solvent stream 117,123 and of the first residual oil stream 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 Point can optionally via pipeline 122 be supplied to stripper 120, and can in stripper 120 with extracted hydrocarbon flow 118 merge.In certain embodiments, the hydrocarbon that can be provided to the recycling of stripper 120 can be generated in solvent regeneration tower 116 Stream 124, in stripper 120, the hydrocarbon flow of recycling can optionally with extracted hydrocarbon flow 118 or mixture flow 114 A part contact, mixture flow 114 can via pipeline 122 be supplied to stripper 120.
Various received streams are separated into stripped oil stream 126 and the second recovered solvent stream 128 by stripper 120, Stripped oil stream 126 includes hydrocarbon present in hydrocarbon raw material 102 and sulphur and nitrogen content are lower than hydrocarbon raw material 102.
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 coker 130, the first residual oil stream 123 includes containing the sulphur through aoxidizing With nitrogen compound and can also include low concentration hydrocarbonaceous material, in coker 130, the first residual oil stream 123 can be with It is converted to recycle hydrocarbon.Coker 130 can be delay coking device, fluid coker, flexicoking device or similar device.At certain In a little embodiments, coker 130 can be delay coking device.Delay coking device 130 may include at least one coker point Evaporate device, coking furnace and at least one coking tower.In one embodiment, other than the first residual oil stream 123, to coker 130 other raw materials of supply from optional technique.
In the basic delay coking process that can be used for certain embodiments, the charging of coker 130 be may include through oxygen The sulphur compound of change, through the nitrogen compound aoxidized or both compounds, and may be also former comprising the Extraction solvent of trace, hydrocarbon Material 102 or both, and the charging can be introduced into the lower part of coker fractionator (not shown).Supplied to coker The substance (comprising containing sulphur or nitrogen compound or both compounds through aoxidizing) of fractionator can also include fractionator column bottom Fraction, the tower bottom distillate may include heavy recycle substance.It is optionally possible to which the second hydrocarbon raw material 133 is supplied to coker 130, which may include the residual oil from vacuum distillation tower or atmospheric distillation tower.
The substance for being supplied to coker 130 is heated to coking temperature in coking furnace (not shown), heated to generate Coker feedstock.In certain embodiments, coking furnace can be at greater than about 400 DEG C, or greater than about 450 DEG C, Huo Zhe great It is run at a temperature of about 475 DEG C.In certain embodiments, coking furnace can about 475 DEG C to 525 DEG C at a temperature of transport Row.
According at least one embodiment, then heated coker feedstock can be supplied to coking tower, the coking Tower is maintained at the coker feedstock decomposition for being enough to make heating or cracking, and to form volatile component stream 134, (it may include low point Son amount hydrocarbon gas) coking condition temperature and pressure under.In certain embodiments, volatile component stream can be collected 134 and merge with stripped oil stream 126.In certain embodiments, volatile component stream 134 can be collected separately and be used for In optional technique.
According at least one embodiment, coking tower can at greater than about 425 DEG C, perhaps about 425 DEG C to 650 DEG C or It is run at a temperature of about 450 DEG C to 510 DEG C, or about 470 DEG C to 500 DEG C.In certain embodiments, coking tower is at least Run at a temperature of 500 DEG C, or at least 525 DEG C at a temperature of run.
Operating pressure in coking tower can be in the range of about 1 bar to 50 bars, or in about 5 bars to 40 bars of range It is interior, or in the range of about 10 bars to 30 bars.In certain embodiments, range of the coker 130 at about 10 bars to 25 bars It is run under interior pressure.In optional embodiment, coker 130 is run under pressure in the range of about 25 bars to 40 bars. In an optional embodiment, coker 130 is transported under pressure in the range of about 1 bar to 10 bars, preferably from about 1 bar to 3 bars Row.
