CN101292013B - Hydrocarbon resid processing and visbreaking steam cracker feed - Google Patents

Hydrocarbon resid processing and visbreaking steam cracker feed Download PDF

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CN101292013B
CN101292013B CN2006800388580A CN200680038858A CN101292013B CN 101292013 B CN101292013 B CN 101292013B CN 2006800388580 A CN2006800388580 A CN 2006800388580A CN 200680038858 A CN200680038858 A CN 200680038858A CN 101292013 B CN101292013 B CN 101292013B
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raw material
oil
residual oil
benchmark
koh
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CN101292013A (en
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P·F·科森克恩
S·H·布朗
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Abstract

The invention concerns integration of hydroprocessing and steam cracking. A feed comprising crude or resid-containing fraction thereof is treated by hydroprocessing and visbreaking and then passed to a steam cracker to obtain a product comprising olefins.

Description

The raw material of processing of hydrocarbon Residual oil and viscosity breaking steam cracker
Related application
The application requires the rights and interests and the right of priority of the US temporary patent application number 60/728,640 (2005B125) of submission on October 20th, 2005, also requires the rights and interests of the US temporary patent application number 60/813,555 (2006B101) of submission on June 14th, 2006.
Technical field
The present invention relates to method by crude oil or its fraction prepared alkene that contains Residual oil.
Background technology
The thermally splitting of hydro carbons is the petrochemical process that is widely used in preparation alkene such as ethene, propylene, butylene class, divinyl and aromatic hydrocarbons such as benzene, toluene and xylene.These compounds all are valuable Industrial products for every kind.For example; Light olefin can be oligomeric (for example oligomeric be lubricant base oil), polymerization (for example being polymerized to Vilaterm, Vestolen PP 7052 and other plastics) and/or functionalized (for example being used to form acid, alcohol, aldehyde etc.), and listed material all has known centre and/or end-use.A kind of method for thermal cracking is steam cracking, and it is included under the existence of hydrogen and/or hydrogenous component such as steam cracking hydrocarbon.
The starting raw material of aforesaid common olefin production plant had carried out the processing of a large amount of (with expensive) before reaching olefin production plant.Normally, whole crude is in distillation or in addition fractionation or cracking are that a plurality of parts (cut) are at first carried out desalination before like gasoline, kerosene, petroleum naphtha, gas oil (it comprise high boiling point residual oil (" Residual oil ")) such as (vacuum gas oil and atmospheric gas oils).Residual oil fraction has the boiling point that under atmospheric pressure is higher than 650 ℉ (343 ℃) usually.Usually after desalination and removing residual oil fraction, except 650 ℉+(343 ℃+) any of these cut the Residual oil can be transported to steam cracker or the olefin production plant raw material as this device.
Usually, in steam cracking, steam cracking is with hydrocarbon feed petroleum naphtha for example, other of gas oil or whole crude do not contain Residual oil cut (they for example can through distillation or in addition the fractionation whole crude obtain) be incorporated in the steam cracker, usually and steam.The pyrolysis oven that has two main sections is usually adopted in the common steam cracking: convection zone and radiation section.In common pyrolysis oven; Hydrocarbon feed gets into not too strict pyrolysis oven convection zone (except the lightweight material that gets into as steam) as liquid, there it through be heated and vaporize with choosing wantonly from the hot flue gases indirect contact of radiation section through directly contacting with steam.The raw material of vaporization and vapour mixture (if existence) are incorporated into radiation section through tubing jumper then; It is rapidly heated to strict hydrocarbon cracking temperature under the pressure of common 10-30psig there; For example 1450 ℉ (788 ℃) are to the scope of 1550 ℉ (843 ℃), with the thorough thermally splitting of the stream of supplying raw materials.The product that gained comprises alkene leaves pyrolysis oven and is used for further downstream separation and processing.
After cracking, the elute of pyrolysis oven contains various gas hydro carbons (it for example is saturated, single unsaturated and polyunsaturated, and can be aliphatic series and/or aromatics), and contains a large amount of molecular hydrogens.Crackate is for example further handled in olefin production plant to produce the various independently above-mentioned high purity logistics as device product then, that is, hydrogen, light olefin ethene, propylene and butylene class and aromatic substance also have other products such as pyrolysis gasoline.
Because the whole world is increasing the demand of light olefin; Handy crude resources is consumed; So must utilize heavy crude (that is, having those of higher proportion Residual oil), this capital investment that need increase is processed and is handled the purified by product and buys more high-grade raw material.Hope very much to have the method that more effectively to utilize lower cost, heavy crude and produce the product mixture of better light olefin.
The someone had proposed before steam cracking through at first the raw material hydrotreatment being improved the grade of some crude oil fractions.For example, US patent Nos.3,855,113 and 6,190,533 relate to a kind of method, and it comprises lets raw material through the hydrotreatment district, subsequently through the steam cracking district.Yet not having a kind of situation is that whole crude or the cut that comprises Residual oil are delivered directly to the hydrotreatment district.Also referring to GB2071133 and Erdoel & Kohle, Erdgas, Petrochemie (1981), 34 (1), 443-6.
Conventional Residual oil hydrotreatment or " residual hydrogenation is refining " are the known methods of quality that a part contains the crude oil fractions of Residual oil that improves.Usually be more valuable logistics by fractionation by refining hydrogenated liq and the vapor product (but not being the Residual oil product) that obtains of residual hydrogenation, oil fuel for example, diesel oil, heated oil, jet propulsion fuel (jet), kerosene, gasoline, LPG and stack gas.All these materials itself can be used as fuel and/or are used as the midbody of for example producing petroleum chemicals.For example, oil fuel can also cracking to form more for example gasoline of lower boiling fuel, LPG and fuel gas and/or petroleum chemicals ethene, propylene and butanes.Residual oil fraction is low-value product normally.Yet, after hydrotreatment and before the further distillation of Residual oil logistics or during, the crude oil fractions that contains Residual oil can transform, diasphaltene or other processing.
US 3,898, and 299 disclose the method that removes residual oil fraction and produce alkene by non-Residual oil, low boiling point hydrocarbon.Atmospheric resids by distillation obtains is carried out hydrotreatment and liquid hydrotreater elute " pyrolysis zone is given in direct charging in the presence of steam; wherein before the overhead product cut entering of vaporization remained on the pyrolysis zone under the thermally splitting condition, the raw material of vaporization was not removed in the disengaging zone as residual cut ".Yet ' 299 reference has only been instructed the conventional hydrotreatment and the hot steam cracking of the overhead stream that does not contain Residual oil, does not have suitably to propose or instruct and how to use from the unitary raw material that contains the elute of Residual oil as steam cracker of Residual oil hydrotreatment.650 ℉+(343 ℃) boiling point fraction need separated and remove to ' 299 patent usually from the hydrotreater elute of handling before steam cracking.Have only the overhead product cut to be processed to alkene.Those skilled in the art know that very steam cracking contains the practical difficulty of the raw material of Residual oil, the equipment scaling of the common equipment of ' 299 patent that it comprises.The Residual oil hydrotreatment is to be used for Residual oil is promoted the currently known methods for fuel such as oil fuel, diesel oil, heated oil, jet propulsion fuel, kerosene, gasoline, LPG and fuel gas.These materials all can be used as fuel and/or for example produce the midbody of petroleum chemicals.
Other patent relevant with cracking heavy feedstocks comprises the US patent No.4 of Wernicke, 257,871; The US patent No.4 of Soonawala, 065,379; The US patent No.4 of Franck, 180,453; And the US patent No.4 of Wernicke, 210,520.Yet above-mentioned patent does not all have hydrocarbon stream steam cracking that how abundant instruction will contain Residual oil to produce alkene.
At US4, in 257,871, use decompression residual oil to produce alkene: at first to separate the pitch that wherein contains,, then this blend is carried out conventional catalytic hydrogenation, thermally splitting afterwards with poor bitumeniferous cut of gained and more light-weight cut blend through following method.Also referring to US4,297,204.
Japan Kokai patented claim Sho58 [1983]-98387 relates to the method for preparing gas alkene and monokaryon aromatic hydrocarbons, it is characterized in that with hydrogen and hydrogenation catalyst crude oil hydrogenation, thermally splitting subsequently.In embodiments, can be with hydrogenation crude distillation or flash distillation separating each component, and give thermocracking process with the overhead stream charging.Also referring to Japanese Kokai patented claim Sho58 [1983]-005393 and Japanese Kokai patented claim Sho57 [1982]-212294.
US6,303,842 have instructed through containing the Residual oil that boiling point is higher than 565 ℃ short boiling range Residual oil and have carried out the method that the hot steam cracking prepares alkene, and wherein the short boiling range Residual oil of 3wt% has the boiling point that is greater than or equal to 650 ℃ at least.Raw material prepares through common hydrotreatment.Significant other reference comprises US patent Nos.3,855,113; 4,057,490; 4,179,355 and 6,743,961.Other patent relevant with cracking heavy feedstocks comprises the US patent No.4 of Wernicke, 257,871; The US patent No.4 of Soonawala, 065,379; The US patent No.4 of Franck, 180,453; And the US patent No.4 of Wernicke, 210,520.
WO2004/005431 discloses the method that some is comprised the raw material steam cracking of Residual oil, wherein before steam cracking, removes a large amount of unconverted liquid residue cuts.' 5431 inventions not have open or instruction hydrogenation as the method that is used to improve heavy, tart crude oil and residual feedstocks (it comprises residual oil fraction) quality, the feasible whole crude that comprises residual oil fraction can steam cracking and is converted into petroleum chemicals.Heavy, tart raw material do not contain the linear alkanes of high density, the steam cracker feed stock of their known formation extra best bests.Contain＞normal pressure and the decompression residual oil cut of the crude oil of 2.0wt% sulphur almost always have＜hydrogen richness of 12.5wt%, and they have＜hydrogen richness of 11.0wt% usually.As everyone knows, common Residual oil hydrotreatment has produced the product of very easy fouling.
Whole crude that contains Residual oil that this area need be handled heavy economically and their hydrocarbon-fraction that contains Residual oil are with the apparatus and method of preparation alkene, aromatic hydrocarbons and other valuable petroleum chemicals.All prior aries before the present invention exist deficiency, shortcoming or unfavorable aspect.
Summary of the invention
The contriver is surprisingly found out that; Through integrating at least one step of hydrogenation, at least one viscosity breaking step and at least one thermally splitting step; Can use strict degree to improve and prepare useful product, for example alkene and/or aromatic substance with the Residual oil hydrotreatment of steam cracker heat integration.
The invention provides a kind of method,, can use the hydrotreatment that contains residual oil fraction to flow out thing as steam cracker feed stock through this method.The contriver finds that also crude oil or its cut that contains Residual oil can carry out hydrotreatment, so that as steam cracker feed stock.The raw material that contains Residual oil of hydrotreatment can carry out steam cracking, to produce useful product such as alkene and/or aromatic hydroxy compound.The hydrogenation and the steam cracking that the present invention relates to contain the material of Residual oil are integrated to obtain the method for olefin product.
One embodiment of the invention are by comprising crude oil or contain the method for feedstock production alkene of the crude oil fractions of Residual oil, and this method comprises hydrotreating step, viscosity breaking step and thermally splitting step.This method and apparatus can only be got rid of the Residual oil component of heavy and least desirable feedstream, and only the component of vaporization is transported to (it comprises the vaporized component that is obtained by Residual oil) radiation section of steam cracker basically.
In the preferred embodiment of any aforesaid method, before the steam cracking step, have the viscosity breaking step and/or have the vapor liquid tripping device of integrating with pyrolysis oven, for example viscosity breaking device.Viscosity breaking can be carried out in the vapor liquid tripping device of integrating, thereby does not need independent common viscosity breaking technology or equipment.
Another preferred embodiment is a kind of method; It is included in the step of hydrogenation the cracking of a part of Residual oil component; From Residual oil hydrotreatment unit, obtain elute, with the elute viscosity breaking, and the radiation section that will be transported to steam cracker from the top product of viscosity breaking step.Here viscosity breaking once more can be in the vapor liquid tripping device of integrating or in the viscosity breaking device that separates with steam cracker, is carried out.
In a preferred embodiment; This method further comprises the fractionating step of an integration; For example raw material is being transported to before the unitary radiation section of steam cracker through using flash drum from raw material, to remove bituminous matter and/or the cut of remaining boiling point 1050 ℉ (about 566 ℃) more than, preferably only boiling point be higher than 1100 ℉ (about 593 ℃) those remain cuts.Surprisingly, do like this and can make scaling rate be parity with or superiority over the scaling rate of VGO steam cracker feed stock.Preferably, choke at least one flash drum or other flashing apparatus such as the pipeline is provided, or orifice plate, to reduce the pressure in the hydrotreater elute and to cause that some liquid are converted into steam.Preferably, the charging of flashing apparatus and steam cracker pyrolysis unit is integrated.Integration is meant heat integration, makes that can and/or from steam cracker, obtain heat from one or more steps (for example between the warming up period of hydrotreatment, convection zone) of this method is used for conversion, cracking, flash distillation and separating technology.In preferred embodiments, the pressure of the elute of hydrotreater is flashed releases or lowers, its at least one time in before separating or between separation period.Flash distillation also comprises elute is incorporated into very aerial possibility.
In a further preferred embodiment, the present invention includes the method that hydrocarbon feed that preparation contains Residual oil is used for steam cracking.The inventive method comprises the raw material hydrotreatment with raw material hydrogenation in one aspect, thereby improves the hydrogen saturation ratio of cracking elute.The inventive method further comprises through in the viscosity breaking device, further handling the hydrotreater elute that contains Residual oil improves the hydrotreater elute that contains the hydrogenation Residual oil to reclaim the improved steam elute that contains Residual oil that from viscosity breaking method, obtains with undesirable elute thermally splitting with in Vapor-Liquid Separator (that for example can in the viscosity breaking separation method, use is the sort of).The present invention includes through integrating viscosity breaking and/or separate the material that viscosity breaking handles and further improve the quality of raw material in viscosity breaking device of more preferably integrating with the convection zone of steam cracker and/or the Vapor-Liquid Separator with steam cracker.
In an embodiment of various embodiments of the present invention, wherein elute obtains from Residual oil hydrotreatment unit, and charging comprises the crude oil fractions that does not have fractionated crude oil or contain Residual oil for the unitary feedstream of Residual oil hydrotreatment.In another embodiment, hydrotreatment uses at least one fixed bed hydrogenation reactor drum, boiling reactor or fluidisation hydrogenation reactor before pyrolysis unit is given in charging, to carry out.
In other embodiments; Want the raw material of hydrotreatment to comprise in recycled vapour cracker tar, heavy crude or the topped oil one or more, the raw material of steam cracking to comprise recycled vapour cracker tar, heavy crude or the topped oil of hydrotreatment.In a further preferred embodiment, the hydrogen source that is used for hydrotreatment is from remote methane.
Some embodiment preferred also comprise the combination of two or more above embodiments (comprising preferred embodiment).In still another preferred embodiment; Raw material such as desalination or the whole crude of desalination not; Or the product of refinery pipe still; Or containing chemical intermediate stream such as the normal pressure Residual oil or the decompression residual oil of bituminous matter or Residual oil, or the tar of steam cracking uses fixed bed hydrogenation reactor drum or boiling or fluidisation hydrogenation reactor to carry out hydrotreatment before giving the pyrolysis unit that has with the vapor liquid separating device of its integration in charging.
The invention still further relates to and comprise hydrotreater, pyrolysis unit and at least one viscosity breaking system with the vapor liquid separating device; Wherein the vapor liquid separating device is advantageously integrated with pyrolysis unit, also relates to a kind of method that the raw material charging that contains Residual oil is comprised the product of light olefin (one or more C2-C6 alkene) with acquisition that comprises.In preferred embodiments, this system comprises that further being used for methane conversion is hydrogen so that the steam reformer of hydrogen is provided for hydrotreater.An object of the present invention is Residual oil is supplied with the olefin production merchant as preferred charging, therefore can use low-quality crude oil material.Another object of the present invention is to improve the hydrogen richness of steam cracker feed stock, reduces the increase of raw material Residual oil content simultaneously to greatest extent.
Can know these and other purpose, feature and advantage with reference to following detailed description, preferred embodiment, embodiment and accompanying claims.
Description of drawings
In institute's drawings attached, reference number, label or other mark of expression parts or technology component are used to represent same parts or component.
Fig. 1-the 6th explains the process flow sheet of some exemplary of the present invention.
Embodiment
In one embodiment; From hydrotreater; Preferred resid hydrotreater contain Residual oil, further fully cracking of initial stage thermally splitting elute (it comprises that those residual oil fractions that boiling point is lower than 1050 ℉ (about 566 ℃) and preferred boiling point are lower than those residual oil fractions of 1100 ℉ (about 593 ℃)); For example in viscosity breaking device/separator, and as the raw material of steam cracker or other pyrolysis unit.In pyrolysis unit, the cut of vaporization is converted into required product, and it comprises alkene.Here term pyrolysis unit and steam cracker have same implication; All be meant the device that is commonly referred to steam cracker, even steam is chosen wantonly.
According to the present invention, crude oil or its cut fraction hydrogenation that will contain Residual oil are handled.Usually can be according to Residual oil hydrotreatment of the present invention at least 600 ℉ (315 ℃), preferably at least 650 ℉ (343 ℃) more preferably carry out under the temperature of at least 750 ℉ (399 ℃).Preferably, pressure is 1800psig at least.Purpose is in step of hydrogenation, to cause the thermally splitting of at least a portion of 650 ℉+(343 ℃+) Residual oil, for example initial stage thermally splitting.This processing of heavy crude or heavy still bottoms cut possibly need the temperature of at least 750 ℉ (399 ℃+) to cause the thermally splitting of lightweight residual oil fraction usually.Therefore, in some embodiments of the inventive method, the unitary initial stage thermally splitting of hydrotreater temperature is at least 750 ℉ (399 ℃), or at least 780 ℉ (451 ℃), and in other embodiments, this temperature must be at least 800 ℉ (427 ℃).Preferred processing temperature scope can be that 650 ℉ (343 ℃) are to 900 ℉ (482 ℃).Other alternative embodiment according to the inventive method; Hydrotreatment can be at 500 ℉ (260 ℃) to 900 ℉ (482 ℃); Preferred 650 ℉ (343 ℃) are to 900 ℉ (482 ℃); More preferably 700 ℉ (371 ℃) are to 900 ℉ (482 ℃), and more preferably 750 ℉ (399 ℃) are to 900 ℉ (482 ℃), and also more preferably 750 ℉ (399 ℃) carry out under the temperature of 800 ℉ (427 ℃).In some embodiments, preferred pressure is 500-10,000psig, preferred 1000-4000psig, also more preferably 1500-3000psig.The temperature of selecting can change according to the composition and the condition of hydrocarbon feed.Preferred liquid hourly space velocity can be 0.1-5, preferred 0.25-1.The hydrogen delivery rate of hydroconversion zone (replenish and recycle hydrogen) can be 500-20, and 000 standard cubic feet per barrel hydrocarbon feed is preferred 2,000-5,000 standard cubic feet per barrel.Hydrotreatment can be adopted a district or a plurality of hydrotreatments district, and for example two or more parallel connections or placed in-line hydrotreatment district carry out.For example; In one embodiment, first district can comprise first catalyzer, and it can be designed as the most metal of from raw material, removing of accumulation; Placed in-line second district can comprise second catalyzer, and it can be designed at utmost remove heteroatoms and aromatic hydrocarbons hydrogenation.In another embodiment; First catalyzer can be designed as the most metal of from raw material, removing of accumulation; Second district with second catalyzer can be designed at utmost remove heteroatoms, and the 3rd district with the 3rd catalyzer can be designed as increases aromatic hydrocarbons hydrogenation.First and second catalyzer can load with pipeline in placed in-line reactor drum, and perhaps series connection is loaded in same district.Design details does not become key component of the present invention, and this is because it only relates to resid hydrotreater.
The catalyzer that uses in the typical industry hydroconversion zone is formed by having active material of hydrogenation-dehydrogenation and amorphous carrier.Exemplary amorphous carrier comprises aluminum oxide, silica-alumina, silica, zirconium white or titanium oxide.The hydrogenation-dehydrogenation component of catalyzer preferably includes hydrogenation component and the hydrogenation component at least a VIII of being selected from family's metal and the VIII family metallic compound at least a VI of being selected from family's metal and the VI family metallic compound.The preferred combination of hydrogenation component comprises nickelous sulfide and moly-sulfide, cobaltous sulfide and moly-sulfide, cobalt and molybdenum, and nickel and tungsten.The catalyzer that uses among the present invention can also be by forming without the active material of hydrogenation-dehydrogenation that has of amorphous carrier preparation.Exemplary catalysts is drawn together Nebula.
According to the present invention, the Residual oil hydrotreatment can preferably be carried out under the temperature and pressure stricter than common hydroprocessing process.In one embodiment, hydrotreatment preferably can be more than 650 ℉ (343 ℃) and the temperature that in hydrogenation process, produces significant hydrocarbon cracking at the most, and for example 750 ℉ (399 ℃) carry out to 800 ℉ (427 ℃).This has not only produced hydrogenation Residual oil component, and with the cracking of most Residual oil component or be decomposed into light ends.Light ends helps in the steam cracker with the steam of injection, for example the further vaporization and the thermal treatment of conversion, cracking and the steam in the cracker pipeline.
The Residual oil hydrotreatment comprises any method of hydrogenant that causes Residual oil basically and/or contain the cut of Residual oil, and includes, but is not limited to commercial Residual oil hydrotreatment technology.The instance of these commercial methods is H-Oil methods, Chevron RDS, VRDS, OCR and LC-Fining method, HYVAHL method and ENI-Snamprogetti EST method.The hydroprocessing process that is fit to can comprise for example fixed bed catalyst system, liquid bed system, fluidized-bed system and/or their combination.The employed hydrotreatment of this paper also comprises some gentle crackings of 650 ℉+(343 ℃+) Residual oil component of hydrocarbon feed; Preferred in addition from 650 ℉ (343 ℃) to 1100 ℉ (593 ℃) boiling point fraction, more preferably 650 ℉ (343 ℃) are to some crackings of 900 ℉ (482 ℃) cut.
The hydrogenated raw material of hydrotreater is further fractionation or vaporization then, and all steam cracker is given in charging again.In the steam cracker system, can take place to vaporize completely basically.The combination of separator, flash separator and/or separating tank can provide between hydrogenation and cracking as required.In preferred embodiments, separating technology can with heating and cracking technology, for example integrate with steam cracker.For example, steam-liquid trap or separating technology can be in the convection zones of steam cracker or between the convection zone of cracker and radiation section, are provided.
The Residual oil hydrotreatment preferably includes whole crude or contains the hydrogen richness increase 1wt% at least of the crude oil fractions of Residual oil, preferably increases 1.5wt% and most preferably reaches from the effusive feedstream of hydrotreater near saturated or saturated fully.In some embodiments, maybe be preferably, the elute of hydrotreater has above 12.5wt%, more preferably surpasses the hydrogen richness of 13wt%.The hydrogen richness that improves whole crude, crude oil fractions or other raw material can be used to make their hydrogenated products to be suitable for charging and be used for cracking to pyrolysis unit, thereby produces more valuable end product, like alkene.Thereby can using more cheaply, steam cracker feed stock is used to produce alkene.The raw material of the lesser value that is fit to can comprise heavy crude usually, has those hydrocarbon feeds of high density Residual oil, high-sulfur, high TAN, high aromatic hydrocarbons and/or low hydrogen content.The hydrogenation of crude oil or crude oil fractions and the removal of pollutent can help with this elute charging give can the rejection feedstream heavy component such as the steam cracker system or the device of bituminous matter and 1100 ℉+(593 ℃+) cut.(it comprises the residual oil fraction of vaporization to the residue elute; 650 ℉ of cracking and vaporization (343 ℃) for example, up to 1050 ℉+(565 ℃) cut, even until 1100 ℉+(593 ℃+) cut; Until with the low boiler cut that comprises some 1400 ℉ (760 ℃) cut and vaporization) charging is used for strict cracking for the radiation section of steam cracker and produces valuable petroleum chemicals; For example alkene does not have undesirable fouling, and does not produce undesirable tar and coke.
Surprisingly, the carrying out of this method can not can cause the tar and the by product that contains Residual oil of equipment scaling out of control or undesirable real estate growing and high yield amount.Also have, surprisingly, the petroleum chemicals yield that complete hydrogenant crude oil can be vaporized fully basically and cause increasing in steam cracker.Conversion and vaporization can also obtain the assistance of the flash of steam of steam booster.In addition, the hydrogenation of strictness can also significantly reduce the generation of steam cracker tar.
In preferred embodiments, select to want the hydrotreater elute of steam cracking to comprise that boiling point is the big cuts of 700 ℉ (371 ℃) to 900 ℉ (482 ℃).In a further preferred embodiment; If the hydrotreater elute contains Residual oil, it can at first be handled, to remove a part of Residual oil; Bituminous matter for example will be handled convection zone or radiation section that the material feeding that contains Residual oil with hydrogenant is given pyrolysis unit (steam cracker) afterwards.Discuss the method for preferably removing undesirable Residual oil part below.