From the volatile component (coker steam) as the volatile component stream 134 from coking tower of overhead collection It can be recycled from tower and return to coker fractionator.It can be by lightweight and heavy gas oil fraction from coker fractionator Supplied to the flash zone of coker fractionator, wherein heavy gas oil can be used for condensing from coker steam it is most heavy at Point.Fraction most heavy in coking tower steam can also be condensed by other technologies, such as utilize heat exchange, but in certain embodiment party In case, the steam of the coking tower of entrance preferably in coker fractionator lightweight or heavy gas oil condensed.Certain In embodiment, the conventional heavy end for being recycled to coker fractionator may include the hydrocarbon condensed by coking tower steam and not The heavy gas oil of flash distillation.In continuous feed technique, coke can be accumulated in coking tower, so that when coking tower is full of coke When, charging can be converted to another tower, and cool down by conventional method and empty the tower being full of to generate coke stream 136.To enable the technique continuous operation.
In certain embodiments, coker 130 includes two or more coking towers, as described above, these coking towers It can run in an alternating manner.For example, can be by raw material supply to the first coking tower, and can be heated in the first coking tower Raw material is to generate coker steam and solid coke.After having gathered the solid coke of predetermined amount in the first coking tower, Ke Yiting It only supplies raw material to the first coking tower and can be by raw material supply to the second coking tower, the second coking tower is with similar to the first tower Mode run, until having gathered the coke of predetermined amount in the second coking tower.The second coking tower operation during, can stop to First coking tower provides charging and heating, and can remove the coke in the first coking tower.As described above, by being used alternatingly First coking tower and the second coking tower can stop using a tower in the case where not stopping entire coking process.Work as stopping When using a coking tower, the coke in the coking tower can be removed by conventional method, to generate coke produced stream 136.
Referring to Fig. 2, the second embodiment is provided, wherein adsorption tower can will be supplied to through steam stripped oil plant stream 126 240, in adsorption tower 240, it can be contacted with one or more adsorbents through steam stripped oil plant stream 126, to generate hydrocarbon products material Stream 242 and absorbing unit residual oil stream 244, adsorbent is designed as removing one or more different impurity, such as walks in oxidation Sulfur-containing compound, the sulphur compound through aoxidizing, the nitrogenous chemical combination remained in hydrocarbon product stream after rapid and solvent extraction step Object, nitrogen compound and metal through aoxidizing.
According at least one embodiment, adsorbent may include active carbon, silica gel, aluminium oxide, natural clay and other Inorganic adsorbent.In certain embodiments, adsorbent may include being applied or having coated various high-surface area support materials The polar polymer of (such as silica gel, aluminium oxide and active carbon).Example for coating the polar polymer of various backing materials can With include polysulfones, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane, the sulfur material through aoxidizing is shown it is affine The other similar polymer material and their combination of property.
According at least one embodiment, adsorption tower 240 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 or about 35 DEG C to about 75 DEG C.In certain embodiments, adsorption tower 240 can be greater than about 20 DEG C or temperature below about 60 DEG C at a temperature of run.Adsorption tower 240 can be up to about 15 bars, preferably of up to about 10 bars, It is run under even more preferably about 1 bar to about 2 bars of pressure.In certain embodiments, adsorption tower 240 can be at about 2 bars to about 5 Bar pressure under run.In an exemplary embodiment, adsorption tower 240 can about 25 DEG C to about 35 DEG C temperature, about 1 It is run under the pressure that 2 bars of Ba Zhiyue.
According at least one embodiment, it is very low (for example, lower than 15ppmw that charging is separated into sulfur content by adsorption tower 240 Sulphur) and the nitrogen content very low nitrogen of 10ppmw (for example, be lower than) extracted hydrocarbon product stream 242 and the second residual oil stream 244.Adsorbing the second residual oil stream 244 may include the sulphur compound through aoxidizing and the nitrogen compound through aoxidizing, and can appoint Selection of land merges with the first residual oil stream 123, and is supplied to coker 130, and handled as described above.
According to another embodiment, as shown in Fig. 2, adsorbent is after completing its circulation, can in coker 130 into Row processing.As further shown in Figure 2, the spent sorbents stream containing residual oil is supplied from adsorption tower 240 via pipeline 246, with Carry out the coking step in coker 130.Spent sorbents stream can be converted to valuable product.Spent sorbents stream can To be supplied in continuous or intermittent manner via pipeline 246.