The employed crude oil of this paper is meant from well head, production fields facility, transportation facilities or the effusive whole crude of other initial oil field processing facility, optional comprising through desalination, treatment step and/or in order in refinery, to carry out the crude oil that other required step of common distillation is processed.The employed crude oil of this paper is contained Residual oil by supposition, unless otherwise prescribed.
Crude oil fractions is obtained by the refinery pipe still usually.Though any crude oil fractions that is obtained by the refinery pipe still can be used for the present invention; But remarkable advantage provided by the invention is, still contains the crude oil or the crude oil fractions that are present in all or part of the initial Residual oil in the whole crude that is obtained by well head and can carry out hydrotreatment and the raw material that is used as steam cracker subsequently.In one embodiment, charging can comprise 1wt% Residual oil at least for the unitary crude oil of hydrotreatment or other raw material, preferred 5wt% Residual oil at least, more preferably 10wt% Residual oil at least, also more preferably 20wt% Residual oil at least.
The employed Residual oil of this paper is meant the compounding mixture of the heavy crude compound that is called residual oil or residue in this area in addition.Atmospheric resids is the bottoms of when the end points nominal of the product of distillation of heavy is 650 ℉ (343 ℃), in air distillation, producing, and is called as 650 ℉+(343 ℃+) Residual oil.Decompression residual oil is the bottoms that when the product of distillation nominal of heavy is 1050 ℉ (565 ℃), is obtained by the tower under vacuum, is called as 1050 ℉+(565 ℃+) Residual oil.(word " nominal " is meant that here sensible expert possibly have different opinions to the definite cut point of these words, but possibly be no more than+/-50 ℉ (or ℉) at the most+/-100.This 1050 ℉+(565 ℃) part contains bituminous matter, and they are considered to the unfavorable factor of steam cracker traditionally, cause the corrosion and the fouling of device.Term as used herein " Residual oil " is meant 650 ℉+(343 ℃+) Residual oil and 1050 ℉+(565 ℃+) Residual oil, unless otherwise prescribed; Notice that 650 ℉+(343 ℃+) Residual oil comprises 1050 ℉+(565 ℃+) Residual oil.According to the present invention; 650 ℉ of at least a portion+(343 ℃) Residual oil until at least 1050 ℉+(565 ℃) boiling point fraction, are vaporized; For example in (i) hydrotreatment process; (ii) when combining with steam, and/or (iii) between hydrotreater and steam cracking, for example pressure is lowered or flash distillation when releasing in flash separation.
Residual oil can also contain a high proportion of undesirable impurity usually, for example sulphur and nitrogen and HMW (C12+) naphthenic (pressing TAN according to ASTM D-664 measures).Another advantage of the present invention is easily to handle the raw material that contains one or more a large amount of these impurity.As a kind of instance of concrete impurity, a large amount of sulphur may reside in many ring heterocycles.Contain the Residual oil of these materials through hydrotreatment, not only sulphur is as H 2S is removed, and heterocycle is opened, and produces a large amount of mononuclear aromatics materials, and they itself are valuable commodity usually, still preferred steam cracker feed stock.
Term as used herein " hydrotreatment " is defined as processing hydrocarbons raw material under the existence that is included in hydrogen with hydrogenation or cause those methods of hydrogen and at least a portion raw material reaction in addition.This preferably also heats the method for the step of the hydrocarbon feed stream that contains Residual oil including, but not limited under the existence that is included in hydrogen in hydrotreating step under pressure.Hydrotreatment can also be including, but not limited to the method that is called unifining, hydrotreatment, hydrogenating desulfurization (HDS), hydrodenitrification (HDN), hydrogenation deoxidation (HDO), unifining and hydrogen cracking.
Term as used herein " steam cracker " also more generally is called pyrolysis unit or thermal decomposition furnace or pyrolysis oven.Though steam is chosen wantonly,,, control the residence time and/or reduce coke formation to greatest extent for example in order to reduce hydrocarbon partial pressure usually because of one or more former thereby interpolations.In preferred embodiments, steam can be superheated, and for example in the convection zone of pyrolysis unit, and/or steam can be tart or the process steam handled.
Usually before raw material being transported to pipe still, carry out desalination.When the Residual oil from pipe still will carry out hydrotreatment, it usually was the secondary desalination that the crude oil material of refinery is given in charging.For example NaCl of metal-salt is removed in desalination usually.Yet one or more impurity that the crude oil of desalination and crude oil fractions still can contain relative high density are naphthenic acid, sulphur and/or nitrogen for example.Another advantage of the present invention is, one or more crude oil and the crude oil fractions that contains this naphthenic acid, sulphur and/or nitrogen impurity is easy to handle.
In preferred embodiments; Wherein raw material comprises 1050 ℉+(the 565 ℃+) Residual oil that contains more amount; For example 10wt% or more Residual oils; Or the crude oil of 20wt% or more Residual oils or atmospheric resids, the raw material that contains Residual oil can be transported to the convection zone of pyrolysis installation after hydrotreatment, and it is heated there.Then, can the raw material of heating be transported to viscosity breaking device or other vapor liquid tripping device to remove the cut (for example mainly being bituminous matter and 1050 ℉+(565 ℃+) cut) of heavy.Preferably, this device is a heat integration.Heat integration is that viscosity breaking device or separator provide additional efficient.
Except the initial thermally splitting of the residual oil fraction that takes place during the hydrotreatment, most additional cracking, conversion and flash separation occur in viscosity breaking device/separator.This further cracking causes with transforming through applying, thereby reduce coking to greatest extent or coking is controlled to acceptable level the duration of contact that unusual high separating/viscosity breaking temperature reaches unusual weak point.When the raw material that contains Residual oil in convection zone, be heated to be lower than 650 ℉ (343 ℃) and even when only reaching 700 ℉ and raw material at the most and in liquid-steam separator, having than short residence time(SRT); Thermally splitting is rare to not taking place; The molecule of mostly just under these conditions, vaporizing can be separated; For example, common non-Residual oil class component.Yet; When the raw material that in convection zone, contains Residual oil according to the present invention is heated to more than 700 ℉ (371 ℃); When preferred 750 ℉ (399 ℃) are above; Also more preferably 780 ℉ (415 ℃) are above and when in liquid-steam separating device, having than long residence time, a large amount of further thermally splitting has taken place residual oil fraction.In order at utmost Residual oil to be converted into low boiler cut, hope in technology, to begin as early as possible the cracking residual oil fraction.According to the present invention, in the hydrotreatment unit, cause early stage thermally splitting, in viscosity breaking/separating step, support then the raw material of vaporization partly to be maximized further thermally splitting.According to theory, help or promote Residual oil further fracture, cracking and/or be converted into low boiler cut at the low boiler cut of the early stage increased concentrations that produces of technology.This comprises that boiling point reaches and surpass the residual oil fraction of 1100 ℉+(593 ℃) cut, even a part is up to the conversion and the cracking of the residual oil fraction of 1400 ℉ (760 ℃).
When the unitary elute of hydrotreatment is heated (comprising reheat) to more than 780 ℉ (415 ℃); For example 780 ℉ (415 ℃) are to 900 ℉ (482 ℃) and when in viscosity breaking device or other separator, handling; Still also have the thermally splitting of 650 ℉+(343 ℃+) residual oil fraction to take place, comprise that boiling point ranges up to and beyond those residual oil fractions of 1050 ℉+(565 ℃).Under the higher temperature near 900 ℉, the residence time can foreshorten to than prior art hydrotreatment or Residual oil hydrorefined duration of contact shorter duration of contact usually.
Surprisingly, in unconverted 1050 ℉+(565 ℃) Residual oil, take place like this and do not form a large amount of coke, fouling or solid.This type thermally splitting and vapor liquid sepn process can be described to " viscosity breaking ".Preferably, separation and heating are integration methods.Term as used herein " integration " is meant that " heat integration " is that vapor liquid separating device or viscosity breaking device pass through pipe connection in steam cracker; And it is adjacent with steam cracker or relatively near steam cracker; Make raw material in the convection zone of cracker, to heat; The viscosity breaking device is given in charging, then with the top product of viscosity breaking device back into giving cracker, have like this minimal heat loss with preferably need separately relevant heating with the viscosity breaking process.
The vapor liquid separating device is called as " viscosity breaking device " in addition, and " separator tank ", " separating tank " and " vapor-liquid separator ", these terms can exchange use.Also mention at this paper by " viscosity breaking device ", it is as the vapor liquid separating device, and distinguishing characteristics is that it is operated under than the higher temperature of some other separators usually, also helps the further thermal destruction and the cracking of raw material.Term " flash drum ", " flash tank ", " viscosity breaking device ", " Vapor-Liquid Separator " and " flash separator " also are the known terms that has similar meaning usually, can exchange use basically here.For example, separating tank can also be called as viscosity breaking device, perhaps steam-liquid trap.Term " flash distillation " typically refers to through decompression and/or heats up, and at least a portion material in container or the logistics gets into the change mutually that becomes steam from liquid.Therefore, " flash separation " can in " flash drum ", take place owing to the import of flash drum or the decompression in the flash drum.
In a more preferred embodiment, this material is handled through viscosity breaking or gentle thermally splitting, to improve the ratio of vapor phase through the sacrifice bottoms.In some separation methods, for example in HP separator and/or flash separator, starting material can also be separated into bottom fraction, and it is liquid distillate basically, and overhead fraction, and it is the vapor phase cut basically.Bottom fraction or liquid phase can comprise residual oil fraction therein.Vapor fraction can also contain the component that derives from residual oil fraction.Preferably, bottom fraction and vapor fraction elute contain the component that derives from residual oil fraction separately, though the composition of the residual oil fraction of bottom elute is different from the steam elute.Thereby each of vapor stream and bottoms can be carried out steam cracking.
Viscosity breaking is known, non-catalytic, gentle method for thermal cracking, and it uses heat that heavy hydrocarbon oil and Residual oil conversion or cracking are light component more, more valuable sometimes product, and NO for example, overhead product and tar, but heat is unlikely to cause carbonization.Hydrocarbon feed can be heated to temperature required under required pressure, for example in stove or cracking reaction container.Employed method can be a coil-type for example, and it is used for high temperature-short residence time(SRT), perhaps cracking reaction method, and it is used for low temperature-short residence time(SRT) processing, optionally obtains the product mixtures of required fracture.Hydrocarbon feed stream can carry out thermally splitting, to lower the viscosity and the chain length of hydrocarbon molecule through cracking molecule in liquid phase.For example referring to Hydrocarbon Processing, in September, 1978,106 pages.When in quenching with heavy hydrocarbon before the stopped reaction or Residual oil at high temperature, viscosity breaking down during the thermally splitting several minutes, has taken place to 900 ℉ (371 ℃ to 482 ℃) in common 700 ℉ (371 ℃).Some cracking of Residual oil molecule or fractures, the component that generation can be removed through standard atmospheric pressure and vacuum distilling.Residual oil transformation efficiency in the viscosity breaking device increases with increasing with the increase of the residence time of temperature.The HS viscosity breaking makes the transformation efficiency maximization of 1050 ℉+Residual oil, through with viscosity breaking device raw material be higher than 840 ℉ (450 ℃) down cracking reasonably maximum duration accomplish, and do not form a large amount of coke or carbonization.
A critical aspects of the present invention surprisingly; Crude stream that contains Residual oil or cut with at first strict hydrotreatment; Like the saturated and most Residual oil of height hydrogen cracked crude oil; Compare with the heavy crude of not hydrotreatment, can obtain to be higher than the viscosity breaking transformation efficiency of previously known.Improved viscosity breaking method of the present invention and characteristic it is believed that owing to the high hydrogen richness of the Residual oil of hydrotreater elute part with owing to the increase of the light ends that initial cracking produced that in method for hydrogenation, carries out.
In a preferred embodiment of the invention; Cause especially strict viscosity breaking; For example take place in vapor liquid separating device (viscosity breaking device) in the viscosity breaking that surpasses under the temperature of 800 ℉ (427 ℃), preferably this equipment and steam cracker are integrated (heat integration) as stated.The vapor liquid separating device of integrating can whenever biweekly be discharged materials flow to remove coke.This can make this separating device with the coking yield operation obviously higher than typical viscosity breaking device; This typical case's viscosity breaking device possibly move some months between for the shut-down of removing coke, part is because the complicacy and the required time of the decarbidizing of this system at least.The vapor overhead product of viscosity breaking (it comprises the cut from the cracking Residual oil) can charging be given steam cracker then, and being used for further cracking is the other products that comprises stream of light olefins.
Though lightweight viscosity breaking Residual oil molecule (especially boiling point is lower than the Residual oil material of 750 ℉ (＜400 ℃)) is vaporized without additional processing, steam stripped possibly be necessary and helpful for the vaporization of heavy viscosity breaking molecule (for example its boiling point surpasses 750 ℉ (＞400 ℃)).Viscosity breaking reaction is enough fast, feasible can be with purging steam and/or light hydrocarbons joins in the vapor liquid separating device, with the molecule of stripping viscosity breaking.This has increased the ratio of the hydrocarbon of vaporizing in steam-fluid separation device.Heating can also be used to improve the Residual oil transformation efficiency.
Viscosity breaking can be controlled through the residence time that changes liquid phase in the vapor liquid separating device.Therefore in a preferred embodiment, the liquid phase level can be increased to the headspace of filling the vapor liquid separating device basically, and residence time of Residual oil molecule being increased to is enough to influence the degree of part viscosity breaking at least.Preferably, half at least (50%) full of liquid of viscosity breaking device, more preferably at least 75% full of liquid, in certain embodiments, at least 90% full of liquid most preferably is a benchmark in the TV of this container.Heating can also be quickened the viscosity breaking in the liquid phase, and its liquid residue is collected in the bottom of steam-fluid separation device as bottoms.In one embodiment of the invention, the well heater in the hypomere of steam-fluid separation device and the convection zone of steam cracker furnace are united use, if desired, and so that additional heat to be provided.Additional heat can help to keep enough heat of Residual oil, transforms to continue reaction and to make 750 ℉ (399 ℃) reach significant viscosity breaking to 1050 ℉ (565 ℃) Residual oil.
The integration of preferred vapor liquid separating device or flash drum and they and pyrolysis unit had description in the past in US patent application publication number 2004/0004022,20040004027 and 2004/0004028, recently in 10/851 of the US application serial submission on May 21st, 11/068,615,2004 of submission on February 28th, 2005; 10/851,878 of the submission of submitting on May 21st, 486,2004 on May 21st, 10/851,546,2004; 10/851 of the submission of on May 21st, 10/851,494,2004 of submitting on May 21st, 2004 on May 21st, 10/851,487,2004; 10/851,730 of the submission of submitting on May 21st, 434,2004 on May 21st, 10/851,495,2004; 11/134,148 of the submission of submitting on May 21st, 2004 on May 20th, 10/851,500,2005; 10/891,795 of the submission of submitting on October 28th, 2004 on July 14th, 10/975,703,2004; 10/893,716 of the submission of submitting on July 14th, 2004 on July 16th, 10/891,981,2004; 11/177,076 of the submission of submitting on December 10th, 2004 on July 8th, 11/009,661,2005; With submitted on September 20th, 2005 11/231,490 in description is arranged.Another kind of effectively as the preferred embodiment of steam-fluid separation device of the present invention at US patent No.6, be described to " vapour/liquid separator " in 632,351, for example the viscosity breaking device.Viscosity breaking is in above-mentioned US patent Nos.10/851,486; 11/134,148; Argumentation is arranged in 11/009,661.
In the method for the invention; Viscosity breaking device or steam-fluid separation device preferably at 700 ℉ (371 ℃) to 900 ℉ (482 ℃); More preferably 750 ℉ (399 ℃) are to 900 ℉ (482 ℃), also more preferably 780 ℉ (415 ℃) to 900 ℉ (482 ℃) and most preferably 800 ℉ (427 ℃) under the temperature of 875 ℉ (468 ℃), operate.Let the material that contains Residual oil of hydrotreatment and partial cracking through steam-liquid separation drum,,, can also be called " flash distillation " (or other variant, depend on context) here to obtain overhead vapor and bottom liquid simultaneously by its some pressure drops of experience.
Another aspect of the present invention relates to the api gravity and the sulphur content of steam cracker raw material.Be known that steam cracker raw materials quality is along with the reduction of the increase of the api gravity of raw material and sulphur content and improve.The wonderful discovery of the inventor is rich in sulphur and is rich in the raw material (it often has lower api gravity) of the polynuclear aromatic hydrocarbons of high boiling point polycyclic ring alkane, polynuclear aromatic hydrocarbons and fractional saturation, when hydrotreatment at first, can be the preferred feedstock of steam cracker.
This area also is well known that, the proportion of crude oil and sulphur content increase and increase with boiling point.For this reason, being rich in the raw material from the decompression residual oil of crude oil with 15-40API proportion and 1-4wt% sulphur possibly be some preferred raw material of the inventive method.The Residual oil hydrotreatment removes desulfuration in the whole boiling range of raw material.A large amount of hydrogen are consumed, and from decompression residual oil, remove heteroatoms, and make the polynuclear aromatic hydrocarbons that contains in the decompression residual oil saturated.The Residual oil hydrotreatment can turn to the cracking of Residual oil Journal of Molecular Catalysis and hot tearing can pass through standard fractionating process components separated.At first, the contriver seeks and obtains to be higher than 50%1050 ℉+transform and the be higher than Residual oil hydroprocessing condition of 90% desulfurization.The contriver has invented a kind of method astoundingly; Wherein 1050 ℉+conversions in the Residual oil hydrofinisher (resid hydrotreater) are unnecessary, this be because this function can ground through in the step viscosity breaking of Residual oil hydrofinisher elute being realized separately.
The Residual oil hydrotreatment is being used for pre-treatment atmospheric resids (it contains the 25-35wt% decompression residual oil) in other method of refining in the industry, so that as the unitary raw material of FCC.In the method, the coking yield of the Residual oil of hydrotreatment 5-8wt% normally.This means that charging is converted into the liquids and gases hydrocarbon product for the Residual oil hydrofinisher of integration and the 92-95% of the unitary residual feedstocks of FCC, only 5-8wt% loses as the low value coke.
The contriver is surprisingly found out that, through Residual oil hydrotreatment, viscosity breaking and steam cracking are integrated to produce alkene, can obtain similar result.In the method for the invention, the Residual oil of hydrotreatment is by viscosity breaking, from the vaporization top product of viscosity breaking device by steam cracking.The contriver is surprisingly found out that this method has produced 6-9wt% viscosity breaking device bottoms (be similar to the coke of producing among the FCC, but be worth higher) and 91-94wt% steam cracker product.
In order to make full use of the viscosity breaking ability of the inventive method, preferred in embodiments raw material can contain the 20-50wt% decompression residual oil, some raw materials even can be whole crude.The Residual oil hydrotreatment has consumed a large amount of hydrogen.The contriver notices that hydrogen will be incorporated in the decompression residual oil raw material, produces the hydrotreatment that only can be used as oil fuel and flows out the thing material, and its value is lower than the value of required chemical (for example light olefin).As previously mentioned, a purpose of method of the present invention is to improve the hydrogen richness of steam cracker feed stock, reduces the increase of residue Residual oil hydrogen richness simultaneously to greatest extent, and this residue Residual oil is sold as low value oil fuel usually.The strict hydrotreatment and the integration of viscosity breaking have realized this purpose astoundingly.The side chain of high hydrogen richness is removed in viscosity breaking effectively from the nuclear of polycyclic ring alkane and aromatic hydrocarbons formation.Fouling in the viscosity breaking device was limited through the limit temperature and the control residence time, thereby had avoided the transition formation of coke or the fouling of equipment.
Crude oil or its cut that contains Residual oil, atmospheric resids especially, decompression residual oil or any Residual oil or bitum refinery or chemical intermediate stream of containing also can be the preferred feedstock of the inventive method hydrotreater.When raw material comprises when being higher than 0.1wt% or preferably being higher than the 5.0wt% bituminous matter, advantageously use the vapor liquid separating device before the radiation section that gets into pyrolysis unit, to remove bituminous matter.Preferably, as stated, vapor liquid separating device (viscosity breaking device) can be advantageously and the pyrolysis unit heat integration, makes raw material preheating in the convection zone at pyrolysis unit before getting into the vapor liquid separating device.Therefore, term " the vapor liquid separating device of integration " is just as employed that kind in this article.As substituting; Steam-fluid separation device can be basically not with the cracker heat integration; Make the viscosity breaking utensil that independence or the supplemental heat source of himself arranged, make bituminous matter and any unsaturated or uncracked residue be removed get into the radiation section of pyrolysis unit at raw material before.Integration and nonconformable configuration are all within the scope of the invention.
Preferred raw material can comprise hydrocarbon feed stream and crude oil fractions such as the topped oil (" topped oil " is cut and the more senior cut of about 500-600 ℉ (260-315 ℃)) with high density tar.Usually, topped oil and atmospheric resids synonym use.Then, any crude oil or the crude oil fractions that contains Residual oil can advantageously be handled obtaining chemical products (light olefin and/or mononuclear aromatics) according to the method for the invention, no matter wherein the content of Residual oil how.
Following examples are used for explanation and do not limit the present invention.Many transformations and modification are possible, it should be understood that within the scope of the appended claims, and enforcement of the present invention can be with institute be specifically described different here.
In following accompanying drawing; " HDP " is hydrotreater; " HPS " is high pressure separating device (for example, the groove with liquid level control of divided gas flow and liquid under pressure), and " steam cracker " is pyrolysis installation; And " recovery of steam cracker product " is to comprise one or common several separating step, the for example system of distillation tower.All these devices or system can be common units separately basically, and are well known in the art respectively.
Reference example property accompanying drawing, Fig. 1 are the process flow sheets of explanation one embodiment of the invention, wherein contain raw material 8 hydrotreatment in hydrotreatment unit 10 of Residual oil, are transported to steam cracker 20 then to obtain a plurality of product 41-44, and it comprises alkene 42.Steam cracker 20 design detailss own are not themes of the present invention.Processing conditions can be easy to confirmed by those skilled in the art usually.Unconventional steam cracking design as known in the art for example directly mixes the stove that heats with the liquid starting material that comprises Residual oil and also is used for the present invention described herein by contriver's consideration through crossing hot solids or gas.
An embodiment for preparing the inventive method of the raw material that contains Residual oil that is used for steam cracking comprises through raw material is being surpassed 700 ℉ (371 ℃); Preferably be higher than 750 ℉ (399 ℃), more preferably surpass hydrotreatment under the temperature of 780 ℉ (415 ℃) and strict hydrotreated feed.This method also comprises further improves the hydrotreater elute through the hydrotreater elute being kept, heats and further transforming in viscosity breaking device class steam-liquid trap.Preferably, viscosity breaking device and steam cracker heat integration.In heat integration method shown in Figure 1, atmospheric resids 8 is transported to common hydrotreater (HDP) 10, for example fixed bed hydrogenation treater.Many HDP unit can be commercial, especially changes with catalyzer and configuration, for example can buy from ExxonMobil.The design details of HDP itself is not a theme of the present invention.The processing conditions of HDP is easy to confirmed by those skilled in the art usually.Petroleum chemicals reclaim the influence that (light olefin and aromatic hydrocarbons) largely receives the processing conditions of selection in HDP 10, viscosity breaking device class Vapor-Liquid Separator 30 and the steam cracker 20.
The unitary hydrogenated raw material 14 of HDP is transported to one or more tripping device (not shown) then, to reclaim hydrogen, reduces pressure and reduces temperature.For example C2 and following logistics can recycling 12 to comprise hydrogen and lightweight carbon products, and the hydrogenation outflow logistics 14 that reclaims the product that comprises C2 boiling range (C2+) and more senior (for example reaching 1500 ℉) is used for further processing.Notice that in many cases, recirculation stream 12 can contain H 2S, it preferably was removed before getting into HDP unit 10, for example through film, absorption agent etc.The bottoms (not shown) of HPS can be divided into two or more logistics.Except being used for method of the present invention, this bottoms (not shown) can be recycled to resid hydrotreater 10, perhaps comes further processing through routine distillation and refining.
Still contain under the bitum situation at raw material 14, they can advantageously be removed before the radiation section that gets into steam cracker 20 24.Preceding text and following embodiment have more expounded the instance of removing bitum method adequately.Though in Fig. 1, be not shown specifically; But hydrogenation C2+ logistics 14 can preheating in the convection zone 22 at steam cracker 20 before getting into steam-fluid separation device 30, can be used as bottoms 32 and from steam-fluid separation device 30, removes if wherein comprise bitum (nominal) 1050 ℉+Residual oil of not removing in advance.Steam 34 turns back to convection zone 22, preferably need not cool off or condensation.The device that schematically is called " S/C stove " 20 among Fig. 1 is the common instance of steam cracker furnace, and its details neither theme of the present invention, and except the integration of vapor liquid separating device 30, it has description in other local reference of discussing of this paper.Separating device 30 preferably plays the viscosity breaking device is that equipment 30 separates, temporarily keeps and further heating is heated in advance in hydrotreater logistics.Thereby, in hydrotreater, cause initial cracking, produce some light ends, in the viscosity breaking device, cause follow-up cracking then.Through the lighting end that produces in the hydrotreater; The lighter molecules that additional viscosity breaking produces; The further additional steam that is injected into the viscosity breaking device and/or before the viscosity breaking device, injects, and optional through the flash distillation pressure drop, can realize vaporizing completely basically.Separator 30 is also preferred to be that with cracker 20 heat integrations this separator and steam cracker 20 are enough approaching, makes this separator preferably need not add or independent heating, to help the viscosity breaking class separation in the separator 30.Thereby, separator 30 can with steam cracker 20 " integration ".Pressure preferably was reduced to 50-100psig before isolating materials flow being transported to steam cracker.