According at least one embodiment, the spent sorbents stream comprising sulfone is supplied to coker 130.In the embodiment party In case, adsorbent is that pore volume is 0.429 cubic centimetre/gram (cc/g) and surface area is 820.5 meters squared per gram (m2/ g) work Property charcoal.Adsorption tower 240 is run in a continuous manner, and the amount of adsorbent is calculated according to sulfone to be adsorbed.It can will inhale Attached tower 240 is designed to run within 2 years periods.The amount of acticarbon is calculated as 109 tonnes (MT)/two year.Supply is extremely The amount of the useless hypersober of coker 130 based on total adsorbent daily equivalent (therefore be based on 1 period/2 109MT/ period * * 1 year/333 days year).The condition of coker 130 remains unchanged.5 kgs/hr (Kg/h's) based on supply to adsorption step The amount of sulfone calculating adsorbent.In this example, adsorption tower 240 is used as purification step (polishing step), is extracted with removing A small amount of sulfone in stream is stayed in afterwards.The adsorbent from adsorption tower 240 can be collected and supplied to coker 130.Additive amount Depending on operating condition.It by total amount tropical revolution phase number of days and can add daily, or be added with the maximum rate that delay coking device designs Add adsorbent.It is assumed to be daily amount, then the adsorbent added is 6.9Kg/h or 165kg/ days.According to an example, these additions The material balance that rate provides is shown in table 1:
Table 1: material balance
Ingredient stream No. 123 132 134 136
Kg/h Kg/h Kg/h Kg/h
Decompression residuum 1,000.00
Sulfone 107.60
Adsorbent 6.90
Lightweight coker product 668.60
Coke 440.90
It is total 114.50 1,000.00 668.60 440.90
It can balance or readjust the sulfur removal technology efficiency of both extraction vessel 112 and adsorption tower 240.In the reality provided In example, the sulfone of 98.96wt% is eliminated in extraction step, and remaining part is eliminated in adsorption step.It can incite somebody to action The unit is designed to respectively remove the sulfone of 50wt% in extraction unit and absorbing unit.In such a situation it is necessary to more inhale Attached dose separates sulfone.When desulfurization degree is 50wt% in adsorption step, the amount of required adsorbent is 5,224MT.With this rate, There to be more adsorbents to supply to coker 130.Under given battery limit condition (battery limit condition), The balance between extraction step and adsorption step can be adjusted according to the design of unit.
According to various embodiments, adsorbent may include carbon-based adsorbent.It can be by carbon-based adsorbent together with absorption Residual oil and pollutant are delivered to coker 130 together, to generate the volatile component 134 for not generating ash content.Implemented according to one Scheme, carbon-based adsorbent can in one cycle using and be delivered to coker 130, and without any in adsorption step The solvent reclamation of adsorbent.If adsorbent is carbon-based adsorbent (such as active carbon), not significant to delay coking device coke Quality influence.
According to various embodiments, adsorbent may include solid non-carbon base adsorbent, be used as slag material with cooling The reactor wall (especially in membranous wall) of coker 130, and eventually become ash content.It can be by the residual oil of absorption and pollutant one It rises and is delivered to coker 130, to generate volatile component stream 134.The example of non-carbon base adsorbent includes (for example) titanium dioxide Silicon-aluminium oxide, aluminium oxide, titanium dioxide, zeolite, oil refinery waste catalyst and natural clay.If adsorbent be not it is carbon-based, It then will affect the quality of coke.Such adsorbent can improve the content of ashes of coke, it is thus possible to can not obtain target quality.To The amount of processing depends on the coke quality of production.There are three types of types for delay coking device coke: 1) fuel-grade (shot coke) coke, and 2) Anode grade coke (sponge coke) and 3) anode grade coke (needle coke).Table 2 shows the property of the coke of these types.From coke The Oil Generation coke for changing tower recycling generates these coker coke after firing, and calcining is that one kind is waved for removing moisture and reducing The heat treatment of hair property combustible.
Table 2: the property of coker coke
Referring to Fig. 3, third embodiment is provided, wherein the first residual oil stream 123 is supplied to thermal cracking unit 330, First residual oil stream 123 includes sulfur-containing compound through aoxidizing, through the nitrogenous compound aoxidized or both compounds.Thermal cracking Unit 330 includes a series of pipelines, these pipelines are heated by feedstock portions to be converted into low-boiling fraction hydrocarbon 334.It can be with The residual oil from thermal cracking unit 330 is collected via pipeline 336.In certain embodiments, it can will be come from via pipeline 133 The hydrocarbon in optional source is supplied to thermal cracking unit 330.In some embodiments, from effluent (its of thermal cracking unit 330 It is made of low-boiling fraction hydrocarbon) the flash zone (not shown) of stripper 120 can be directed to.