Though in Fig. 1, be not shown specifically; But in a preferred embodiment; Hydrogenant C2+ logistics 14 is being enough to cause heating be transported to the vapor liquid separating device through pipeline 33 before under the temperature of thermally splitting of hydrogenation Residual oil in the convection zone 22 of steam cracker 20, wherein comprise bitum (nominal) 1050 ℉+Residual oil and remove from vapor liquid separating device 30 as bottoms 32.The steam (not shown) can add in the vapor liquid separating device, to increase the ratio of the raw material of removing as steam 34.Another aspect of the present invention is that for set treatment temp (especially high boiling point Residual oil), the liquid level in the rising viscosity breaking device separator can increase liquid residence time, thereby further improves the transformation efficiency of residual oil fraction.The viscosity breaking device comprises liquid distillate and the isolating steam of vapor fraction-liquid separation container or equipment, and wherein this separation vessel comprises at least 50% the liquid volume that preferably accounts for container volume.Preferably, the liquid level of separation vessel is equal to or higher than 75 volume % of container at least, also more preferably is higher than 80 volume %, most preferably is higher than 90% of container volume.
Steam 34 (it comprises the Residual oil molecule of (also being called destructive distillation) of thermally splitting) can turn back to convection zone 22.Like this, the convection zone 22 of steam cracker 20 can be converted into lighter molecules with 1050 ℉+decompression residual oil.Finally, oil fuel output lowers, and petroleum chemicals output (for example required light olefin and mononuclear aromatics) increases.If the temperature residence time too high or raw material is oversize, in hot viscosity breaking device steam-fluid separation device 30, can cause that coke forms.If this thing happens, this method can be filled coke undesirablely in steam-fluid separation device 30, and this need interrupt this method.In preferred embodiments, the temperature and the residence time in the control vapor liquid separating device 30 are only to allow a small amount of coking.For example, every at a distance from the 15-40 days steam crackers of can stopping work, with easily from radiation section 24, the pipeline of stove 20 and/or from separator 30, remove if necessary can the acceptance amount coke.Method of the present invention can adopt currently known methods and facility from the pipeline of the convection zone 22 of steam-fluid separation device 30 and steam cracker furnace 20 and radiation section 24, to remove coke.Because this synergistic effect between viscosity breaking and steam cracking; Method of the present invention can be under than the higher severity of common viscosity breaking device the Residual oil in the viscosity breaking raw material, conventional viscosity breaking device is designed to before the needs decoking, move some months.
The device that schematically shows among Fig. 1 to " S/C stove " 20 is the common instance of steam cracker furnace; Except the integration (Fig. 1 is not shown) of vapor liquid separating device; Its details neither theme of the present invention, and in the reference that other place of this paper is mentioned, description has been arranged.
In another embodiment, comprising whole or any cuts of the hydrotreater elute 14 of 1050 ℉+(565 ℃+) Residual oil can be in steam cracker 20 or be heated to through independent thermal source and be enough to cause thermally splitting but be unlikely to cause remarkable pyrogenic temperature.Cracked-stream can keep the sufficiently long time to arrive the transformation efficiency (that is, material is converted into the lower boiling material from the high boiling point Residual oil that comprises 1050 ℉ (565 ℃) Residual oil) of 60wt% (high severity) with the 5wt% (low severity) that obtains 1050 ℉+Residual oil under this temperature but be unlikely to cause significantly pyrogenic enough short period of time.The optimum temps of each concrete raw material all is different with the time (" time under certain temperature "), can be confirmed through normal experiment by those skilled in the art.Time under certain temperature is through with hot base material quenching and selectivity stops, to avoid fouling or coking.Based on present disclosure, those skilled in the art think viscosity breaking with this usually.In viscosity breaking steam-liquid separation step; Wherein (nominal) 1050 ℉+Residual oil and/or bituminous matter of not rupturing removed from steam-fluid separation device as bottoms; And all or part of viscosity breaking device steam elute 34 was transported to steam cracker 20 before getting into radiation section 24, preferably was transported to convection zone 22.Isolating steam is in further processing and cracking of radiation section 24, thereby acquisition comprises the steam cracker elute 26 of required light olefin 42.
A significant advantage provided by the invention is high severity hydrotreatment and the viscosity breaking through hydrotreater elute 14; Dispose before the steam cracker and have in the viscosity breaking device additional or thermal source separately no matter be; Or viscosity breaking device with the steam cracker integration; All can obtain high conversion; For example rich hydrogenous 750 ℉+(399 ℃+) Residual oil with in addition the most 50wt% at least of 1050 ℉+(565 ℃+) material, or even be higher than 50wt%, for example up to 55wt% with in addition up to 60wt%.Provide like this and had the steam cracker feed stock 34 (perhaps the raw material of radiation section 24 is given in charging, under the situation that the convection zone 22 of viscosity breaking device and steam cracker is integrated) that is higher than 13wt% hydrogen.The bottoms 32 of viscosity breaking equipment 30 can comprise in certain embodiments and is lower than 11.5wt% hydrogen, can and/or be recycled to hydrotreater as oil fuel, and perhaps for example catalytic conversion system of another processing unit is given in charging.
In the embodiment of schematic illustration, method of the present invention is integrated the Residual oil viscosity breaking 30 of Residual oil hydrotreatment 10, hydrotreatment and the step of steam cracking 20 in Fig. 6.Can carry out operating parameters of the present invention by operating routine viscosity breaking device, thereby distilled steam and/or liquid are separated with unconverted residual feedstocks.From resid hydrotreater 10 and/or viscosity breaking device 30 obtain distillate liquid and/or steam is handled steam cracker 20, to produce petroleum chemicals.The obvious advantage of at least one of this embodiment is need the convection zone of vapor liquid separating device and steam cracker 20 directly not integrated.
The product of steam cracker 20 is transported to steam cracker product recovery zone (Fig. 6 is not shown), can reclaims various products through distillation usually through separating there." chemical " logistics comprises ethene, propylene and butylene class.Separation itself is routine techniques and is not theme of the present invention.
Some modification is that those skilled in the art institute is conspicuous.For example, one or more steam-fluid separation devices can exchange with other separating device such as film, though and to integrate with steam cracker be a preferred embodiment, choose wantonly.Yet it is highly preferred before the radiation section of pyrolysis unit (steam cracker), removing bituminous matter.Film especially can be used for for example polar material being separated with apolar substance (for example, before the HDP unit).
In the embodiment depicted in fig. 6; Method wherein of the present invention is integrated the Residual oil viscosity breaking 30 of Residual oil hydrotreatment 10, hydrotreatment and the step of steam cracking 20, can operating routine viscosity breaking device be separated from unconverted residual feedstocks by distilled steam and/or liquid.From resid hydrotreater and/or viscosity breaking device obtain distillate liquid and/or steam is handled conventional steam cracker, to form petroleum chemicals.At least one significant advantage of this embodiment is need the convection zone of steam-fluid separation device and steam cracker directly not integrated.
Fig. 2 is the process flow sheet of explanation embodiment of the present invention, and the raw material 8 that wherein contains Residual oil carries out hydrotreatment 10 and carries 14 then to steam cracker 20, to obtain to comprise the various products of alkene.
In the embodiment of method shown in Figure 2, raw material 8 (it is atmospheric resids in preferred embodiments) is transported to conventional hydrotreater (HDP) 10, for example fixed bed hydrogenation treater.Once more, the design details of HDP itself is not a theme of the present invention.The exemplary process conditions of HDP step 10 is provided among Fig. 2, yet like what those skilled in the art recognized, these conditions can change and can confirm through normal experiment.The concrete raw material of physical condition basis of one or more HDP devices and/or required product and steam cracker condition and viscosity breaking device condition are integrated and are changed; But it is 2200 ± 500psig (total pressure) that good rising named a person for a particular job; 725 ± 100 ℉ (measuring) at reactor outlet, 3000 ± 200SCFB hydrogen of under 0.1-0.3WHSV, handling.
Hydrotreated feed 14 is transported to the HP separator of in Fig. 2 for example, operating under the defined terms 15; This condition also can change; And measure through normal experiment by those skilled in the art, depend on raw material with shown in the operational condition of other device in the system.Overhead stream 16 is through passing the interchanger 17 that round usual manner is represented with arrow, can be made up of for for example 650 ℉ or lower overhead product boiling point.Refrigerative overhead stream 18 can be transported among the 2nd HPS19 shown in Figure 2; Separate down this logistics like be shown in 90 ℉ point, with obtain to comprise the C3 material and more number of carbons material (comprising petroleum naphtha and heavy overhead product) bottoms 21 (it can be transported to steam cracker 20) and comprise hydrogen, methane, ethane and H 2The overhead stream 23 of S, overhead stream recycling is preferably for example being removed H through film, absorption agent etc. 2After the S.
In the exemplary of shown in Figure 2 and explanation, the bottoms 35 that obtains from a HPS15 can comprise the material of boiling point more than 650 ℉.In some embodiments, bottoms 35 can recycling or is mixed with the bottoms 21 of the 2nd HPS19, reduces pressure 55 then.In fact, usually a part of (for example 0-90wt% or 40-60wt%) recycling (not shown), a part 35 (for example 10-100wt% or 40-60wt%) mix and decompression.Cooled off liquid 35 with 90 ℉ liquid mixing, reduced the flash distillation amount that when decompression, takes place from a HPS15.
In another embodiment; What comprise Residual oil and for example vacuum gas oil (VGO) can preheating in the convection zone of steam cracker 20 from the merging liquid efflunent 14 of resid hydrotreater 10; To feed back to convection zone from the steam of steam-fluid separation device of integrating then; Introduce or be transported to the radiation section of steam cracker then, there by cracking.The bottoms from the vapor liquid separating device of integrating by 1050 ℉+fractions consisting (in this preferred embodiment) comprises bituminous matter.
The product 26 of steam cracker 20 can be transported to steam cracker product recovery zone 40, can reclaim various product 41-44 through distillation usually through separating there, and is as shown in Figure 2." chemical " logistics 42 for example comprises ethene, propylene and butylene class.Each steam cracker 20 can be integrated with the product retrieving arrangement 40 of itself, and perhaps single product reclaims unit 40 and can handle two steam cracker elutes 26,38.
Some modification it will be apparent to those skilled in the art that.For example, can increase other separating device, for example film or vacuum column.Film for example especially can be used for, and separating polar substance (for example separates with non-aromatic hydrocarbon substance with apolar substance (for example before the HDP unit) or with aromatic hydrocarbons; After the 2nd HPS unit in Fig. 2 and before steam cracker, non-aromatic hydrocarbons is transported to steam cracker and aromatic hydrocarbons is recycled to the hydrotreatment unit).
Fig. 3 shows another preferred embodiment of the present invention.Fig. 3 and Fig. 2 are similar; Just in Fig. 3; Be heated to 100-200 ℃ to keep the tar 44 from product retrieving arrangement 40 mobile, that be substantially free of metal and comprise few sulphur now can be transported to HDP10; Preferably use one or more 650 ℉+recirculation stream 23 and/or raw material 8, perhaps one or both part dilution of these materials.
Fig. 4 shows another embodiment of the present invention.Fig. 4 and Fig. 3 are similar, only provide the 2nd HDP unit 70, second interchanger 72 and the 3rd HPS unit 74.As shown in Figure 4, be transported to the 2nd HDP unit 70 from the material 76 (for example 400-650 ℉ (204-343 ℃) liquid) of the 3rd HPS unit 74 as raw material.Tar 44 optional the 2nd HDP unit 70 that are recycled to.Fig. 4 further uses steam-fluid separation device 25 (flash distillation among Fig. 4), so that 900 ℉-steam 36 is separated with 900 ℉+Residual oil 37.900 ℉-steam 36 (mixing with steam 31) can be delivered directly to conventional steam cracker 20, the steam-fluid separation device that need not to integrate.900 ℉+Residual oil 37 can be transported to comprise to carry out the steam cracker 50 of steam-fluid separation device 30 of the integration of viscosity breaking.Steam-fluid separation device 30 can be operated under various conditions, and this is easy to understood by those skilled in the art.In another modification (not shown), the tar 44 of a part can mix with atmospheric resids 8, and a part is mixed with the unitary bottoms 76 of the 3rd HPS.
Based on present disclosure, those of ordinary skill in the art will appreciate that, in any one of above-mentioned Fig. 1-4, the viscosity breaking device can be arranged in before one or more steam crackers.If the viscosity breaking step before pyrolysis step, according to the present invention, will be chosen wantonly with the vapor liquid separating device that pyrolysis oven is integrated.This can explain with reference to following examples and following other accompanying drawing.
With reference to figure 5, viscosity breaking is accomplished in the vapor liquid separating device of integrating with steam cracker 20 30.In the embodiment shown in fig. 5, crude oil distills under 1 normal atmosphere, reaches 600 ℉ (about 315 ℃) up to remaining oil.BO (Residual oil) is analyzed (referring to table 1).BO (Residual oil) mixes with hydrogen, through hydrotreater 10, under 0.2WHSV, 695 ℉ and 2000psig total pressure, handles.Analyze 14 (referring to table 1) of hydrotreater elute.The product liquid 14 of hydrotreater carries out vacuum distilling (Fig. 5 is not shown) then to isolate decompression residual oil.Distillation obtains 82wt% overhead product (1050-) and 18wt% decompression residual oil (1050+).Analytical results provides in table 1.
Can estimate result with 18wt% decompression residual oil viscosity breaking 30.Because the high hydrogen richness (12.5wt%) of raw material 14, before a large amount of coke began to form, the high conversion in the viscosity breaking device 30 was possible.Strict viscosity breaking produces the top product of the hydrogen richness with 13.5wt%H of the decompression residual oil that contains 10.8wt% hydrogen at the most and the 60wt% yield of 40% yield.Hydrogen (H) content of the viscosity breaking device top product that calculates is near the H content of distilled Residual oil unifining liquid.Therefore, can suppose, viscosity breaking device top product is joined in the distilled hydrotreatment liquid can significantly not change the steam cracking yield.Distillate material logistics 34 from the 93wt% of Residual oil hydrotreating step and can be used as steam cracker feed stock then.Table 2 provides the yield of steam cracking, and it is identical with the yield shown in Fig. 5 basically.The plant-scale operation of the experimental simulation of reporting among these embodiment, specification sheets as shown in Figure 5 and whole is described.
Table 1
The crude oil atmospheric resids The hydrotreater elute 1050- 1050+
Api gravity 17.8 27.0 30.0 17.5
Wt％H 11.3 12.9 13.1 12.5
Wt％S 4.2 0.15 0.01 0.3
Wt％C5- 0.0 3.0 5.0 0.0
Wt％C5-1050℉ 64.0 80.0 95.0 0.0
Wt％1050+ 36.0 18.0 0.0 100.0
Paraffinic hydrocarbons 16.0 27.0
Naphthenic hydrocarbon 19.0 39.0
Mononuclear aromatics 8.0 26.0
Double ring arene 15.0 7.0
Thrcylic aromatic hydrocarbon 17.0 2.0
Fourth Ring aromatic hydrocarbons 13.0 0.0
Table 2-steam cracking yield: hydrotreater 1050-liquid
The steam cracker yield, wt%
Fuel gas
10
Ethane/propane 5
Ethene 21
Propylene 13
C4’s 10
BTX 9
Other SCN 11
Tar and gas oil 21
Result in the table 1 shows that charging contains the material of boiling point more than 1050 ℉ of 36wt% for the raw material of Residual oil hydrotreating step.The product of hydrotreating step contains the material of boiling point more than 1050 ℉ of 18wt%.Conventional hydrotreatment causes 50% transformation efficiency of the decompression residual oil cut of raw material.This means that hydrotreatment and vacuum distilling have subsequently obtained to have the 18wt% decompression residual oil and has been suitable as the product of the liquid of steam cracker feed stock near 80wt%.The 18wt% decompression residual oil mainly is rich in hydrogen, but only can sell as low sulphur fuel oil, only if further handle.Hope to reduce the yield and the yield that improves steam cracker feed stock of low sulphur fuel oil.The viscosity breaking step is converted into steam cracker feed stock with 12.5wt%H, the 1050 ℉+hydrotreater elute of about 60wt%.Unconverted 1050 ℉+Residual oil unifining elute contains 10.8wt%H, and it is similar to the H content (11.3wt%) that the raw material of resid hydrotreater is given in charging.The combination of Residual oil hydrotreatment and viscosity breaking causes charging partly to have 80% total conversion rate for the decompression residual oil of the raw material of hydrotreater.7wt% low sulphur fuel oil (" Residual oil " among Fig. 5) has and the similar hydrogen richness of resid hydrotreater raw material, so in resid hydrotreater, almost there is not hydrogen consumption, the oil that acts as a fuel is sold to the human consumer.On the contrary, raw material carries out the Residual oil hydrotreatment viscosity breaking is carried out with uncommon high conversion.Also it is believed that to the viscosity breaking device resid feed of strict hydrotreatment is the significant advantage of former embodiment of the present invention of not recognizing in this area; Because unclear completely why it can be used for viscosity breaking according to raw material of the present invention, with in the prior art that this raw material charging is opposite to coker or FCC unit.
Those the similar raw materials that use and in last table, enumerate and the Residual oil hydrotreatment of condition are used for the Residual oil of pre-treatment as the unitary raw material of FCC.In the FCC unit, the coking yield that the Residual oil of hydrotreatment can 5-6wt% is converted into the liquids and gases product.Very surprisingly, Residual oil hydrotreatment and viscosity breaking subsequently and steam cracking have obtained similar total Residual oil transformation efficiency to the liquids and gases product.The by product of Residual oil hydrotreatment, viscosity breaking and steam cracking is low sulphur fuel oil (among Fig. 5 " Residual oil "), and it has obviously higher value than the coke on the FCC catalyzer.
Two key parameters of steam cracker feed stock are wt% hydrogen and wt% polynuclear aromatic hydrocarbons.Yield of ethene can be closely related with wt% hydrogen, and the tar yield can be closely related with the wt% polynuclear aromatic hydrocarbons.The product that the Residual oil hydrotreatment of Fig. 6 obtains has the typical hydrogen content of the common VGO that uses in the steam cracking field, but has lower polynuclear aromatic hydrocarbons concentration.
Have＞result of the steam cracking raw material of 20wt% aromatic hydrocarbons is the tar yield of 10-20wt%.Method of the present invention provides through tar being recycled to hydrotreater and has eliminated or significantly reduce the chance as the tar of product.Hydrogenation of tar and steam cracking subsequently can be converted into light-end products basically fully with tar.This is an ideal of method of the present invention, but just unnecessary aspect.The undesired in advance hydrotreatment of steam cracker tar.Expection has the problem of fouling, incompatible and low reactivity.
Though above embodiment uses atmospheric resids to explain that as raw material any crude oil or its cut can be benefited from the present invention.In preferred embodiments, raw material is selected from heavy crude, decompression residual oil, oil fuel, FCC turning oil, coker gas oil, cracker tar, topped oil and any other contains at least a in the raw material of Residual oil and/or high density polycyclic aromatic hydrocarbons material.The mixture of this raw material, the mixture that is for example provided by crude oil also is preferred.Fig. 1-6 only representes to relate to a few in the countless possibility prioritization schemes that reduce use of refinery energy and the effective use that improves hydrogen and hydrocarbon feed source to greatest extent to greatest extent.
As the other limiting examples (it possibly be preferred embodiment) of another embodiment of explanation, the hydrogen source that uses in the system (for example HDP unit) can be originated especially remote methane from methane.Remote methane at US patent No.6, has description in 784,329 as the purposes of hydrogen source.
The value that improves remote methane resource to greatest extent is an old problem in the industry.Though methane has the high-quality value that is used to produce hydrogen, the remote transportation of common any chemical is not economical.The source of using the under-utilized capacity of methane or other heavy body and/or the methane of far zone has the raw material hydrogenation of hydrotreater to be beneficial to from improving economically by steam cracking and produces valuable product.Word " remote " is not limited to distance, is comprised any basically suitable methane and/or hydrogen source but more be broadly defined as, and they possibly be not too valuable selection in said method or not have an opportunity to be used for said method very much.This is included in mass-produced methane from all parts of the world, possibly be limited, expensive or unsuitable coming into the market or limiting aspect the purposes.This methane can be converted into the hydrogen that is used for the inventive method.
Crude oil contains the hydrogen of minimum 10wt% usually.Fully hydrogenant crude oil (wherein crude oil only contains paraffinic hydrocarbons and naphthenic hydrocarbon basically, has＞transformation efficiency of the impurity of sulfur-bearing, nitrogen and the oxygen of 95wt%) can contain the nearly hydrogen of 14-15wt%.This saturated cracker raw material is highly preferred raw material in the present invention.Petroleum chemicals yield with crude oil of 14.5wt% hydrogen can significantly increase than the crude oil with 10-11wt% hydrogen.
Is that the facilitated method of hydrogen is to adopt steam reformer unit at remote place with methane conversion, and this unit can obtain from many commercial source.In steam reformation, light hydrocarbons such as methane and steam reaction form hydrogen and carbon monoxide.This reacts available known synthetic gas equilibrium equation and explains:
CH 4+H 2O《---》3H 2+CO
Usually, for example through being converted into lower paraffin hydrocarbons utilization with fischer-tropsch catalysts, it can charging give the petroleum naphtha cracker to produce ethene to synthetic gas.Yet according to the present invention, hydrogen can extract from equational product side, and is used for hydrogenation crude oil or its cut that contains Residual oil.Carbon monoxide can be in water gas shift reaction further with steam reaction, form other hydrogen (and carbonic acid gas).Other reaction can produce hydrogen by methane, and for example methane and oxygen react and formation hydrogen and carbon monoxide (partially oxidation).
The present invention therefore allow the manufacturer with hydrotreatment HDP unit near in the methane source (for example remote methane) arrange; To comprise the raw material hydrogenation (for example by being positioned near the remote methane well head or the transportation of materials through will containing Residual oil) of Residual oil, then the unitary product of HDP will be shipped to steam cracker (perhaps steam cracker being arranged in remote place, source) to remote methane place.
Except above those that point out, the present invention also provides many advantages.In preferred embodiments, the invention provides one or more following advantages: the raw material (1050 ℉ of raw material+Residual oil and/or polynuclear aromatic hydrocarbons and/or the content of heteroatoms height that (a) use least cost; Use the methane in remote place); (b) when will when the conversion in Residual oil hydrofinisher and the viscosity breaking device combines, having high total 1050 ℉+transformation efficiency; (c) low cost that comprises raw material and the steam cracker facility of hydrogen is integrated, and does not have transportation cost basically; (d) single charging has been simplified the pyrolysis unit design and/or has been safeguarded; (e) reduced the processing/handling problems of Residual oil/bituminous matter/sulphur and nitrogen multinuclear molecule (" bed material of oil drum "); (f) for the naphtha reforming of producing aromatic hydrocarbon product replacement scheme is provided.
Though described the present invention substantially with reference to specific embodiments; In preferred embodiments; The method that the present invention relates to comprise the following steps: (i) obtain under relatively stricter condition; For example, more preferably surpass the raw material of handling under the temperature of 750 ℉ (399 ℃) that comprises from the elute of Residual oil hydrotreater at preferred 700 ℉ (371 ℃) that surpass; (ii) this elute being separated (for example viscosity breaking) in separator is overhead stream and bottoms, and wherein overhead stream comprises steam; (iii) the overhead stream of viscosity breaking device is transported to the radiation section of steam cracker then; (iv) from steam cracker, obtain the elute that comprises alkene.