Embodiment
In one embodiment, oxidation sweetening is carried out to hydrotreating straight-run diesel oil stream 102, it is mono- that it includes 500ppmw Matter sulphur, 0.28wt% density be 0.85 kg/liter (Kg/l) organic sulfur.It will be through oxidation and extracted sulphur compound and slag Oil plant flows into the mixing of stream 136, and property is shown in Table 3, and combined stream is supplied to coker 130.
Table 3:
Property Value
Api gravity 4.60
Specific gravity 1.04
Sulfur content, wt.% 5.42
Nitrogen content, wt.% 0.44
Oxygen content, wt.% 0.10
CCR, wt.% 24.60
C5Asphalitine, wt.% 23.50
Nickel, ppmw 44.00
Vanadium, ppmw 162.00
Reaction condition is as follows: the molar ratio of hydrogen peroxide and sulphur is 4:1.Catalyst is molybdenum (VI) base catalyst.When reaction Between be 30 minutes.About 80 DEG C are kept the temperature at, and pressure is maintained at about 1 bar.Coker is in about 482 DEG C of temperature and about 1 Bar pressure under run.The material balance of oxidation step is provided in table 4.
Table 4: material balance
The material balance of the extraction step of embodiment is provided in table 5.
Table 5: material balance
The material balance of the coker step of embodiment is provided in table 6.
Table 6: material balance
Stream No. 123 132 334 336
Ingredient
Kg/h Kg/h Kg/h Kg/h
Decompression residuum 1,000.00
Sulfone 102.60
Lightweight coker product 668.62
Coke 433.98
It is total 102.60 1,000.00 668.62 433.98
It is shown in Table 7 with the yield that coker handles charging.
Table 7: coker yield
Think that method described herein and system will be by by oxidation sweetening and denitrification process and cracking units or thermal cracking Unit connection, to improve the amount of the liquid hydrocarbon from aromatic sulphur compound, nitrogen compound and aromatic stream.In addition, recognizing Oxidation reaction by-products (that is, sulphur compound and nitrogen compound through aoxidizing) is handled for no any effective method.Implement Scheme provides the method for sulphur compound and nitrogen compound without handling compound handled through aoxidizing.
Although various 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 It includes the situation of generation event or situation and the situation of event or situation does 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 or to all combinations in another particular value and the range.

Claims (26)

1. the method that a kind of pair of hydrocarbon raw material carries out upgrading, the method is characterized in that following steps:
The hydrocarbon raw material is supplied to oxidation reactor, the hydrocarbon raw material includes sulfur-containing compound；
In the presence of a catalyst, in the oxidation reactor, be enough selectively to aoxidize present in the hydrocarbon raw material Under conditions of sulphur compound, contact the hydrocarbon raw material with oxidant, to generate the sulfur-containing compound for including hydrocarbon and through aoxidizing Hydrocarbon flow；
The hydrocarbon flow is supplied to extraction vessel, and the hydrocarbon flow is extracted by using polar solvent, thus by the hydrocarbon Stream is separated into extracted hydrocarbon flow and mixture flow, and the mixture flow includes the polar solvent and described through aoxidizing Sulfur-containing compound, and wherein the concentration of the sulfur-containing compound of the extracted hydrocarbon flow is lower than the institute of the hydrocarbon raw material State the concentration of sulfur-containing compound；
The mixture flow is separated into the polar solvent stream and the first residual oil stream of the first recycling using destilling tower；
The first residual oil stream is supplied to coker, to generate volatile component stream；
The extracted hydrocarbon flow is supplied to adsorption tower, the adsorption tower is equipped with adsorbent, which is suitable for removing Compound through aoxidizing present in the extracted hydrocarbon flow, the adsorption tower generate high-purity hydrocarbon product stream and second Residual oil stream, the second residual oil stream include a part of the compound through aoxidizing；And
After the completion of sorption cycle, the spent sorbents comprising residual oil from the adsorption tower are supplied to the coker, with The spent sorbents are handled.
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, to the warp The hydrocarbon and the sulfur-containing compound through aoxidizing in the hydrocarbon flow of oxidation are separated.
3. method according to claim 1 or 2, wherein the oxidant is selected from consisting of the following group: empty Gas, oxygen, nitrogen oxide, peroxide, hydroperoxides, organic peracid and their combination.
4. according to the method in any one of claims 1 to 3, wherein the catalyst of the oxidation reactor is with formula MxOyMetal oxide, wherein M is the element of group ivb selected from the periodic table of elements, VB race and group vib.
5. method according to claim 1 to 4, wherein the oxidation reactor is made to be maintained at about 20 DEG C extremely At 150 DEG C of temperature and about 1 bar to 10 bars of pressure.
6. the method according to any one of claims 1 to 5, wherein sulphur present in the oxidant and the hydrocarbon raw material The ratio of compound is between about 4:1 and 10:1.
7. method according to any one of claim 1 to 6, wherein the Hildebrand value of the polar solvent is greater than About 19.
8. method according to any one of claim 1 to 7, 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.
9. method according to any one of claim 1 to 8, wherein the polar solvent is acetonitrile.
10. method according to any one of claim 1 to 9, wherein the polar solvent is methanol.
11. method according to any one of claim 1 to 10, wherein temperature of the solvent extraction at about 20 DEG C to 60 DEG C It is carried out under degree and about 1 bar to 10 bars of pressure.
12. method according to any one of claim 1 to 11 makes wherein the hydrocarbon raw material also includes nitrogenous compound The step of hydrocarbon raw material must being made to contact in the presence of the catalyst with the oxidant aoxidizes to be contained described at least part Nitrogen compound, and include wherein the nitrogenous compound through aoxidizing supplied to the residual oil stream of the coker.
13. method according to any one of claim 1 to 12, it is further characterized in that following steps:
The second residual oil stream is supplied to the coker.
14. method according to any one of claim 1 to 13, wherein the adsorbent is selected from consisting of the following group: Active carbon, silica gel, aluminium oxide, natural clay and their combination.
15. according to the method for claim 14, wherein the adsorbent is the carrier of coated polymer, 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 and their combination.
16. according to claim 1 to method described in any one of 15, wherein the spent sorbents stream is continuously or intermittently Ground is supplied to one of described coker.
17. according to claim 1 to method described in any one of 16, wherein the adsorbent includes carbon-based adsorbent or non-carbon One of base adsorbent.
18. according to the method for claim 17, wherein when the adsorbent is the carbon-based adsorbent, the coking Device generates the ash free volatile component stream.
19. according to the method for claim 17, wherein described useless when the adsorbent is the non-carbon base adsorbent Adsorbent is used as slag material with the reactor wall of the cooling coker, and the coker generates the volatility containing ash content Component stream.
20. a kind of method for carrying out upgrading to the hydrocarbon raw material comprising sulfur-containing compound, carries out described in upgrading the hydrocarbon raw material Method is characterized in that following steps:
About 500 DEG C of boils up till of the hydrocarbon raw material is supplied to reaction zone, in the reaction zone, in the presence of a catalyst, Contact the hydrocarbon raw material with oxidant, to aoxidize at least part sulfur-containing compound in the hydrocarbon raw material and generate packet The intermediate product stream of sulfur-containing compound hydrocarbonaceous and through aoxidizing；
The intermediate product stream of sulfur-containing compound comprising hydrocarbon and through aoxidizing is supplied to extraction vessel, is held in the extraction In device, contact the intermediate product stream with polar solvent, wherein the polar solvent is selected from the intermediate product stream The sulfur-containing compound through aoxidizing is extracted, selecting property to generate the first hydrocarbon product stream and mixture flow, the first hydrocarbon products material Concentration of the stream comprising hydrocarbon and the concentration of sulfur-containing compound that has lower than the sulfur-containing compound of the hydrocarbon raw material, the mixture Stream includes the polar solvent and the sulfur-containing compound through aoxidizing extracted；
It is separated by distillation the mixture flow, to generate the polar solvent stream and residual oil stream of recycling, the pole of the recycling Property solvent stream include the polar solvent major part, the residual oil stream include the sulfur-containing compound through aoxidizing；
The residual oil stream is supplied to coker, to generate the hydrocarbon product stream of recycling, the hydrocarbon product stream packet of the recycling Coker steam and gas oil and solid coke containing condensation, wherein the coker includes coking furnace and coking tower, and Wherein the coking furnace at least about 400 DEG C at a temperature of run, and the coking tower is at least about 425 DEG C of temperature peace treaty It is run under pressure in the range of 1 bar to 50 bars；
The sulfur-containing compound through aoxidizing extracted is supplied to adsorption tower, the adsorption tower is equipped with adsorbent, the absorption Agent is suitable for removing the compound present in extracted hydrocarbon flow through aoxidizing, and the adsorption tower generates high-purity hydrocarbon products material Stream and the second residual oil stream, the second residual oil stream include a part of the compound through aoxidizing；And
After the completion of sorption cycle, the spent sorbents comprising residual oil from the adsorption tower are supplied to the coker, with The spent sorbents are handled.