This can improve or improve through also preferred embodiments below one or more: wherein step is characterised in that (iii) the overhead stream with the viscosity breaking device arrives steam cracker as vapor, need not cool off or condensation; Step comprises that (iii) the overhead stream with the viscosity breaking device is transported to the convection zone of steam cracker, is transported to the radiation section of steam cracker then; Step (ii) comprises the convection zone that elute is transported to steam cracker, then in the vapor liquid separating device with the elute viscosity breaking; Step (ii) in, viscosity breaking device/vapor liquid separating device and steam cracker heat integration; Step (i) is further characterized in that the raw material hydrotreatment that comprises crude oil or crude oil fractions, thus the crude oil of acquisition hydrotreatment or the crude oil fractions of hydrotreatment, and wherein the crude oil fractions of hydrotreatment comprises Residual oil; Step (i) be further characterized in that have comprising＞20wt% or＞25wt%; Or＞30wt%1050 ℉+Residual oil and＞20wt% or＞25wt% or＞30wt% aromatic hydrocarbons and＜25wt% or＜20wt% or＜crude oil of 15wt% paraffinic hydrocarbons or the raw material hydrotreatment of crude oil fractions; With the crude oil of acquisition hydrotreatment or the crude oil fractions of hydrotreatment, wherein the crude oil fractions of hydrotreatment comprises Residual oil; Viscosity breaking carries out under the condition that is fit to that (common 700 ℉ (371 ℃) are to 900 ℉ (482 ℃); Or be higher than 850 ℉ (＞450 ℃) in other embodiments to 900 ℉ (482 ℃); Perhaps in the preferred operations scope of steam-fluid separation device of 425-467 ℃; Any lower limit that perhaps in this bracket statement, provides arrives in the scope of any upper limit, for example 425-482 ℃ and 450-467 ℃) be higher than 5wt% to provide, preferred 5-60wt%; More preferably 50-60wt%; Also more preferably＞50wt% is to 60wt%, also more preferably＞55wt% to 60wt%＞transformation efficiency (in other words, being enough to provide " time under certain temperature " of above-mentioned transformation efficiency) of 1050 ℉+Residual oil to＜1050 ℉+material; Comprise the step of the crude oil fractions viscosity breaking of the crude oil of hydrotreatment or hydrotreatment and follow-up obtaining are contained the cut of Residual oil and do not contain the fraction separation step of Residual oil that the cut steam cracking that will not contain Residual oil then is the step that comprises the product of alkene; Raw material comprises crude oil or the crude oil fractions that contains at least a impurity, and said impurity is selected from: be benchmark in the raw material weight (a), greater than 1wt%, more preferably greater than the sulphur of 3wt%; (b) weight in raw material is benchmark, greater than 10wt%, is preferably greater than 20wt%; More preferably greater than the Residual oil of 30wt%, the TAN that (c) measures through ASTM D-664 is >=1.0, preferred >=1.5; More preferably >=2.0, also more preferably >=2.5mg KOH/g oil, further more preferably >=the oily naphthenic acid of 3.0mg KOH/g; Step (i) is with the 20wt% at least of the aromatic hydrocarbon substance in the raw material, and preferably 40wt% is saturated at least; Step product (ii) further comprises tar, and this tar is recycled in the charging of step (i); Charging comprises steam cracker tar.
Another preferred embodiment of the present invention relates to hydrotreatment and the steam cracker system that is used for being prepared by crude oil that comprises Residual oil and crude oil fractions the integration of alkene; This system comprises at least one hydrotreater; At least one HP separator; At least one viscosity breaking device, at least one optional steam cracker and at least one steam cracker product retrieving arrangement with steam-fluid separation device of integrating with it.This can improve or improve through one or more following characteristics: this system further comprises the steam reformer that is arranged on same position with hydrotreater, disposes with the mode of hydrogen being supplied with this hydrotreater; This system is further characterized in that and comprises by following order and placed in-line viscosity breaking device and at least one optional steam cracker with steam-fluid separation device of integrating with it; This system does not comprise the steam-fluid separation device of integration; This system comprises the steam-fluid separation device of integration; The viscosity breaking device is integrated with steam cracker between convection zone and radiation section.Another embodiment preferred comprises the method that is prepared alkene by hydrocarbon feed; This method comprises the raw material charging to having the system of hydrotreater and steam cracker; Improvements comprise the material hydrotreatment that the direct charging of the material that contains Residual oil is given hydrotreater and will be contained Residual oil; In the viscosity breaking device with the elute viscosity breaking of hydrotreater; Elute as steam cracker obtains at least a of C2-C6 alkene and mononuclear aromatics material then; It can improve or improve through an embodiment, in this embodiment, the elute of all basically viscosity breaking devices is supplied with the convection zone of steam cracker; It and steam there; Be transported to then in steam-fluid separation device of integrating with steam cracker, to provide basically by steam material first logistics of forming and second logistics of forming by non-steam material basically, then the radiation section of steam cracker with the cracking of steam material also recovery comprise at least a steam cracker elute of C2-C6 alkene and mononuclear aromatics material.Also preferred embodiment of the present invention is a kind of method; This method comprises to be supplied with the feedstream that contains Residual oil in any one system according to the said system implementation plan of present disclosure; In the system of the preferred embodiment of setting forth in preferred this paragraph, obtain at least a product that is selected from C2-C6 alkene and the mononuclear aromatics material from steam cracker product retrieving arrangement.
Some other preferred embodiments that also have of the inventive method can be described below: (i) from Residual oil hydrotreatment unit, obtain elute, wherein this elute comprises 650 ℉+(343 ℃+) Residual oil; (ii) in separator, elute is separated into overhead stream and bottoms; (iii) overhead stream is transported to steam cracker from separator then; (iv) with overhead stream steam cracking and from steam cracker, obtain the steam cracker product in steam cracker, this product comprises alkene.Preferably, step (iii) is characterised in that overhead stream is transported to the steam cracker from separator as steam.This separator can comprise at least a in viscosity breaking device, flash drum, HP separator and the Vapor-Liquid Separator.It should be understood that to prove having very little difference between these equipment, and these terms exchange use usually.Separating step can comprise with the elute viscosity breaking with vapor fraction is separated with liquid distillate.
Preferably, this method also be included in the steam cracker with before the elute steam cracking through the step of at least one pressure drop with the elute flash distillation, this pressure drop reduces the half at least of elute pressure in the hydrogen cracking unit with the pressure of elute.In fact, this pressure drop can be operated unite with viscosity breaking basically and carry out, and is vapor fraction in viscosity breaking device/separator, to cause a part of liquid distillate flash distillation.At least one pressure drop is basically just before the separator or in separator, produce.Preferably, the thermally splitting of raw material begins in the hydrotreatment unit, and cracking continues in viscosity breaking device/separator.Surprisingly, strict hydrotreatment adds that strict viscosity breaking is used for most 650 ℉+(343 ℃+) Residual oil and even most 1050 ℉+(565 ℃+) Residual oil cracking.Thereby most of bottom fraction (by weight) that separating step obtains comprises that boiling point is at least 900 ℉ (482 ℃), the preferably Residual oil of at least 1050 ℉+(565 ℃+).In preferred embodiments; Separating step is included in steam-liquid separation container such as flash drum or the viscosity breaking device and separates elute; Wherein this container is at least a of following situation: (i) with the steam cracker heat integration; For example pass through location and/or connecting tube, thereby do not need independent thermal source, and/or (ii) use the thermal source heating except steam cracker.
In preferred embodiments; Elute in separator/viscosity breaking device is heated to the temperature of at least 750 ℉ (399 ℃); More preferably be heated to the temperature of at least 800 ℉, also more preferably be heated to 850 ℉ (454 ℃), also most preferably 750 ℉ (399 ℃) to the temperature of 900 ℉ (482 ℃).Further preferably, the elute in separator/viscosity breaking device keeps the determined at least shortest time in separator, and no longer than determined maximum duration.This is the conventional way of viscosity breaking and flash drum generic operation; Need the logistics of quenching bottom liquid, so that stopped reaction is avoided fouling or coking; Also allow the sufficient reaction times simultaneously, making the abundant cracking of most Residual oil (it comprises 1050 ℉+(565 ℃+) Residual oil) is light component.The performance of elute in crude oil material performance and the separator is depended in definite timing.
Preferably, the inventive method is included in the step of handling the hydrocarbon feed that contains Residual oil in the hydrotreatment unit, and wherein, this processing comprises raw material and hydrogen are merged under the temperature of 900 ℉ (482 ℃) at 750 ℉ (399 ℃).Preferably, hydrogen is from remote source.Method for hydrogenation can carry out under the pressure of 1000-4000psig, and hydrotreatment makes the 20wt% at least in the raw material, and the aromatic hydrocarbon substance of preferred 40wt% at least is saturated.Preferable methods also comprises adds steam at least one elute of hydrotreater and separator to.After the cracked vapors cut, required alkene can reclaim through other known method with other product in steam cracker.
The implication of term as used herein adopts their its ordinary meaning in the art; Especially, with reference to Handbook of Petroleum Refining Processes, the third edition, RobertA.Meyers, editor, McGraw-Hill (2004).In addition, all patents and patented claim, other file that testing sequence (for example ASTM method) and this paper are quoted is introduced for referencial use with all authorities that this open degree consistent with the present invention and this introducing are allowed in full.Also have, when enumerating numerical lower limits and numerical lower limits in the text, the scope from any lower limit to any upper limit is taken into account.Be noted that the employed trade(brand)name usefulness of this paper in addition TMSymbol or
Figure S2006800388580D00341
Symbolic representation shows that this title receives the protection of some trade mark right, and for example, they can be the registered trademarks in many compasses of competency.
Many embodiments of above reference and specific embodiment have been described the present invention.Based on above detailed description, many modification are that those skilled in the art institute is conspicuous.All these tangible modification are in the complete scope of accompanying claims.

Claims (202)

1. method comprises:
(i) in the hydrotreatment unit, be enough to promote the raw material hydrotreatment that will comprise crude oil under the temperature of initial stage thermally splitting of Residual oil or contain the crude oil fractions of Residual oil, wherein the initial stage thermal cracking residual oil constitutes elute and is enough to promote that the temperature of initial stage thermally splitting is that 750 ° of F (399 ℃) are to 900 ° of F (482 ℃);
(ii) obtain said elute from said hydrotreatment unit;
(iii) in separator, said elute is separated into overhead stream and bottoms, wherein said overhead stream is a steam, and wherein this separator comprises at least a in viscosity breaking device, flash drum, HP separator and the Vapor-Liquid Separator; Then
(iv) said overhead stream is transported to steam cracker from separator;
(v) in said steam cracker with this overhead stream steam cracking with from said steam cracker, obtain the steam cracker product, said product comprises alkene.
2. method according to claim 1 is enough to wherein promote that the temperature of initial stage thermally splitting is at least 780 ° of F (415 ℃).
3. according to claim 1 or 2 each described methods, wherein separating step comprises with said elute viscosity breaking and with vapor fraction and separating with liquid distillate.
4. the method for claim 1, further be included in the said steam cracker with before the elute steam cracking of said hydrotreatment through at least one lower said elute pressure pressure drop and with the step of said elute flash distillation.
5. the method for claim 4, wherein at least one of this at least one pressure drop is basically just before said separator or in said separator, take place.
6. according to claim 1 or 2 each described methods, the unitary elute of wherein said hydrotreatment has carried out thermally splitting in separator.
7. according to claim 1 or 2 each described methods, comprise that further the elute with hydrotreatment is transported to the convection zone of steam cracker, be transported to separator then and in said separator with overhead stream and bottoms separation steps.
8. the method for claim 7; Wherein separating step is included in and separates said elute in the vapor liquid separation vessel, and wherein this container is at least a of following situation: (i) with the steam cracker heat integration with (ii) use the thermal source except steam cracker to heat.
9. according to claim 1 or 2 each described methods, wherein separating step comprises said separator is applied heat.
10. according to claim 1 or 2 each described methods, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
11. according to claim 1 or 2 each described methods, wherein said separator and said steam cracker heat integration.
12. according to claim 1 or 2 each described methods, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
13. according to claim 1 or 2 each described methods, wherein the said elute in the separator keeps the determined at least shortest time and no longer than determined maximum duration in separator.
14. the method for claim 1; Wherein the step with the raw material hydrotreatment further is included in the step of handling said raw material in the hydrotreatment unit, and wherein said processing comprises said raw material and hydrogen are merged under the temperature of 900 ° of F (482 ℃) at 750 ° of F (399 ℃).
15. the method for claim 14, wherein said processing further comprise said raw material and hydrogen are merged under the pressure of 1000-4000psig.
16. the method for claim 1; Wherein step (i) is further characterized in that and is higher than 30wt%1050 ° of F+ Residual oil, is higher than 30wt% aromatic hydrocarbons and is lower than the raw material hydrotreatment of the crude oil or the crude oil fractions of 15wt% paraffinic hydrocarbons comprising to have; With the crude oil of acquisition hydrotreatment or the crude oil fractions of hydrotreatment, wherein the crude oil fractions of the crude oil of hydrotreatment or hydrotreatment comprises the Residual oil of hydrotreatment.
17. according to claim 1 or 2 each described methods, wherein said raw material comprises crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
18. method according to claim 17 is a benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
19. method according to claim 17 is a benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
20. method according to claim 17 is a benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
21. method according to claim 17, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
22. method according to claim 17, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
23. method according to claim 17, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
24. method according to claim 17, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
25. method according to claim 1, wherein hydrotreating step makes the 20wt% at least of the aromatic hydrocarbon substance in the raw material saturated.
26. method according to claim 1, wherein hydrotreating step makes the 40wt% at least of the aromatic hydrocarbon substance in the raw material saturated.
27. according to claim 1 or 2 each described methods; Be used for by comprising that the system of crude oil with at least a feedstock production alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
28. the method for claim 27, wherein Vapor-Liquid Separator comprises the viscosity breaking device, and said viscosity breaking device and steam cracker heat integration.
29. method according to claim 27 further is included as the steam reformer that hydrotreater is supplied with hydrogen.