21. according to the method for claim 20, it is further characterized in that following steps:
The polar solvent stream of at least part recycling is set to be recycled to the extraction vessel, wherein by least part institute State merging with the polar solvent for the polar solvent stream of recycling.
22. the method according to any one of claim 20 or 21, wherein aoxidizing at least part in the hydrocarbon raw material The step of sulfur-containing compound, is further characterized in that, in the oxidation reaction, makes the hydrocarbon raw material and the oxidant and catalysis Agent contact, wherein oxidation reactor is maintained under about 20 DEG C to 150 DEG C of temperature and about 1 bar to 20 bars of pressure, time of contact It is about 5 minutes to 60 minutes.
23. according to the method for claim 22, wherein the ratio of catalyst and oil is about 0.1 weight % to 10 weight %.
24. the method according to any one of claim 20 to 23, wherein the Hildebrand of the polar solvent is molten Solution angle value is greater than about 19.
25. the method according to any one of claim 20 to 24, wherein the extraction vessel is maintained at about 20 DEG C to 60 DEG C temperature.
26. the method according to any one of claim 20 to 25 makes wherein the hydrocarbon raw material also includes nitrogenous compound It obtains and supplies the hydrocarbon raw material in the presence of catalyst to aoxidize at least part institute the step of contact with the oxidant Nitrogenous compound is stated, and includes wherein the nitrogenous compound through aoxidizing supplied to the residual oil stream of the coker.
CN201880012795.4A 2017-02-20 2018-02-20 Using coker desulfurization and remove sulfone Pending CN110392728A (en)

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US20210179945A1 (en) * 2019-12-11 2021-06-17 Saudi Arabian Oil Company Needle coke production from hpna recovered from hydrocracking unit
CN114133954A (en) * 2020-09-03 2022-03-04 中国石油化工股份有限公司 Method and device for preparing low-sulfur petroleum coke by processing slag oil
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070151901A1 (en) * 2005-07-20 2007-07-05 Council Of Scientific And Industrial Research Process for desulphurisation of liquid hydrocarbon fuels
CN101117595A (en) * 2006-07-31 2008-02-06 中国石油化工股份有限公司 Combined process for petrol adsorption desulfurising and hydrocarbon oil catalytic cracking
US20120055845A1 (en) * 2010-09-07 2012-03-08 Saudi Arabian Oil Company Desulfurization and Sulfone Removal Using A Coker
CN103890142A (en) * 2011-07-29 2014-06-25 沙特***石油公司 Delayed coking process utilizing adsorbent materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9598647B2 (en) * 2010-09-07 2017-03-21 Saudi Arabian Oil Company Process for oxidative desulfurization and sulfone disposal using solvent deasphalting

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070151901A1 (en) * 2005-07-20 2007-07-05 Council Of Scientific And Industrial Research Process for desulphurisation of liquid hydrocarbon fuels
CN101117595A (en) * 2006-07-31 2008-02-06 中国石油化工股份有限公司 Combined process for petrol adsorption desulfurising and hydrocarbon oil catalytic cracking
US20120055845A1 (en) * 2010-09-07 2012-03-08 Saudi Arabian Oil Company Desulfurization and Sulfone Removal Using A Coker
CN103890142A (en) * 2011-07-29 2014-06-25 沙特***石油公司 Delayed coking process utilizing adsorbent materials

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