30. method according to claim 28 further is included as the steam reformer that hydrotreater is supplied with hydrogen.
31. according to claim 1 or 2 each described methods, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
32., further comprise steam is joined the step at least one in hydrotreatment unit elute, overhead stream and the separator according to claim 1 or 2 each described methods.
33. according to claim 1 or 2 each described methods, wherein separating step is included in the step with the Residual oil of vapor fraction and the isolating heats hydrotreatment of liquid distillate.
34. the method for claim 33, wherein heating steps comprises that the Residual oil with hydrotreatment is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
35. the method for claim 28, wherein the viscosity breaking device comprises separating device and pressure regulating equipment, and this viscosity breaking device separates vapor fraction after elute is through pressure regulating equipment with liquid distillate.
36. the method for claim 35, wherein separating device comprises separation vessel, and this container comprises the half at least liquid capacity that accounts for the separation vessel cubic capacity.
37. the method for claim 1 is used for preparing alkene by hydrocarbon feed, this method comprises the steps:
The hydrotreatment unit is given in the hydrocarbon feed charging that (i) will contain Residual oil;
(ii) the hydrogen charging is given hydrotreater and contained the hydrocarbon feed of Residual oil under the temperature of 900 ° of F (482 ℃) with the hydrogen hydrotreatment at 750 ° of F (399 ℃), with the hydrogenation elute of generation initial stage thermally splitting;
(iii) with the elute charging of hydrotreater give the viscosity breaking device and 750 ° of F (399 ℃) under the temperature of 900 ° of F (482 ℃) with this elute viscosity breaking;
(iv) from the viscosity breaking device, separate vapor fraction and bottom fraction, wherein by weight most bottom fraction comprises that boiling point is the Residual oil of at least 1050 ° of F (565 ℃);
(v) in steam cracker with the vapor fraction steam cracking to produce the steam cracker elute; And
(vi) separate this steam cracker elute, to reclaim at least a in C2-C6 alkene and the mononuclear aromatics material.
38. method according to claim 3, the unitary elute of wherein said hydrotreatment have been carried out thermally splitting in separator.
39. according to claim 4 or 5 each described methods, the unitary elute of wherein said hydrotreatment has carried out thermally splitting in separator.
40. method according to claim 3 comprises that further the elute with hydrotreatment is transported to the convection zone of steam cracker, be transported to separator then and in said separator with overhead stream and bottoms separation steps.
41. the method for claim 40; Wherein separating step is included in and separates said elute in the vapor liquid separation vessel, and wherein this container is at least a of following situation: (i) with the steam cracker heat integration with (ii) use the thermal source except steam cracker to heat.
42. according to claim 4 or 5 each described methods, comprise that further the elute with hydrotreatment is transported to the convection zone of steam cracker, be transported to separator then and in said separator with overhead stream and bottoms separation steps.
43. the method for claim 42; Wherein separating step is included in and separates said elute in the vapor liquid separation vessel, and wherein this container is at least a of following situation: (i) with the steam cracker heat integration with (ii) use the thermal source except steam cracker to heat.
44. according to the described method of claim 38, comprise that further the elute with hydrotreatment is transported to the convection zone of steam cracker, be transported to separator then and in said separator with overhead stream and bottoms separation steps.
45. the method for claim 44; Wherein separating step is included in and separates said elute in the vapor liquid separation vessel, and wherein this container is at least a of following situation: (i) with the steam cracker heat integration with (ii) use the thermal source except steam cracker to heat.
46. according to the described method of claim 39, comprise that further the elute with hydrotreatment is transported to the convection zone of steam cracker, be transported to separator then and in said separator with overhead stream and bottoms separation steps.
47. the method for claim 46; Wherein separating step is included in and separates said elute in the vapor liquid separation vessel, and wherein this container is at least a of following situation: (i) with the steam cracker heat integration with (ii) use the thermal source except steam cracker to heat.
48. method according to claim 3, wherein separating step comprises said separator is applied heat.
49. according to claim 4 or 5 each described methods, wherein separating step comprises said separator is applied heat.
50. method according to claim 6, wherein separating step comprises said separator is applied heat.
51. method according to claim 7, wherein separating step comprises said separator is applied heat.
52. method according to claim 8, wherein separating step comprises said separator is applied heat.
53. method according to claim 3, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
54. according to claim 4 or 5 each described methods, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
55. method according to claim 6, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
56. method according to claim 7, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
57. method according to claim 8, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
58. method according to claim 9, wherein the pressure of the unitary elute of hydrotreatment before separating or between separation period flash distillation release at least once.
59. method according to claim 3, wherein said separator and said steam cracker heat integration.
60. according to claim 4 or 5 each described methods, wherein said separator and said steam cracker heat integration.
61. method according to claim 6, wherein said separator and said steam cracker heat integration.
62. method according to claim 7, wherein said separator and said steam cracker heat integration.
63. method according to claim 8, wherein said separator and said steam cracker heat integration.
64. method according to claim 9, wherein said separator and said steam cracker heat integration.
65. method according to claim 10, wherein said separator and said steam cracker heat integration.
66. method according to claim 3, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
67. according to claim 4 or 5 each described methods, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
68. method according to claim 6, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
69. method according to claim 7, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
70. method according to claim 8, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
71. method according to claim 9, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
72. method according to claim 10, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
73. method according to claim 11, wherein the said elute in the separator is heated to the temperature of 750 ° of F (399 ℃) to 900 ° of F (482 ℃).
74. method according to claim 3, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
75. according to the described method of claim 74, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
76. according to the described method of claim 74, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
77. according to the described method of claim 74, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
78. according to the described method of claim 74, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
79. according to the described method of claim 74, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
80. according to the described method of claim 74, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
81. according to the described method of claim 74, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
82. according to claim 4 or 5 each described methods, wherein said raw material comprises crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
83. 2 described methods are benchmark in said raw material weight wherein according to Claim 8, the quantity of sulphur is greater than 3wt%.
84. 2 described methods are benchmark in said raw material weight wherein according to Claim 8, the quantity of Residual oil is greater than 20wt%.
85. 2 described methods are benchmark in said raw material weight wherein according to Claim 8, the quantity of Residual oil is greater than 30wt%.
86. 2 described methods according to Claim 8, wherein naphthenic acid through the TAN that ASTM D-664 measures be >=1.5mg KOH/g is oily.
87. 2 described methods according to Claim 8, wherein naphthenic acid through the TAN that ASTM D-664 measures be >=2.0mg KOH/g is oily.
88. 2 described methods according to Claim 8, wherein naphthenic acid through the TAN that ASTM D-664 measures be >=2.5mg KOH/g is oily.
89. 2 described methods according to Claim 8, wherein naphthenic acid through the TAN that ASTM D-664 measures be >=3.0mg KOH/g is oily.
90. method according to claim 6, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
91. according to the described method of claim 90, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
92. according to the described method of claim 90, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
93. according to the described method of claim 90, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
94. according to the described method of claim 90, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
95. according to the described method of claim 90, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
96. according to the described method of claim 90, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
97. according to the described method of claim 90, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
98. method according to claim 7, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
99. according to the described method of claim 98, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
100. according to the described method of claim 98, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
101. according to the described method of claim 98, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
102. according to the described method of claim 98, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
103. according to the described method of claim 98, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
104. according to the described method of claim 98, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
105. according to the described method of claim 98, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
106. method according to claim 8, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
107. according to the described method of claim 106, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
108. according to the described method of claim 106, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
109. according to the described method of claim 106, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
110. according to the described method of claim 106, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
111. according to the described method of claim 106, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
112. according to the described method of claim 106, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
113. according to the described method of claim 106, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
114. method according to claim 9, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
115. according to the described method of claim 114, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
116. according to the described method of claim 114, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
117. according to the described method of claim 114, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
118. according to the described method of claim 114, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
119. according to the described method of claim 114, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
120. according to the described method of claim 114, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
121. according to the described method of claim 114, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
122. method according to claim 10, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
123. according to the described method of claim 122, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
124. according to the described method of claim 122, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
125. according to the described method of claim 122, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
126. according to the described method of claim 122, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
127. according to the described method of claim 122, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
128. according to the described method of claim 122, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
129. according to the described method of claim 122, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
130. method according to claim 11, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
131. according to the described method of claim 130, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
132. according to the described method of claim 130, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
133. according to the described method of claim 130, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
134. according to the described method of claim 130, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
135. according to the described method of claim 130, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
136. according to the described method of claim 130, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
137. according to the described method of claim 130, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
138. method according to claim 12, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
139. according to the described method of claim 138, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
140. according to the described method of claim 138, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
141. according to the described method of claim 138, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
142. according to the described method of claim 138, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
143. according to the described method of claim 138, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
144. according to the described method of claim 138, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
145. according to the described method of claim 138, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
146. method according to claim 13, wherein said raw material comprise crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
147. according to the described method of claim 146, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
148. according to the described method of claim 146, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
149. according to the described method of claim 146, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
150. according to the described method of claim 146, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
151. according to the described method of claim 146, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
152. according to the described method of claim 146, wherein naphthenic acid through the TAN that ASTMD-664 measures is >=2.5mg KOH/g oil.
153. according to the described method of claim 146, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
154. according to each described method of claim 14-16, wherein said raw material comprises crude oil that contains at least a impurity or the crude oil fractions that contains Residual oil, said impurity is selected from:
(a) be benchmark in said raw material weight, greater than the sulphur of 1wt%;
(b) weight in said raw material is benchmark, greater than the Residual oil of 10wt%; And
(c) TAN that measures through ASTM D-664 is >=the oily naphthenic acid of 1.0mg KOH/g.
155. according to the described method of claim 154, be benchmark in said raw material weight wherein, the quantity of sulphur is greater than 3wt%.
156. according to the described method of claim 154, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 20wt%.
157. according to the described method of claim 154, be benchmark in said raw material weight wherein, the quantity of Residual oil is greater than 30wt%.
158. according to the described method of claim 154, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=1.5mg KOH/g oil.
159. according to the described method of claim 154, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.0mg KOH/g oil.
160. according to the described method of claim 154, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=2.5mg KOH/g oil.
161. according to the described method of claim 154, wherein naphthenic acid through the TAN that ASTM D-664 measures is >=3.0mg KOH/g oil.
162. method according to claim 3; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
163. the method for claim 162, wherein Vapor-Liquid Separator comprises the viscosity breaking device, and said viscosity breaking device and steam cracker heat integration.
164., further be included as the steam reformer that hydrotreater is supplied with hydrogen according to the described method of claim 162.
165., further be included as the steam reformer that hydrotreater is supplied with hydrogen according to the described method of claim 163.
166. according to claim 4 or 5 each described methods; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
167. method according to claim 6; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
168. method according to claim 7; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
169. method according to claim 8; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
170. method according to claim 9; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
171. method according to claim 10; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
172. method according to claim 11; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
173. method according to claim 12; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
174. method according to claim 13; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
175. according to each described method of claim 14-16; Be used for by comprising that the system of crude oil with at least a preparation alkene of the crude oil fractions that contains Residual oil carries out; Said system comprises at least one hydrotreater, at least one Vapor-Liquid Separator and at least one steam cracker.
176. method according to claim 3, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
177. according to claim 4 or 5 each described methods, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
178. method according to claim 6, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
179. method according to claim 7, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
180. method according to claim 8, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
181. method according to claim 9, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
182. method according to claim 10, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
183. method according to claim 11, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
184. method according to claim 12, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
185. method according to claim 13, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
186. according to each described method of claim 14-16, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
187. method according to claim 17, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
188. method according to claim 18, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
189. method according to claim 19, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
190. method according to claim 20, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
191. method according to claim 21, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
192. method according to claim 22, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
193. method according to claim 23, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
194. method according to claim 24, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
195. method according to claim 25, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
196. method according to claim 26, wherein this method comprises that further (i) uses the well heater of heating raw before the viscosity breaking device with (ii) at least one position in the viscosity breaking device.
197. method according to claim 27, wherein this system further comprise (i) before the viscosity breaking device with the (ii) well heater of at least one the position heating raw in the viscosity breaking device.
198. method according to claim 28, wherein this system further comprise (i) before the viscosity breaking device with the (ii) well heater of at least one the position heating raw in the viscosity breaking device.
199. method according to claim 3 further comprises steam is joined the step at least one in hydrotreatment unit elute, overhead stream and the separator.
200. method according to claim 17 further comprises steam is joined the step at least one in hydrotreatment unit elute, overhead stream and the separator.
201. method according to claim 3, wherein separating step is included in the step with the Residual oil of vapor fraction and the isolating heats hydrotreatment of liquid distillate.
202. method according to claim 17, wherein separating step is included in the step with the Residual oil of vapor fraction and the isolating heats hydrotreatment of liquid distillate.
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